HK1262996A1

HK1262996A1 - High strength polyurethane foam compositions and methods

Info

Publication number: HK1262996A1
Application number: HK19122956.6A
Authority: HK
Inventors: S·D·艾伦; V·森迪亚雷维克; A·森迪亚雷维克
Original assignee: 沙特阿美技术公司
Priority date: 2012-11-07
Filing date: 2019-04-25
Publication date: 2020-01-24

Description

High strength polyurethane foam compositions and methods

The application is a divisional application of an application with the application date of 2013, 11 and 7, and the application number of 201380069670.2, and the name of the invention is 'high-strength polyurethane foam composition and method', and the original application is a Chinese national stage application with the international application number of PCT/US 2013/068932.

Technical Field

The present invention relates to the field of polyurethane foams. More particularly, the present invention relates to additives and methods for improving the strength of polyurethane foams.

Background

Polyurethane foams derived from the reaction between a polyisocyanate and a reactive polymer are widely used in a range of applications for insulation and the manufacture of furniture, cushions, consumer goods, building materials, automotive parts and the like.

The cost of polyurethane foams has increased dramatically in recent years due to the increase in the cost of petroleum-based raw materials and the energy used to make them. At the same time, there is an increasing market demand for tough, high performance materials with long service life and improved sustainable characteristics. Unfortunately, existing solutions to these problems tend to increase one performance at the expense of the other.

For example, to obtain a stronger foam, the density of the foam is typically increased, which results in greater use of the material and greater waste of energy required to transport the material. This is exacerbated in transportation applications when the foam is part of a vehicle, as heavier foams will charge capital and environmental costs by increasing the fuel usage throughout their useful life. Therefore, a compromise is often made in which a less durable or lower performance foam is selected based on cost or weight considerations.

Similarly, efforts to make foam compositions more sustainable by the addition of bio-based raw materials have yielded good and bad results. Incorporation of soy or corn based feedstocks into polyurethane foam formulations often results in a sacrifice in desired properties and requires additional changes in the formulation to obtain acceptable properties-even with such concessions, it is difficult to incorporate more than about 10% of the biobased material. The true sustainability of this process is also questionable, especially as a whole, including the use of land and water and petroleum resources required to produce bio-based feedstocks-especially if additional effort or petroleum-based additives are required to offset the negative impact of these materials on the foam formulation.

It has been previously reported that it can be derived from CO₂The polyols produced formulate polyurethane foams (see, e.g., commonly owned patent applications WO2010/028362 and PCT/US 12/047967). These foam compositions have an improved carbon footprint because of the possibility to remove CO from waste₂Up to 50% of the polyol mass is obtained, otherwise these waste CO' s₂Will be released to the atmosphere. In addition to sequestering potential greenhouse gases, this strategy also allows the amount of fossil fuel-derived feedstocks used to make polyols to be reduced by up to 50%.

Nonetheless, there remains a need for polyurethane foam compositions having improved performance characteristics, particularly for formulations having excellent strength and durability at equal or lower weights than existing materials.

Disclosure of Invention

Incorporation of epoxide CO, as described above₂Polyurethane foams of copolymers (aliphatic polycarbonate polyols) have been described. Nevertheless, in certain aspects, these foams present challenges. From epoxidesCO₂Foams formulated with the copolymer as the primary polyol component in the B-side (B-side) can be difficult to formulate (e.g., due to high viscosity). In addition, the foams produced are sometimes brittle or lack certain other physical properties desirable for foams-especially in flexible foams. In one aspect, the invention includes the recognition that when used as an additive in the B side of a conventional foam formulation, the inclusion of an epoxide CO₂Copolymers do not have these negative effects, but instead their presence unexpectedly increases desirable properties such as strength, compression force deflection, solvent resistance, and the like.

Accordingly, in one aspect, the present invention includes a high strength polyurethane foam composition comprising the reaction product of a polyol component and a polyisocyanate component, wherein the polyol component comprises a blend of polyols comprising from about 2 weight percent to about 50 weight percent of a polycarbonate polyol copolymerized from one or more epoxides and carbon dioxide. In certain embodiments, the remainder of the polyol component includes conventional polyether or polyester polyols as used in current commercial foam formulations. The foam compositions of the present invention unexpectedly exhibit improved physical strength, including higher compression deflection and higher tear resistance, than foams formulated without the polycarbonate polyol. Importantly, these improved foam compositions do not have a higher density than the original foam and do not sacrifice other factors related to comfort, durability, insulation value, and the like.

In another aspect, the invention includes a method of reinforcing a polyurethane foam composition. In certain embodiments, the method comprises the step of replacing from about 2 weight percent to about 50 weight percent of the polyol content of the polyurethane foam formulation with a polycarbonate polyol derived from the copolymerization of one or more epoxides and dioxides.

In another aspect, the present invention provides a strength enhancing additive for foam formulations. The additives of the present invention include aliphatic polycarbonate polyols suitable for blending with polyether or polyester polyols, and are characterized in that their presence in the foam formulation increases one or more of the compression force deflection value, tear resistance, or hysteresis of the final foam composition.

In another aspect, the invention includes articles made from high strength polyurethane foam compositions resulting from the addition to the foam formulation of polycarbonate polyols derived from the copolymerization of one or more epoxides and carbon dioxide. Such articles include low density seating materials for transportation applications, non-seating foam components for automotive manufacturing, footwear foams, office furniture, cushions, sporting goods, building materials, and consumer products.

Definition of

The definitions of specific functional groups and chemical terms are described in more detail below. For the purposes of the present invention, chemical elements are identified according to the periodic Table of the elements, CAS version, Handbook of Chemistry and Physics, 75 th edition, inner cover and specific functional groups are generally defined as described therein. In addition, the general principles of Organic Chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausaltito, 1999; smith and March March's Advanced Organic Chemistry, 5 th edition, John Wiley & Sons, Inc., New York, 2001; larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; carrousers, Some model Methods of organic Synthesis, 3 rd edition, Cambridge University Press, Cambridge, 1987; each of which is incorporated herein by reference in its entirety.

Certain compounds of the invention may contain one or more asymmetric centers and may therefore be present in various stereoisomeric forms (e.g., enantiomers and/or diastereomers). Thus, the compounds of the present invention and compositions thereof may be in the form of individual enantiomers, diastereomers, or geometric isomers, or may be in the form of mixtures of stereoisomers. In certain embodiments, the compounds of the present invention are enantiomerically pure compounds. In certain embodiments, a mixture of enantiomers or diastereomers is provided.

Furthermore, as described herein, certain compounds may have one or more double bonds that may be present in either the Z or E isomer (unless otherwise indicated). The invention further encompasses compounds in the form of each isomer substantially free of other isomers and optionally in the form of a mixture of the individual isomers (e.g., a racemic mixture of enantiomers). In addition to the above-mentioned compounds per se, the present invention also encompasses compositions comprising one or more compounds.

The term "isomer" as used herein includes any and all geometric isomers and stereoisomers. For example, "isomers" include cis-and trans-isomers, E-and Z-isomers, R-and S-enantiomers, diastereomers, (D) -isomers, (L) -isomers, racemic mixtures thereof, and other mixtures thereof, all of which fall within the scope of the present invention. For example, in some embodiments, stereoisomers may be provided that are substantially free of one or more corresponding stereoisomers, and may also be referred to as "stereochemically enriched.

In some embodiments, where a particular enantiomer is preferred, it may be provided substantially free of the opposite enantiomer and may also be referred to as "optically enriched". As used herein, "optically enriched" means that a compound or polymer is composed of a significantly larger proportion of one enantiomer. In certain embodiments, the compounds are made up of at least about 90% by weight of the preferred enantiomer. In other embodiments, the compound consists of at least about 95%, 98%, or 99% by weight of the preferred enantiomer. Preferred enantiomers may be isolated from racemic mixtures by any method known to those skilled in the art, including chiral High Pressure Liquid Chromatography (HPLC) and the formation and crystallization of chiral salts or prepared by asymmetric synthesis. See, e.g., Jacques et al, eneriomers, Racemates and solutions (Wiley Interscience, New York, 1981); wilen, S.H et al, Tetrahedron 33:2725 (1977); eliel, E.L. Stereochemistry of Carbon Compounds (McGraw-Hill, NY, 1962); wilen, S.H.tablet of solving Agents and Optical solutions, p.268 (ed. E.L.Eliel, Univ.of Notreddame Press, Notre Dame, IN 1972).

The term "epoxide" as used herein refers to a substituted or unsubstituted oxirane. Such substituted oxiranes include mono-substituted oxiranes, di-substituted oxiranes, tri-substituted oxiranes and tetra-substituted oxiranes. Such epoxides may be further optionally substituted as defined herein. In certain embodiments, the epoxide comprises a single oxirane moiety. In certain embodiments, the epoxide comprises two or more ethylene oxide moieties.

The term "polymer" as used herein refers to a relatively high molecular mass molecule, the structure of which comprises a plurality of repeating units derived, actually or conceptually, from a relatively low molecular mass molecule. In certain embodiments, the polymer is derived from CO₂In some embodiments, the polymers of the present invention are copolymers, terpolymers, heteropolymers, block copolymers, or tapered heteropolymers incorporating two or more different epoxide monomersThese structures should be construed to encompass copolymers incorporating any ratio of the different monomer units described, unless otherwise indicated. The description is also intended to represent random, tapered, block copolymers, and combinations of any two or more of these, and all of these are implicit unless otherwise indicated.

The terms "halo" and "halogen" as used herein refer to an atom selected from the group consisting of fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br) and iodine (iodo, -I).

The term "aliphatic" or "aliphatic group" as used herein denotes a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridged, and spiro-fused polycyclic) and may be fully saturated or may contain one or more units of unsaturation, but which is not aromatic. Unless otherwise specified, aliphatic groups contain 1-40 carbon atoms. In certain embodiments, aliphatic groups contain 1 to 20 carbon atoms. In certain embodiments, aliphatic groups contain 3 to 20 carbon atoms. In certain embodiments, aliphatic groups contain 1-12 carbon atoms. In certain embodiments, aliphatic groups contain 1 to 8 carbon atoms. In certain embodiments, aliphatic groups contain 1-6 carbon atoms. In some embodiments, aliphatic groups contain 1 to 5 carbon atoms, in some embodiments, aliphatic groups contain 1 to 4 carbon atoms, in some embodiments, aliphatic groups contain 1 to 3 carbon atoms, and in some embodiments, aliphatic groups contain 1 or 2 carbon atoms. Suitable aliphatic groups include, but are not limited to, straight or branched chain alkyl, alkenyl, and alkynyl groups, and mixtures thereof such as (cycloalkyl) alkyl, (cycloalkenyl) alkyl, or (cycloalkyl) alkenyl.

The term "heteroaliphatic", as used herein, refers to an aliphatic group in which one or more carbon atoms are independently replaced by one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen, or phosphorus. In certain embodiments, one to six carbon atoms are independently replaced with one or more of oxygen, sulfur, nitrogen, or phosphorus. The heteroaliphatic group can be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and includes saturated, unsaturated, or partially unsaturated groups.

The term "divalent C" as used herein_1-8(or C)_1-3) Saturated or unsaturated, linear or branched hydrocarbon chain "refers to divalent alkyl, alkenyl and alkynyl chains as defined herein as linear or branched.

The term "unsaturated" as used herein means that the moiety has one or more double or triple bonds.

AloneThe terms "alicyclic", "carbocyclic" or "carbocyclic" used or used as part of a larger moiety refer to a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic ring system having 3 to 12 members as described herein, wherein the aliphatic ring system is optionally substituted as defined above and described herein. Cycloaliphatic groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, norbornyl, adamantyl, and cyclooctadienyl. In some embodiments, the cycloalkyl group has 3-6 carbons. The terms "alicyclic," "carbocyclic," or "carbocyclic" also include aliphatic rings that are fused to one or more aromatic or non-aromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the linking group or point of attachment is on the aliphatic ring. In certain embodiments, the term "3-to 7-membered carbocycle" refers to a 3-to 7-membered saturated or partially unsaturated monocyclic carbocycle. In certain embodiments, the term "3-to 8-membered carbocycle" refers to a 3-to 8-membered saturated or partially unsaturated monocyclic carbocycle. In certain embodiments, the terms "3 to 14 membered carbocycle" and "C_3-14Carbocycle "refers to a 3-to 8-membered saturated or partially unsaturated monocyclic carbocycle, or a 7-to 14-membered saturated or partially unsaturated polycyclic carbocycle.

The term "alkyl" as used herein refers to a saturated, straight or branched chain hydrocarbon radical derived from an aliphatic moiety containing one to six carbon atoms by the removal of a single hydrogen atom. Unless otherwise indicated, alkyl groups contain 1-12 carbon atoms. In certain embodiments, the alkyl group contains 1 to 8 carbon atoms. In certain embodiments, the alkyl group contains 1 to 6 carbon atoms. In some embodiments, alkyl groups contain 1 to 5 carbon atoms, in some embodiments, alkyl groups contain 1 to 4 carbon atoms, in some embodiments, alkyl groups contain 1 to 3 carbon atoms, and in some embodiments, alkyl groups contain 1 to 2 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, sec-pentyl, isopentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl and the like.

The term "alkenyl" as used herein, denotes a monovalent group derived from a straight or branched aliphatic moiety having at least one carbon-carbon double bond by the removal of a single hydrogen atom. Unless otherwise indicated, alkenyl groups contain 2-12 carbon atoms. In certain embodiments, alkenyl groups contain 2 to 8 carbon atoms. In certain embodiments, alkenyl groups contain 2-6 carbon atoms. In some embodiments, alkenyl groups contain 2 to 5 carbon atoms, in some embodiments alkenyl groups contain 2 to 4 carbon atoms, in some embodiments alkenyl groups contain 2 to 3 carbon atoms, and in some embodiments alkenyl groups contain 2 carbon atoms. Alkenyl groups include, for example, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl, and the like.

The term "alkynyl" as used herein refers to a monovalent group derived from a straight or branched chain aliphatic moiety having at least one carbon-carbon triple bond by the removal of a single hydrogen atom. Unless otherwise indicated, alkynyl groups contain 2-12 carbon atoms. In certain embodiments, alkynyl groups contain 2-8 carbon atoms. In certain embodiments, alkynyl groups contain 2-6 carbon atoms. In some embodiments, alkynyl groups contain 2-5 carbon atoms, in some embodiments alkynyl groups contain 2-4 carbon atoms, in some embodiments alkynyl groups contain 2-3 carbon atoms, and in some embodiments alkynyl groups contain 2 carbon atoms. Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl, and the like.

The term "alkoxy," as used herein, refers to an alkyl group, as previously defined, attached to the parent molecule through an oxygen atom. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentyloxy, and n-hexyloxy.

The term "acyl", as used herein, refers to a carbonyl-containing functional group, such as, -C (═ O) R ', where R' is hydrogen or an optionally substituted aliphatic, heteroaliphatic, heterocyclic, aryl, heteroaryl, or is a substituted (e.g., substituted with hydrogen or an aliphatic, heteroaliphatic, aryl, or heteroaryl moiety) oxygen-or nitrogen-containing functional group (e.g., to form a carboxylic acid, ester, or amide functional group). The term "acyloxy", as used herein, refers to an acyl group attached to the parent molecule through an oxygen atom.

The term "aryl", used alone or as part of a larger moiety as in "aralkyl", "aralkoxy", or "aryloxyalkyl", refers to monocyclic and polycyclic ring systems having a total of 5 to 20 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains three to twelve ring members. The term "aryl" may be used interchangeably with the term "aryl ring". In certain embodiments of the present invention, "aryl" refers to an aromatic ring system, including but not limited to phenyl, biphenyl, naphthyl, anthracenyl, and the like, which may have one or more substituents. Also included within the scope of the term "aryl" as used herein are groups in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthalimide, phenanthridinyl, or tetrahydronaphthyl, and the like. In certain embodiments, the terms "6 to 10 membered aryl" and "C_6-10Aryl "refers to a phenyl or 8 to 10 membered polycyclic aryl ring.

The terms "heteroaryl" and "heteroar-" used alone or as part of a larger moiety such as "heteroaralkyl" or "heteroaralkoxy" refer to moieties having from 5 to 14 ring atoms, preferably 5, 6, 9, or 10 ring atoms; having 6, 10 or 14 pi electrons shared in a ring arrangement; and has one to five heteroatoms other than carbon atoms. The term "heteroatom" refers to nitrogen, oxygen or sulfur and includes any oxidized form of nitrogen or sulfur and any quaternized form of basic nitrogen. Heteroaryl groups include, but are not limited to, thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, benzofuryl, and pteridinyl. The terms "heteroaryl" and "heteroaryl" as used herein also include groups in which a heteroaromatic ring is fused to one or more aryl, alicyclic or heterocyclic rings, wherein the linking group or point of attachment is on the heteroaromatic ring. Non-limiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzothiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolyl, tetrahydroisoquinolyl, and pyrido [2, 3-b ] -1, 4-oxazin-3 (4H) -one. Heteroaryl groups may be monocyclic or bicyclic. The term "heteroaryl" may be used interchangeably with the terms "heteroaryl ring", "heteroaryl group", or "heteroaromatic", any of these terms including optionally substituted rings. The term "heteroaralkyl" refers to an alkyl group substituted with a heteroaryl group, wherein the alkyl and heteroaryl portions are independently optionally substituted. In certain embodiments, the term "5-to 10-membered heteroaryl" refers to a 5-to 6-membered heteroaryl ring having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-to 10-membered bicyclic heteroaryl ring having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. In certain embodiments, the term "5-to 12-membered heteroaryl" refers to a 5-to 6-membered heteroaryl ring having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8-to 12-membered bicyclic heteroaryl ring having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

The terms "heterocycle", "heterocyclyl", "heterocyclic radical" and "heterocyclic ring" are used interchangeably herein and refer to a stable 5-to 7-membered monocyclic or 7-to 14-membered polycyclic heterocyclic moiety which may be saturated or partially unsaturated and which has, in addition to carbon atoms, one or more, preferably one to four, heteroatoms as defined above. When used in reference to a ring atom of a heterocyclic ring, the term "nitrogen" includes substituted nitrogens. For example, in a saturated or partially unsaturated ring having 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, the nitrogen may be N (as in 3, 4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl) or⁺NR (e.g. in N-substituted pyrrolesIn the alkyl group). In some embodiments, the term "3-to 7-membered heterocyclic ring" refers to a 3-to 7-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 heteroatoms independently selected from nitrogen, oxygen, or sulfur. In some embodiments, the term "3 to 12 membered heterocyclic ring" refers to a 3 to 8 membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or a 7 to 12 membered saturated or partially unsaturated polycyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

The heterocyclic ring may be attached to its pendant group at any heteroatom or carbon atom that results in a stable structure and any of the ring atoms may be optionally substituted. Examples of such saturated or partially unsaturated heterocyclyl groups include, but are not limited to, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidinonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl. The terms "heterocycle", "heterocyclyl group", "heterocyclic moiety" and "heterocyclic group" are used interchangeably herein and also include groups in which the heterocyclyl ring is fused to one or more aryl, heteroaryl or alicyclic rings, such as indolinyl, 3H-indolyl, chromanyl, phenanthridinyl or tetrahydroquinolinyl, wherein the linking group or point of attachment is on the heterocyclyl ring. The heterocyclic group may be monocyclic or bicyclic. The term "heterocycloalkyl" refers to an alkyl group substituted with a heterocyclyl group, wherein the alkyl and heterocyclyl portions are independently optionally substituted.

The term "partially unsaturated" as used herein refers to a cyclic moiety comprising at least one double or triple bond. The term "partially unsaturated" is intended to encompass rings having multiple sites of unsaturation, but is not intended to include aryl or heteroaryl moieties as defined herein.

As described herein, the compounds of the present invention may contain "optionally substituted" moieties. Generally, the term "substituted" whether preceded by the term "optionally" or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent. Unless otherwise indicated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituents at each position may be the same or different. The combinations of substituents envisaged by the present invention are preferably those which result in the formation of stable or chemically feasible compounds. The term "stable" as used herein refers to a compound that is substantially unchanged when subjected to conditions that allow the compound to be produced, detected, and in some embodiments recovered, purified, and used for one or more of the purposes disclosed herein.

Suitable monovalent substituents on the substitutable carbon atom of the "optionally substituted" group are independently halogen; - (CH)₂)_0–4R^○；–(CH₂)_0–4OR^○；–O–(CH₂)_0–4C(O)OR^○；–(CH₂)_0–4CH(OR^○)₂；–(CH₂)_0–4SR^○；–(CH₂)_0– ₄Ph, which may be represented by R^○Substitution; - (CH)₂)_0–4O(CH₂)_0–1Ph, which may be represented by R^○Substitution; -CH ═ CHPh, which may be substituted by R^○Substitution; -NO₂；–CN；–N₃；–(CH₂)_0–4N(R^○)₂；–(CH₂)_0–4N(R^○)C(O)R^○；–N(R^○)C(S)R^○；–(CH₂)_0–4N(R^○)C(O)NR^○ ₂；–N(R^○)C(S)NR^○ ₂；–(CH₂)_0–4N(R^○)C(O)OR^○；–N(R^○)N(R^○)C(O)R^○；–N(R^○)N(R^○)C(O)NR^○ ₂；–N(R^○)N(R^○)C(O)OR^○；–(CH₂)_0–4C(O)R^○；–C(S)R^○；–(CH₂)_0–4C(O)OR^○；–(CH₂)_0–4C(O)N(R^○)₂；–(CH₂)_0–4C(O)SR^○；–(CH₂)_0–4C(O)OSiR^○ ₃；–(CH₂)_0–4OC(O)R^○；–OC(O)(CH₂)_0–4SR–，SC(S)SR^○；–(CH₂)_0–4SC(O)R^○；–(CH₂)_0–4C(O)NR^○ ₂；–C(S)NR^○ ₂；–C(S)SR^○；–SC(S)SR^○，–(CH₂)_0–4OC(O)NR^○ ₂；–C(O)N(OR^○)R^○；–C(O)C(O)R^○；–C(O)CH₂C(O)R^○；–C(NOR^○)R^○；–(CH₂)_0–4SSR^○；–(CH₂)_0–4S(O)₂R^○；–(CH₂)_0–4S(O)₂OR^○；–(CH₂)_0–4OS(O)₂R^○；–S(O)₂NR^○ ₂；–(CH₂)_0–4S(O)R^○；–N(R^○)S(O)₂NR^○ ₂；–N(R^○)S(O)₂R^○；–N(OR^○)R^○；–C(NH)NR^○ ₂；–P(O)₂R^○；–P(O)R^○ ₂；–OP(O)R^○ ₂；–OP(O)(OR^○)₂；SiR^○ ₃；–(C_1–4Straight or branched alkylene) O-N (R)^○)₂(ii) a Or- (C)_1–4Straight or branched alkylene) C (O) O-N (R)^○)₂Wherein each R is^○May be substituted as defined below and independently is hydrogen, C_1–8Aliphatic, -CH₂Ph，–O(CH₂)_0–1Ph or a 5-6 membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or, although defined above, two independent occurrences of R^○Together with their intervening atoms, form a 3-12 membered saturated, partially unsaturated, or aryl mono-or polycyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, which may be substituted as defined below.

At R^○A suitable monovalent substituent on (or two independently occurring R's)^○The ring formed together with the intervening atoms thereof) is independently halogen, - (CH)₂)_0–2R^●- (halogenated R)^●)、–(CH₂)_0–2OH、–(CH₂)_0–2OR^●、–(CH₂)_0–2CH(OR^●)₂(ii) a -O (halo R)^●)、–CN、–N₃、–(CH₂)_0–2C(O)R^●、–(CH₂)_0–2C(O)OH、–(CH₂)_0–2C(O)OR^●、–(CH₂)_0–4C(O)N(R^○)₂；–(CH₂)_0–2SR^●、–(CH₂)_0–2SH、–(CH₂)_0–2NH₂、–(CH₂)_0–2NHR^●、–(CH₂)_0–2NR^● ₂、–NO₂、–SiR^● ₃、–OSiR^● ₃、–C(O)SR^●、–(C_1–4Straight OR branched alkylene) C (O) OR^●or-SSR^●Wherein each R is^●Is unsubstituted or is preceded by "halo" and is independently selected from C_1–4Aliphatic, -CH₂Ph，–O(CH₂)_0– ₁Ph or a 5-6 membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur. R^○Suitable divalent substituents on the saturated carbon atom of (a) include ═ O and ═ S.

Suitable divalent substituents on the saturated carbon atom of the "optionally substituted" group include the following: is one of O, S and NNR^* ₂、＝NNHC(O)R^*、＝NNHC(O)OR^*、＝NNHS(O)₂R^*、＝NR^*、＝NOR^*、–O(C(R^* ₂))_2–3O-or-S (C (R)^* ₂))_2–3S-, wherein each independently occurs R^*Selected from hydrogen, C_1–6Aliphatic (which may be substituted as defined below) or unsubstituted 5-6 membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur. Suitable divalent substituents bound to the carbon substitutable at the ortho position of the "optionally substituted" group include: -O (CR)^* ₂)_2–3O-, in which each occurrence of R is independent^*Selected from hydrogen, C_1–6Aliphatic (which may be substituted as defined below) or unsubstituted 5-6 membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur.

At R^*Suitable substituents on the aliphatic radical of (A) include halogen, -R^●- (halogenated R)^●)、–OH、–OR^●-O (halo R)^●)、–CN、–C(O)OH、–C(O)OR^●、–NH₂、–NHR^●、–NR^● ₂or-NO₂Wherein each R is^●Is unsubstituted or preceded by "halo" and is independently C_1–4Aliphatic, -CH₂Ph，–O(CH₂)_0–1Ph or a 5-6 membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur.

Suitable substituents on the substitutable nitrogen of the "optionally substituted" group includeOrEach of whichIndependently of one another is hydrogen, C_1–6Aliphatic (which may be substituted as defined below), unsubstituted-OPh or an unsubstituted 5-6 membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur, or, although defined above, two independent occurrencesTogether with their intervening atoms, form a 3-12 membered saturated, partially unsaturated, or aryl monocyclic or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

In thatSuitable substituents on the aliphatic radical of (A) are independently halogen, -R^●- (halogenated R)^●)、–OH、–OR^●-O (halo R)^●)、–CN、–C(O)OH、–C(O)OR^●、–NH₂、–NHR^●、–NR^● ₂or-NO₂Wherein each R is^●Is unsubstituted or preceded by "halo" and is independently C_1–4Aliphatic, -CH₂Ph，–O(CH₂)_0–1Ph or a 5-6 membered saturated, partially unsaturated or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen or sulfur.

When substituents are described herein, the term "group" or "optionally substituted group" is sometimes used. In this context, "group" means a moiety or functional group having available positions for attachment to a structure to which a substituent is bound. Typically, if the substituent is a separate neutral molecule than the substituent, then the point of attachment will have a hydrogen atom. Thus, the term "group" or "optionally substituted group" may be used interchangeably with "group" or "optionally substituted group" in this context.

The term "head-to-tail" or "HT" as used herein refers to the regiochemistry (regiochemistry) of adjacent repeat units in a polymer chain. For example, in the context of poly (propylene carbonate) (PPC), the term head-to-tail based on three regiochemical possibilities is shown below:

the term "head-to-tail ratio" or (H: T) refers to the ratio of head-to-tail bonds to the sum of the chemical possibilities of all other regions. With respect to the description of the polymer structure, while specific regiochemical orientations of the monomer units may be shown to represent the polymer structures herein, this is not intended to limit the polymer structure to the regiochemical arrangements shown, but unless otherwise specified, should be construed to encompass all regiochemical arrangements including the described regiochemical arrangements, opposite regiochemistry, random mixtures, isotactic species, syndiotactic species, racemic species and/or enantiomerically enriched species and combinations of any of these.

The term "alkoxylated" as used herein means that one or more functional groups (typically, but not strictly limited to alcohols, amines or carboxylic acids) on the molecule have a hydroxyl-terminated alkyl chain attached thereto. The alkoxylated compounds may contain a single alkyl group or they may be oligomeric moieties such as hydroxyl terminated polyethers. The alkoxylated species may be derived from the parent compound by treating the functional group with an epoxide.

Drawings

FIG. 1 shows a graph of load bearing (CFD) data for PU foams with and without a 58-103-C polyol.

FIG. 2 shows a graph of load bearing (CFD) data for PU foams with and without 74-276 polyol.

Fig. 3 shows a graph of density normalized load bearing data for PU foams with and without the additives of the present invention and with other additives.

Fig. 4 shows a graph of comfort factor data (SAG values) for PU foams with and without the additive of the invention and with other additives.

Fig. 5 shows a graph of comfort factor data (SAG values) for PU foams with and without the additive of the invention and with other additives.

FIG. 6 shows a graph comparing the CFD values of certain Viscoelastic (VE) foams of the present invention to a reference foam.

Fig. 7 shows a graph comparing CFD values for certain VE foams of the present invention and reference foams.

Fig. 8 shows a graph comparing the hysteresis of certain VE foams of the present invention with a reference foam.

Fig. 9 shows a graph comparing CFD values for certain VE foams of the present invention and reference foams.

Fig. 10 shows a graph comparing CFD values for certain VE foams of the present invention and reference foams.

Fig. 11 shows a graph comparing the hysteresis of certain VE foams of the present invention with a reference foam.

Fig. 12 shows a graph comparing CFD values for certain VE foams of the present invention and reference foams.

Fig. 13 shows a graph comparing CFD values for certain VE foams of the present invention and reference foams.

Fig. 14 shows a graph comparing the hysteresis of certain VE foams of the present invention with a reference foam.

Fig. 15 shows a graph comparing CFD values for certain VE foams of the present invention and reference foams.

Fig. 16 shows a graph comparing CFD values for certain VE foams of the present invention and reference foams.

Fig. 17 shows a graph comparing the hysteresis of certain VE foams of the present invention with a reference foam.

Fig. 18 shows DMA plots of reference VE foam and VE foam prepared according to the present invention.

Fig. 19 shows DMA plots of two VE foam samples prepared according to the present invention.

Fig. 20 shows DMA plots of two VE foam samples prepared according to the present invention.

Fig. 21 shows DSC diagrams of reference VE foam and VE foam prepared according to the present invention.

Fig. 22 shows DSC profiles of two VE foam samples prepared according to the present invention.

Fig. 23 shows DSC plots for two VE foam samples prepared according to the present invention.

Fig. 24 shows a graph of the resilience performance of PU foams based on Novomer and commercial polyols.

FIG. 25 shows a graph of hysteresis performance for PU foams based on Novomer and commercial polyols.

Fig. 26 shows a graph of the load bearing properties of PU foams based on Novomer and commercial polyols.

Fig. 27 shows a graph of the load bearing properties of PU foams based on Novomer and commercial polyols.

Fig. 28 shows a graph of the load bearing properties of PU foams based on Novomer and commercial polyols.

Fig. 29 shows a graph of normalized load bearing performance of PU foams based on Novomer and commercial polyols.

Fig. 30 shows a graph of normalized load bearing performance of PU foams based on Novomer and commercial polyols.

Fig. 31 shows a graph of normalized load bearing performance of PU foams based on Novomer and commercial polyols.

Fig. 32 shows a graph of the support factor data for PU foams based on Novomer and commercial polyols.

FIG. 33 shows the Chrysler materials Standard for "Cellular, Molded Polyurethane High Resilience (HR) Type Seat Applications": MS-DC-649.

Detailed Description

The field of polyurethane manufacture and formulation is well developed. In some embodiments, the novel materials presented herein are formulated, processed, and used according to methods well known in the art. Variations, modifications, and applications of the composition will be apparent to the skilled person combining the knowledge in the art with the disclosure and teachings herein, and such variations are expressly contemplated herein. The following references contain information on the formulation, manufacture and use of polyurethane foams and elastomers, and the entire contents of each of these references are incorporated herein by reference.

Vahid sendijrevic, et al;Polymeric Foams And Foam Technologyhanser Gardner Publications, 2 nd edition; 2004(ISBN 978-

David Eaves；Handbook of Polymer Foams,Smithers Rapra Press；2004(ISBN978-1859573884)

Shau-Tarng Lee et al;Polymeric Foams:Science and Technology,CRC Press2006(ISBN 978-0849330759)

Kaneyoshi Ashida；Polyurethane and Related Foams:Chemistry and Technology,CRC Press；2006(ISBN 978-1587161599)

Handbook of Thermoplastic Elastomers,William Andrew Publishers,2007(ISBN 978-0815515494)

The Polyurethanes Book,J.Wiley&Sons,2003(ISBN 978-0470850411)

I. method for reinforcing polyurethane foam

Commercial polyurethane foam compositions are typically made by combining two components: an isocyanate component (often referred to in the art as an a-side mixture) containing one or more polyisocyanate compounds optionally blended with additional materials such as diluents, solvents, co-reactants, and the like, and a polyol component (often referred to in the art as a B-side mixture) comprising one or more polyols optionally blended with additional reactants, solvents, catalysts or additives.

In certain embodiments, the methods of the invention comprise treating a subject with a composition comprising CO₂And one or more epoxides, replacing the polyol component part of the polyurethane foam composition.

In certain embodiments, the method entails replacing between about 1 weight percent and about 50 weight percent of the polyol content of the polyurethane foam formulation with an aliphatic polycarbonate polyol. In certain embodiments, the aliphatic polycarbonate polyols used for this purpose have a primary polymeric repeat unit having the structure:

wherein R is¹Independently at each occurrence in the polymer chain is-H, -CH₃or-CH₂CH₃。

In certain embodiments, the present invention provides a method for increasing the load bearing properties of a polyurethane foam composition comprising the reaction product of a polyol component and a polyisocyanate component, the method comprising the step of incorporating into the polyol component a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide. In certain embodiments, the polycarbonate polyol is added in an amount of from about 1 weight percent to about 50 weight percent of all polyols present in the polyol component of the foam formulation. In certain embodiments, the added polycarbonate polyol is provided in an amount of from about 2 weight percent to about 50 weight percent of all polyols present in the polyol component of the foam formulation. In certain embodiments, the added polycarbonate polyol is provided in an amount from about 5 weight percent to about 25 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of from about 1 weight percent to about 2 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of from about 2 weight percent to about 5 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of from about 2 weight percent to about 10 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount from about 5 weight percent to about 10 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount from about 10 weight percent to about 20 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of from about 20 weight percent to about 30 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of from about 30 weight percent to about 50 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of about 1 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of about 2 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of about 3 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of about 5 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of about 10 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of about 15 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of about 20 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of about 25 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of about 30 weight percent of all polyols present in the polyol component. In certain embodiments, the added polycarbonate polyol is provided in an amount of about 40 weight percent of all polyols present in the polyol component.

In certain embodiments, the other polyols present in the polyol component to which the aliphatic polycarbonate polyol is added are selected from the group consisting of: polyether polyol, polyester polyol, polybutadiene polyol, polysulfide polyol, natural oil polyol, fluorinated polyolAlcohols, aliphatic polyols, polyether carbonate polyols, except from epoxides-CO₂Polycarbonate polyols other than those obtained by copolymerization and mixtures of any two or more of these. In certain embodiments, between about 50% and about 99% of the total weight of the polyols present in the polyol component (i.e., excluding any other non-polyol components that may be present in the B-side composition for the foam, such as catalysts, cell openers, blowing agents, stabilizers, diluents, pigments, etc.) comprise one or more polyols selected from the group consisting of: polyether polyols, polyester polyols, polybutadiene polyols, polysulfide polyols, natural oil polyols, fluorinated polyols, aliphatic polyols, except from the epoxide-CO₂Polycarbonate polyols other than those obtained by copolymerization and mixtures of any two or more of these. In certain embodiments, the other polyols present in the polyol component to which the aliphatic polycarbonate polyol is added comprise essentially polyether polyols. In certain embodiments, the other polyols present in the polyol component to which the aliphatic polycarbonate polyol is added substantially comprise polyester polyols. In certain embodiments, the other polyols present in the polyol component to which the aliphatic polycarbonate polyol is added comprise essentially a mixture of polyether polyols and polyester polyols.

In certain embodiments, the methods of the present invention comprise formulating a high strength flexible polyurethane foam composition by providing a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide as the polyol component in a B-side composition comprising a polyether polyol. In certain embodiments, the polycarbonate polyol is provided in an amount such that the final B-side composition contains from about 1 part to about 100 parts of polycarbonate polyol by weight based on 100 parts of polyether polyol. In certain embodiments, the polycarbonate polyol is provided in an amount such that the polycarbonate polyol comprises about 5 parts, about 10 parts, about 20 parts, about 30 parts, about 40 parts, about 60 parts, about 80 parts, or about 100 parts based on 100 parts of the polyether polyol in the resulting B-side formulation. In certain embodiments, the aliphatic polycarbonate polyol comprises poly (propylene carbonate). In certain embodiments, the added aliphatic polycarbonate polyol comprises poly (ethylene carbonate). In certain embodiments, the added aliphatic polycarbonate polyol comprises poly (ethylene-co-propylene carbonate). In certain embodiments, the method includes the additional step of stirring and/or heating the mixture of the aliphatic polycarbonate polyol and the polyether polyol. In certain embodiments, the method comprising the step of stirring and/or heating is conducted until a substantially homogenous mixture of the polycarbonate polyol and the polyether polyol is formed.

In certain embodiments, the method of the present invention is characterized by a foam formulated using the method having a higher strength than a corresponding foam formulated without the step of providing the polycarbonate polyol. In certain embodiments, the method is characterized by an enhancement of one or more properties selected from the group consisting of: tensile strength at break (measured according to ASTM D3574-08 test E); tear strength (measured according to ASTM D3574-08 test F); compressive Force Deflection (CFD) (measured according to ASTM D3574-08 test C); and tensile strength and elongation (measured according to ASTM D3574-08 test K) after dry heat aging at 140 ℃ for 22 hours.

In certain embodiments, the methods of the present invention are characterized by the resulting foam having a high compressive force deflection. Using the prior art, for flexible foams with good comfort, such CFD can only be achieved by incorporating filled polyols. The use of filled polyols may be undesirable from a cost standpoint and cause concerns due to the presence of residual VOCs (such as styrene). Residual VOCs cause an offensive odor in the finished foam and can have negative health effects on those exposed to articles made from the foam. We have found that CO is produced by the addition of an epoxide₂Copolymer reinforcementHave uniquely high CFD values as measured by ASTM D3574-08 test C, up to or exceeding those achieved by the addition of filled polyols, but without the attendant problems associated with filled polyols. Thus, in certain embodiments, the present invention encompasses methods of making high CFD foams.

In certain embodiments, the present invention provides a method of formulating a high strength polyurethane foam composition, represented as a reinforced foam formulation, comprising the step of adding to a B-side formulation a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide, said method being characterized in that the reinforced foam has a higher Compressive Force Deflection (CFD) value, as measured by ASTM D3574-08 test C, which indicates load bearing capacity, than the CFD value of a corresponding foam composition formulated without the added polycarbonate polyol, represented as a reference foam formulation, (i.e., the comparison is between two similarly formulated foams but the polycarbonate polyol replaces a portion of the polyol present in the B-side of the reference foam; non-limiting examples of such comparisons are provided herein in the examples section below, importantly, no other additions or essential changes to the proportions or characteristics of the other foam components are made for effective comparison). In certain embodiments, the method comprises adding the aliphatic polycarbonate polyol to a B-side formulation by replacing a portion of one or more polyols in a reference formulation such that the-OH number of the B-side formulation for the reinforcing foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the method is characterized in that the CFD value of the fortified foam formulation is at least 10% higher than the CFD value of the reference foam formulation. In certain embodiments, the method is characterized in that the CFD value of the fortified foam formulation is at least 10% higher, at least 20% higher, at least 30% higher, at least 40% higher, at least 50% higher, or at least 100% higher than the CFD value of the reference foam. In certain embodiments, the CFD values of the fortified foam and the reference foam are normalized to the density of the foam prior to comparing them. In certain embodiments, the method is characterized in that the fortified foam composition and the reference foam composition have substantially the same density.

In certain embodiments, the present invention provides a method of formulating a high strength polyurethane foam composition (denoted as a reinforced foam formulation) comprising the step of adding a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide to a B-side formulation, said method characterized in that the reinforced foam formulation has a lower density than a corresponding foam composition formulated without the added polycarbonate polyol (denoted as a reference foam formulation), further characterized in that the load bearing performance (CFD) of the reinforced foam as determined by test C of ASTM D3574-08 is equal to or higher than the load bearing performance of the reference foam. In certain embodiments, the method comprises adding the aliphatic polycarbonate polyol to a B-side formulation by replacing a portion of one or more polyols in a reference formulation such that the-OH number of the B-side formulation for the reinforcing foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the method is characterized in that the density of the fortified foam formulation is at least 10% lower than the density of the reference foam formulation. In certain embodiments, the method is characterized in that the density of the fortified foam formulation is at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% lower than the density of the reference foam. In certain embodiments, the method is characterized in that the density of the fortified foam formulation is at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% lower than the density of the reference foam, while the CFD of the fortified foam is at least equal to or at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 75%, or at least 100% higher than the CFD of the reference foam.

In certain embodiments, the method is characterized in that the reinforced foam formulation has a combination of a density of less than about 2.6 pounds per cubic foot (pcf) and a CFD at 25% deflection of at least 0.4psi as measured by ASTM D3574-08 test C. In certain embodiments, the method is characterized by a consolidated CFD value of at least 0.45psi at 25% deflection, at least 0.5psi at 25% deflection, or at least 0.52psi at 25% deflection. In certain embodiments, the method is characterized in that the CFD value of the reinforced foam formulation is at least 0.5psi at 50% deflection as measured by ASTM D3574-08 test C. In certain embodiments, the method is characterized in that the reinforced foam formulation has a CFD value as measured by ASTM D3574-08 test C of at least 0.55psi at 50% deflection, at least 0.60psi at 50% deflection, at least 0.65psi at 50% deflection, at least 0.7psi at 50% deflection, or at least 0.75psi at 50% deflection. In certain embodiments, the method is characterized in that the reinforced foam formulation has a CFD value of at least 0.7psi at 65% deflection as measured by ASTM D3574-08 test C. In certain embodiments, the method is characterized in that the reinforced foam formulation has a CFD value of at least 0.75psi at 65% deflection, at least 0.80psi at 65% deflection, at least 0.85psi at 65% deflection, at least 0.9psi at 65% deflection, or at least 1psi at 65% deflection, as measured by ASTM D3574-08 test C. In certain embodiments, the CFD values described above are for foam compositions having a density between about 2 and 2.6 pcf. In certain embodiments, the CFD values described above are for a foam composition having a density of between about 2.2 and 2.6pcf or a density of about 2.4 pcf. In certain embodiments, the CFD values described above are for foam compositions having a density between about 2 and 2.6pcf, and are further characterized in that they contain less than 10% filled polyol, less than 5% filled polyol, less than 3% filled polyol, less than 2% filled polyol, less than 1% filled polyol, or in that they are substantially free of filled polyol. In certain embodiments, the foam formulation described above is characterized by having comfort properties suitable for use in seat foams.

In certain embodiments, the method is characterized in that the reinforced foam formulation has a combination of a density of less than about 4pcf and a CFD at 25% deflection of at least 0.8psi as measured by ASTM D3574-08 test C. In certain embodiments, the method is characterized in that the reinforcing foam formulation has a CFD value of at least 0.85psi at 25% deflection, at least 0.9psi at 25% deflection, at least 0.95psi at 25% deflection, or at least 1psi at 25% deflection. In certain embodiments, the method is characterized by a CFD value for a reinforced foam formulation having a density of less than about 4pcf of at least 1psi at 50% deflection as measured by ASTM D3574-08 test C. In certain embodiments, the method is characterized by a consolidated CFD value of at least 1.1psi at 50% deflection, at least 1.2psi at 50% deflection, at least 1.3psi at 50% deflection, or at least 1.4psi at 50% deflection. In certain embodiments, the method is characterized by a CFD value for a reinforced foam formulation having a density of less than about 4pcf of at least 1.4psi at 65% deflection as measured by ASTM D3574-08 test C. In certain embodiments, the method is characterized in that the reinforcing foam formulation has a CFD value of at least 1.5psi at 65% deflection, at least 1.6psi at 65% deflection, at least 1.7psi at 65% deflection, at least 1.8psi at 65% deflection, at least 1.9psi at 65% deflection, or at least 2psi at 65% deflection. In certain embodiments, the CFD values described above are for a foam composition having a density between about 3.2 and 3.8 pcf. In certain embodiments, the CFD values described above are for a foam composition having a density of between about 3.3 and 3.7pcf or a density of about 3.5 pcf. In certain embodiments, the CFD values described above are for foams having a density between about 3.2 and 3.8pcf, and are further characterized in that they contain less than 10% filled polyol, less than 5% filled polyol, less than 3% filled polyol, less than 2% filled polyol, less than 1% filled polyol, or in that they are substantially free of filled polyol. In certain embodiments, the foam formulation described above is characterized by having comfort properties suitable for use in seat foams. In certain embodiments, the present invention provides a method of formulating a high strength polyurethane foam composition (denoted as a reinforced foam formulation) comprising the step of adding a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide to a B-side formulation, said method being characterized in that the tensile strength of the reinforced foam, as measured by ASTM D3574-08 test E, is higher than the tensile strength of a corresponding foam composition (denoted as a reference foam formulation) formulated without the added polycarbonate polyol. In certain embodiments, the method comprises adding the aliphatic polycarbonate polyol to a B-side formulation by replacing a portion of one or more polyols in a reference formulation such that the-OH number of the B-side formulation for the reinforcing foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the method is characterized in that the tensile strength of the fortified foam formulation is at least 10% higher than the tensile strength of the reference foam formulation. In certain embodiments, the method is characterized in that the tensile strength of the fortified foam formulation is at least 20%, at least 30%, at least 40%, at least 50%, or at least 100% higher than the tensile strength of the reference foam. In certain embodiments, the tensile strength of the fortified foam and the reference foam are normalized to the density of the foam prior to comparing them. In certain embodiments, the method is characterized in that the fortified foam composition and the reference foam composition have substantially the same density.

In certain embodiments, the present invention provides a method of formulating a high strength polyurethane foam composition (denoted as a reinforced foam formulation) comprising the step of adding a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide to a B-side formulation, said method characterized in that the reinforced foam formulation has a lower density than a corresponding foam composition formulated without the added polycarbonate polyol (denoted as a reference foam formulation), further characterized in that the tensile strength of the reinforced foam as determined by ASTM D3574-08 test E is equal to or higher than the tensile strength of the reference foam. In certain embodiments, the method comprises adding the aliphatic polycarbonate polyol to a B-side formulation by replacing a portion of one or more polyols in a reference formulation such that the-OH number of the B-side formulation for the reinforcing foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the method is characterized in that the density of the fortified foam formulation is at least 10% lower than the density of the reference foam formulation. In certain embodiments, the method is characterized in that the density of the fortified foam formulation is at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% lower than the density of the reference foam. In certain embodiments, the method is characterized in that the density of the fortified foam formulation is at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% lower than the density of the reference foam, while the tensile strength of the fortified foam is at least equal to or at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 75%, or at least 100% higher than the tensile strength of the reference foam.

In certain embodiments, the present invention provides a method of formulating a high strength polyurethane foam composition (denoted as a reinforced foam formulation) comprising the step of adding a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide to a B-side formulation, said method characterized in that the reinforced foam has a tear strength as measured by ASTM D3574-08 test F that is higher than the tear strength of a corresponding foam composition (denoted as a reference foam formulation) formulated without the added polycarbonate polyol. In certain embodiments, the method comprises adding the aliphatic polycarbonate polyol to a B-side formulation by replacing a portion of one or more polyols in a reference formulation such that the-OH number of the B-side formulation for the reinforcing foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the method is characterized in that the tensile strength of the fortified foam formulation is at least 10% higher than the tensile strength of the reference foam formulation. In certain embodiments, the method is characterized in that the tear strength of the fortified foam formulation is at least 20%, at least 30%, at least 40%, at least 50%, or at least 100% higher than the tear strength of the reference foam. In certain embodiments, the tear strength of the fortified foam and the reference foam are normalized to the density of the foam prior to comparing them. In certain embodiments, the method is characterized in that the fortified foam composition and the reference foam composition have substantially the same density.

In certain embodiments, the present invention provides a method of formulating a high strength polyurethane foam composition (denoted as a reinforced foam formulation) comprising the step of adding a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide to a B-side formulation, said method characterized in that the reinforced foam formulation has a lower density than a corresponding foam composition formulated without the added polycarbonate polyol (denoted as a reference foam formulation), further characterized in that the tear strength of the reinforced foam as determined by test F ASTM D3574-08 is equal to or higher than the tear strength of the reference foam. In certain embodiments, the method comprises adding the aliphatic polycarbonate polyol to a B-side formulation by replacing a portion of one or more polyols in a reference formulation such that the-OH number of the B-side formulation for the reinforcing foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the method is characterized in that the density of the fortified foam formulation is at least 10% lower than the density of the reference foam formulation. In certain embodiments, the method is characterized in that the density of the fortified foam formulation is at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% lower than the density of the reference foam. In certain embodiments, the method is characterized in that the density of the fortified foam formulation is at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% lower than the density of the reference foam, while the tear strength of the fortified foam is at least equal to or at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 75%, or at least 100% higher than the tear strength of the reference foam.

In certain embodiments, the reinforced foam composition made by the above-described method comprises a flexible polyurethane foam. In certain embodiments, the reinforced foam composition made by the above method comprises a viscoelastic polyurethane foam. In certain embodiments, the reinforced foam composition made by the above process comprises a rigid polyurethane foam.

In certain embodiments, the polycarbonate polyols used in the above-described methods have a primary repeat unit having the structure:

wherein R is¹、R²、R³And R⁴Each occurrence in the polymer chain is independently selected from the group consisting of: -H, fluorine, optionally substituted C_1-40Aliphatic radical, optionally substituted C_1-20Heteroaliphatic and optionally substituted aryl, wherein R¹、R²、R³And R⁴May optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms.

In certain embodiments, the polycarbonate polyols used in the above-described methods contain a primary repeat unit having the structure:

wherein R is¹As defined above.

wherein R is¹Independently at each occurrence in the polymer chain is-H or-CH₃。

In certain embodiments, the polycarbonate polyol used in the above-described methods is characterized in that it has a number average molecular weight (Mn) of between about 500g/mol and about 20,000 g/mol. In certain embodiments, the polycarbonate polyol is characterized in that it has an Mn of between about 1,000g/mol and about 5,000 g/mol. In certain embodiments, the polycarbonate polyol is characterized in that it has an Mn of between about 1,000g/mol and about 3,000 g/mol. In certain embodiments, the polycarbonate polyol is characterized in that it has an Mn of about 1,000g/mol, about 1,200g/mol, about 1,500g/mol, about 2,000g/mol, about 2,500g/mol, or about 3,000 g/mol.

In certain embodiments, the polycarbonate polyols used in the above-described methods are characterized by having a high percentage of terminal groups that are reactive with isocyanates. In certain embodiments, greater than 98%, greater than 99%, greater than 99.5%, greater than 99.8%, greater than 99.9%, or substantially 100% of the chain ends are isocyanate-reactive groups. In certain embodiments, the terminal isocyanate-reactive chain contains an-OH group.

In certain embodiments, the aliphatic polycarbonate polyols used in the above-described methods are characterized in that they are substantially compatible with or soluble in other polyols present in the polyol component of the foam formulation. Substantially compatible in this context means that the aliphatic polycarbonate may be mixed with one or more other polyols and provide a homogeneous or near homogeneous mixture. In certain embodiments, the mixture is largely homogeneous at ambient temperature, while in other embodiments, the mixture is homogeneous at elevated temperature (e.g., the mixture is homogeneous at 30 ℃, at 40 ℃, at 80 ℃, at 100 ℃, or at 140 ℃). In certain embodiments, the polyol component of the foam formulation containing the aliphatic polycarbonate polyol is characterized as being a substantially homogeneous, transparent mixture.

In certain embodiments, the structure of the aliphatic polycarbonate polyol used in the above-described method is selected to enhance its compatibility with other polyols in the polyol component of the foam formulation. In certain embodiments, the provided aliphatic polycarbonate polyols are characterized in that they have one or more ether linkages present in the chain transfer agent embedded within the polycarbonate chain. In certain embodiments, such ether linkages result from the use of diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, or polyethylene-co-propylene glycol as chain transfer agents in the preparation of aliphatic polycarbonate polyols. In certain embodiments, such ether linkages are provided by using ethoxylated or propoxylated diols, triols, or higher polyols having four or more-OH groups. In certain embodiments, such ether linkages are provided by using isosorbide or other carbohydrate derived material as a chain transfer agent.

In certain embodiments, provided aliphatic polycarbonate polyols are characterized in that they have a functionality of 2. In certain embodiments, provided aliphatic polycarbonate polyols have a functionality greater than 2. In certain embodiments, the aliphatic polycarbonate polyols provided have a functionality between 2 and 4. In certain embodiments, the aliphatic polycarbonate polyols provided have a functionality between 2 and 3. In certain embodiments, the aliphatic polycarbonate polyols provided have a functionality of between 2 and about 2.6, between 2 and about 2.5, or between 2 and about 2.4. In certain embodiments, provided aliphatic polycarbonate polyols are characterized in that they comprise a mixture of a diol (functional number 2) and a higher functional polyol (e.g., a polyol having a functional number of 3,4, 5, or 6).

In certain embodiments, provided aliphatic polycarbonate polyols are characterized in that they have a number average molecular weight (Mn) of less than about 10,000 g/mol. In certain embodiments, provided aliphatic polycarbonate polyols are characterized in that they have an Mn of between 400 and about 10,000 g/mol. In certain embodiments, provided aliphatic polycarbonate polyols are characterized in that they have an Mn of between 400 and about 5,000g/mol, between 500 and about 3,000g/mol, between 700 and about 2,500g/mol, between 1,000 and 3,000g/mol, or between 700 and 1500 g/mol.

In certain embodiments, provided aliphatic polycarbonate polyols are characterized in that they comprise a copolymer of carbon dioxide and one or both of ethylene oxide and propylene oxide, have a Mn of less than 10,000g/mol, a functionality between 2 and 4, and have one or more ether linkages present in a chain transfer agent embedded within the polycarbonate chain. In certain embodiments, provided polycarbonate polyols comprise poly (propylene carbonate) comprising an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycol, or alkoxylated polyols, characterized in that it has an Mn of less than 5,000g/mol, and a functionality between 2 and 3. In certain embodiments, provided polycarbonate polyols comprise poly (propylene carbonate) containing an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycol, or alkoxylated polyols, characterized in that it has an Mn of less than 3,000g/mol, and a functionality between 2 and 2.5. In certain embodiments, provided polycarbonate polyols comprise poly (propylene carbonate) comprising an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycol, or alkoxylated polyols, characterized in that it has a Mn of between 500 and 2,500g/mol, and a functionality of between 2 and 2.5.

In certain embodiments, provided polycarbonate polyols comprise poly (ethylene carbonate) containing embedded chain transfer agents derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycols, or alkoxylated polyols characterized in that it has a Mn of less than 5,000g/mol, and a functionality between 2 and 3. In certain embodiments, provided polycarbonate polyols comprise poly (ethylene carbonate) containing embedded chain transfer agents derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycols, or alkoxylated polyols, characterized in that it has a Mn of less than 3,000g/mol, and a functionality between 2 and 2.5. In certain embodiments, provided polycarbonate polyols comprise poly (ethylene carbonate) comprising an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycols, or alkoxylated polyols, characterized in that it has a Mn between 500 and 2,500g/mol, and a functionality between 2 and 2.5. In certain embodiments, provided polycarbonate polyols comprise poly (ethylene-co-propylene carbonate) containing an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycols, or alkoxylated polyols, characterized in that it has an Mn of less than 5,000g/mol, and a functionality between 2 and 3. In certain embodiments, provided polycarbonate polyols comprise poly (ethylene-co-propylene carbonate) containing an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycols, or alkoxylated polyols, characterized in that it has an Mn of less than 3,000g/mol, and a functionality between 2 and 2.5. In certain embodiments, provided polycarbonate polyols comprise poly (ethylene-co-propylene carbonate) containing an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycols, or alkoxylated polyols, characterized in that it has an Mn of between 500 and 2,500g/mol, and a functionality of between 2 and 2.5.

The structures and properties of other aliphatic polycarbonate polyols used in the process of the invention are described at the end of the description entitled "Aliphatic polycarbonate polyols"in appendix A. In certain embodiments, the present invention encompasses any of the above methods, wherein the added polycarbonate polyol is selected from any one or more of those described in appendix a.

In certain embodiments, the process of the present invention comprises the additional step of reacting any B-side mixture comprising the above-described aliphatic polycarbonate polyol with an a-side formulation comprising one or more polyisocyanates.

The art of polyurethane synthesis is well developed and very large quantities of isocyanate and related polyurethane precursors are known in the art and are commercially available. It is understood that one skilled in the art of polyurethane formulation can use such isocyanates in conjunction with the teachings of this disclosure to practice a process within the scope of this invention. A description of suitable isocyanate compounds and related methods can be found in the following:Chemistry and Technology of Polyols for Polyurethanesionescu, Mihail 2005(ISBN 978-1-84735-. In certain embodiments, the A-side formulation contains a compound having the formulaIsocyanate reagentOne or more isocyanate reagents as described in appendix B of (a).

As an alternative to the above-described methods, another strategy encompassed by the present invention involves incorporating aliphatic polycarbonate polyols into the foam formulation, not by incorporating them into the B-side polyol mixture, but rather as part of the a-side isocyanate component of the foam. This strategy can achieve the same strength enhancement advantages described above. This variant of the invention can be obtained from the epoxide CO by using known methods₂Polyol of copolymer to make isocyanate-terminated prepolymer and adding these isocyanate-terminated materials insteadPart of the polyisocyanate in the non-fortified reference formulation to the a-side component of the foam formulation. Methods for converting polyols to isocyanate-terminated prepolymers by reacting the polyol with a molar excess of diisocyanate are well known in the art.

In certain embodiments, the method of the present invention comprises the step of providing a strength-enhancing additive comprising a CO-free polyisocyanate in a polyurethane foam composition₂And one or more epoxides. The invention therefore covers all the above variants and embodiments for producing a high-strength polyurethane foam composition, but modified in the step of reinforcing the foam, comprising the following sub-steps:

a) to contain CO₂And one or more epoxides with an excess of polyisocyanate (or reactive equivalent thereof) to provide an isocyanate-terminated polycarbonate polyol, and

b) adding the isocyanate-terminated polycarbonate polyol to an isocyanate component of a foam composition.

Other variations of the above-described method including additional steps required to formulate the finished foam will be apparent to those skilled in the art. Thus, although they are not described in this specification, the present invention specifically encompasses methods that include the additional steps typical of foam formulations. Such additional steps may include, but are not limited to:

adding additional components to the a-side and/or B-side formulation (e.g., catalysts, blowing agents, pigments, stabilizers, flame retardants, cell openers, surfactants, reactive diluents, antimicrobial agents, etc.);

heating, cooling, mixing or combining the a-side and B-side components; and

molding, extruding, blow molding, spraying, heating, curing, aging, or otherwise treating the foam formulation.

High strength polyurethane foam compositions

In another aspect, the present invention encompasses high strength polyurethane foam compositions. In certain embodiments, the compositions of the present invention have a combination of unexpected properties including increased strength at a given density, or higher compressive force deflection in combination with good comfort properties. These foam compositions meet the unmet needs of the foam industry and it is expected that the compositions will have significant value in applications where high strength or good durability properties must now be balanced against the demand for low density or low cost foams.

In certain embodiments, the present invention provides polyurethane foam compositions comprising the reaction product of a polyol component and a polyisocyanate component, wherein the polyol component comprises a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide. In certain embodiments, the polycarbonate polyol is present in an amount of from about 1 weight percent to about 50 weight percent of all polyols present in the polyol component. In certain embodiments, the foam compositions are characterized by their higher load bearing properties than corresponding foams formulated without polycarbonate polyols.

In certain embodiments, the foam compositions of the present invention comprise the reaction product of a polyol component and a polyisocyanate component, wherein the polyol component contains a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide. In certain embodiments, the polycarbonate polyol is present in an amount of from about 1 weight percent to about 50 weight percent of all polyols present in the polyol component of the foam composition. In certain embodiments, the polycarbonate polyol is present in an amount of from about 2 weight percent to about 50 weight percent of all polyols present in the polyol component of the foam composition. In certain embodiments, the polycarbonate polyol is present in an amount from about 5 weight percent to about 25 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount of from about 1 weight percent to about 2 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount of from about 2 weight percent to about 5 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount from about 2 weight percent to about 10 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount from about 5 weight percent to about 10 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount from about 10 weight percent to about 20 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount from about 20 weight percent to about 30 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount from about 30 weight percent to about 50 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount of about 1 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount of about 1 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount of about 2 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount of about 3 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount of about 5 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount of about 10 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount of about 15 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount of about 20 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount of about 25 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount of about 30 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount of about 40 weight percent of all polyols present in the polyol component. In certain embodiments, the polycarbonate polyol is present in an amount of about 50 weight percent of all polyols present in the polyol component.

In certain embodiments, the other polyols present in the polyol component (i.e., polyols other than polycarbonate polyols resulting from the copolymerization of one or more epoxides and carbon dioxide) are selected from the group consisting of: polyether polyols, polyester polyols, polybutadiene polyols, polysulfide polyols, natural oil polyols, fluorinated polyols, aliphatic polyols, polyether carbonate polyols, except from the epoxide-CO₂Polycarbonate polyols other than those obtained by copolymerization and mixtures of any two or more of these. In certain embodiments, between about 50% and about 99% of the total weight of the polyols present in the polyol component (i.e., excluding any other non-polyol components that may be present in the B-side composition for the foam, such as catalysts, cell openers, blowing agents, stabilizers, diluents, etc.) comprise one or more polyols selected from the group consisting of: polyether polyol, polyester polyol, polybutadiene polyol, polysulfide polyol, natural oil polyol, fluorinated polyol, polyether,Aliphatic polyols, except from epoxides-CO₂Polycarbonate polyols other than those obtained by copolymerization and mixtures of any two or more of these. In certain embodiments, the other polyols present in the polyol component substantially comprise polyether polyols. In certain embodiments, the other polyols present in the polyol component substantially comprise polyester polyols. In certain embodiments, the other polyols present in the polyol component comprise essentially a mixture of polyether polyols and polyester polyols.

In certain embodiments, the high strength foam compositions of the present invention comprise a polyol having a primary repeat unit having the structure:

wherein R is¹As defined above.

In certain embodiments, the above-described high strength foam compositions are characterized in that the polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide has a number average molecular weight (Mn) between about 500g/mol and about 20,000 g/mol. In certain embodiments, the polycarbonate polyol has an Mn of between about 1,000g/mol and about 5,000 g/mol. In certain embodiments, the polycarbonate polyol has an Mn of between about 1,000g/mol and about 3,000 g/mol. In certain embodiments, the polycarbonate polyol has an Mn of about 1,000g/mol, about 1,200g/mol, about 1,500g/mol, about 2,000g/mol, about 2,500g/mol, or about 3,000 g/mol.

In certain embodiments, the high strength foam compositions described above are characterized in that the polycarbonate polyol incorporated as an additive has a high percentage of terminal groups reactive with isocyanate. In certain embodiments, greater than 98%, greater than 99%, greater than 99.5%, greater than 99.8%, greater than 99.9%, or substantially 100% of the polycarbonate polyol chain ends are isocyanate-reactive groups. In certain embodiments, the terminal isocyanate-reactive chain contains an-OH group.

In certain embodiments, the high strength foam compositions described above are characterized in that the polycarbonate polyol incorporated as an additive is substantially compatible with or soluble in other polyols present in the polyol component of the foam formulation. Substantially compatible in this context means that the aliphatic polycarbonate may be mixed with one or more other polyols and provide a homogeneous or near homogeneous mixture. In certain embodiments, the mixture is largely homogeneous at ambient temperature, while in other embodiments, the mixture is homogeneous at elevated temperature (e.g., the mixture is homogeneous at 30 ℃, at 40 ℃, at 80 ℃, at 100 ℃, or at 140 ℃). In certain embodiments, the polyol component of the foam formulation containing the aliphatic polycarbonate polyol is characterized as being a substantially homogeneous, transparent mixture.

In certain embodiments, the high strength foam compositions of the present invention are characterized in that the structure of the aliphatic polycarbonate polyol incorporated is selected to enhance its compatibility with other polyols in the polyol component of the foam formulation. In certain embodiments, the aliphatic polycarbonate polyol is characterized in that it has one or more ether linkages present in the chain transfer agent embedded within the polycarbonate chain. In certain embodiments, such ether linkages result from the use of diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, or polyethylene-co-propylene glycol as chain transfer agents in the preparation of aliphatic polycarbonate polyols. In certain embodiments, such ether linkages are provided by using ethoxylated or propoxylated diols, triols, or higher polyols having four or more-OH groups. In certain embodiments, such ether linkages are provided by using isosorbide or other carbohydrate derived material as a chain transfer agent.

In certain embodiments, the high strength foam compositions of the present invention are characterized in that the aliphatic polycarbonate polyols used in the compositions have a functionality of 2 or about 2. In certain embodiments, the aliphatic polycarbonate polyol has a functionality greater than 2. In certain embodiments, the aliphatic polycarbonate polyol has a functionality between 2 and 4. In certain embodiments, the aliphatic polycarbonate polyol has a functionality between 2 and 3. In certain embodiments, the aliphatic polycarbonate polyol has a functionality of between 2 and about 2.6, between 2 and about 2.5, or between 2 and about 2.4. In certain embodiments, the aliphatic polycarbonate polyol is characterized in that it comprises a mixture of a diol (functional number 2) and one or more higher functional polyols (e.g., polyols having a functional number of 3,4, 5, or 6).

In certain embodiments, the high strength foam compositions of the present invention are characterized in that they incorporate aliphatic polycarbonate polyols having a number average molecular weight (Mn) of less than about 10,000 g/mol. In certain embodiments, the incorporated aliphatic polycarbonate polyol has an Mn of between 400 and about 10,000 g/mol. In certain embodiments, the incorporated aliphatic polycarbonate polyol is characterized in that it has an Mn of between 400 and about 5,000g/mol, between 500 and about 3,000g/mol, between 700 and about 2,500g/mol, between 1,000 and 3,000g/mol, or between 700 and 1500 g/mol.

In certain embodiments, the high strength foam compositions of the present invention are characterized in that they incorporate carbon dioxide and a copolymer of one or both of ethylene oxide and propylene oxide, have a Mn of less than 10,000g/mol, a functionality number between 2 and 4, and have one or more ether linkages present in a chain transfer agent embedded within the polycarbonate chain. In certain embodiments, the incorporated polycarbonate polyol comprises a poly (propylene carbonate) comprising an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycol, or alkoxylated polyols, characterized in that it has an Mn of less than 5,000g/mol, and a functionality between 2 and 3. In certain embodiments, the incorporated polycarbonate polyol comprises a poly (propylene carbonate) containing an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycols, or alkoxylated polyols, characterized in that it has an Mn of less than 3,000g/mol, and a functionality between 2 and 2.5. In certain embodiments, the incorporated polycarbonate polyol comprises a poly (propylene carbonate) containing an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycols, or alkoxylated polyols, characterized in that it has an Mn of between 500 and 2,500g/mol, and a functionality of between 2 and 2.5.

In certain embodiments, the incorporated polycarbonate polyol comprises a poly (ethylene carbonate) containing an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycols, or alkoxylated polyols, characterized in that it has an Mn of less than 5,000g/mol, and a functionality between 2 and 3. In certain embodiments, the incorporated polycarbonate polyol comprises a poly (ethylene carbonate) comprising an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycols, or alkoxylated polyols, characterized in that it has a Mn of less than 3,000g/mol, and a functionality between 2 and 2.5. In certain embodiments, the incorporated polycarbonate polyol comprises a poly (ethylene carbonate) containing an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycols, or alkoxylated polyols, characterized in that it has a Mn between 500 and 2,500g/mol, and a functionality between 2 and 2.5.

In certain embodiments, polycarbonate polyols are provided comprising poly (ethylene-co-propylene carbonate) containing an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycols, or alkoxylated polyols, characterized in that it has an Mn of less than 5,000g/mol, and a functionality between 2 and 3. In certain embodiments, the incorporated polycarbonate polyol comprises a poly (ethylene-co-propylene carbonate) containing an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycols, or alkoxylated polyols, characterized in that it has an Mn of less than 3,000g/mol, and a functionality between 2 and 2.5. In certain embodiments, the incorporated polycarbonate polyol comprises a poly (ethylene-co-propylene carbonate) containing an embedded chain transfer agent derived from diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, higher polyethylene glycols, higher polypropylene glycols, polyethylene-co-propylene glycols, or alkoxylated polyols, characterized in that it has an Mn of between 500 and 2,500g/mol, and a functionality of between 2 and 2.5.

The structure and properties of the aliphatic polycarbonate polyols that may be incorporated into the high strength foam compositions of the present invention are more fully described at the end of this specification entitled "Aliphatic polycarbonate polyols"in appendix A. In certain embodiments, the present invention encompasses any of the above-described foam formulations, wherein the polycarbonate polyols used in their formulation are selected from any one or more of those described in appendix a.

The high strength foam composition of the present invention comprises the reaction product of any B-side mixture comprising the above aliphatic polycarbonate polyol with an A-side formulation comprising one or more polyisocyanates. In certain embodiments, the high strength foam compositions of the present invention comprise MDI-based polyurethane foams. In certain embodiments, the high strength foam compositions of the present invention comprise a TDI-based polyurethane foam.

The art of polyurethane synthesis is well developed and very large quantities of isocyanate and related polyurethane precursors are known in the art and are commercially available. It is understood that one skilled in the art of polyurethane formulation is able to select and use such isocyanates in conjunction with the teachings of this disclosure to produce high strength foams within the scope of this invention. A description of suitable isocyanate compounds and the like may be found in the following:Chemistry and Technology of Polyols for Polyurethanesionescu, Mihail 2005(ISBN 978-1-84735-Herein incorporated. In certain embodiments, the foam of the present invention comprises any of the above polyol formulations and contains a compound having the formulaIsocyanate reagentThe reaction product of an a-side formulation of one or more isocyanate reagents as described in appendix B of (a).

In certain embodiments, the high strength foam compositions of the present invention comprise flexible polyurethane foam. In certain embodiments, the high strength foam compositions of the present invention comprise a viscoelastic polyurethane foam. In certain embodiments, the high strength foam compositions of the present invention comprise rigid polyurethane foam.

In certain embodiments, the high strength foams of the present invention described above comprise flexible foam compositions. In certain embodiments, the high strength foams of the present invention described above comprise high viscoelasticity flexible foam compositions. In certain embodiments, the present invention provides articles made from such flexible foam compositions. Such articles include, but are not limited to: slabstock foams, home and office seat cushions, personal protective equipment, sports equipment, office furniture, traffic seats, automotive upholstery, and surfaces such as dashboards, door panels, ceilings, and the like.

A.Flexible foam composition

In certain embodiments, the compositions of the present invention comprise high strength flexible polyurethane foam compositions derived from B-side compositions comprising polyether polyols in combination with polycarbonate polyols derived from the copolymerization of one or more epoxides and carbon dioxide. In certain embodiments, the polycarbonate polyol is present in an amount such that the final B-side composition contains from about 1 part to about 100 parts of polycarbonate polyol by weight based on 100 parts of polyether polyol. In certain embodiments, the polycarbonate polyol is present in an amount such that the polycarbonate polyol comprises about 5 parts, about 10 parts, about 20 parts, about 30 parts, about 40 parts, about 60 parts, about 80 parts, or about 100 parts based on 100 parts of the polyether polyol in the resulting B-side formulation. In certain embodiments, the aliphatic polycarbonate polyol comprises poly (propylene carbonate). In certain embodiments, the aliphatic polycarbonate polyol present comprises poly (ethylene carbonate). In certain embodiments, the aliphatic polycarbonate polyol present comprises poly (ethylene-co-propylene carbonate).

In certain embodiments, the high strength flexible foam compositions of the present invention are characterized by foams having higher strength than corresponding foams formulated without the polycarbonate polyol. In certain embodiments, the inventive foams are characterized by an enhancement in one or more properties selected from the group consisting of: tensile strength at break (measured according to ASTM D3574-08 test E); tear strength (measured according to ASTM D3574-08 test F); compressive Force Deflection (CFD) (measured according to ASTM D3574-08 test C); and tensile strength and elongation (measured according to ASTM D3574-08 test K) after dry heat aging at 140 ℃ for 22 hours.

In certain embodiments, the present invention provides high strength flexible polyurethane foam compositions (denoted as reinforced foam formulations) comprising polycarbonate polyols obtained from the copolymerization of one or more epoxides and carbon dioxide, and characterized in that the reinforced foam has a Compressive Force Deflection (CFD) value (which indicates load bearing capacity) as measured by ASTM D3574-08 test C that is higher than the CFD value of a corresponding foam composition (denoted as reference foam formulation) formulated without added polycarbonate polyol. In certain embodiments, the aliphatic polycarbonate polyol is present in the B-side formulation in place of a portion of the one or more polyols in the reference foam. Preferably, this is achieved such that the-OH number of the B-side formulation for the reinforcing foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the high strength foam of the present invention is characterized in that the CFD value of the fortified foam is at least 10% higher than the CFD value of the reference foam formulation. In certain embodiments, the high strength foam is characterized by a CFD value of the fortified foam that is at least 10% higher, at least 20% higher, at least 30% higher, at least 40% higher, at least 50% higher, or at least 100% higher than the CFD value of the reference foam. In certain embodiments, the CFD values of the fortified foam and the reference foam are normalized to the density of the foam prior to comparing them. In certain embodiments, the foam compositions of the present invention are characterized in that they have a density that is substantially the same as a reference foam composition to which they are compared.

In certain embodiments, the present invention provides high strength flexible polyurethane foam compositions (denoted as reinforced foam formulations) containing additives comprising polycarbonate polyols derived from the copolymerization of one or more epoxides and carbon dioxide, and characterized in that the reinforced foam formulation has a lower density than a corresponding foam composition formulated without additives (denoted as reference foam formulation), further characterized in that the load bearing performance (CFD) of the reinforced foam as determined by test C of ASTM D3574-08 is equal to or higher than the load bearing performance of the reference foam. In certain embodiments, the composition is characterized by providing the additive in a B-side formulation from which the foam is produced by replacing a portion of one or more polyols in a reference formulation such that the-OH number of the B-side formulation used to reinforce the foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the polyurethane foam composition of the present invention is characterized in that the enhanced foam formulation has a density at least 10% lower than the density of the reference foam formulation. In certain embodiments, the reinforced polyurethane foam composition of the present invention is characterized in that the density of the reinforced foam formulation is at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% lower than the density of the reference foam. In certain embodiments, the inventive foam composition is characterized by a density that is at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% lower than the density of the reference foam, while the CFD of the fortified foam is at least equal to or at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 75%, or at least 100% higher than the CFD of the reference foam.

In certain embodiments, the present invention provides high strength flexible TDI-based polyurethane foam compositions having a combination of a density of less than about 2.6 pounds per cubic foot (pcf) and a CFD at 25% deflection of at least 0.4psi as measured by ASTM D3574-08 test C. In certain embodiments, the method is characterized by the consolidated CFD value being at least 0.45psi at 25% deflection, at least 0.5psi at 25% deflection, or at least 0.52psi at 25% deflection. In certain embodiments, the high strength flexible TDI-based polyurethane foam is characterized by a CFD value of at least 0.5psi at 50% deflection as measured by ASTM D3574-08 test C. In certain embodiments, the high strength flexible TDI-based polyurethane foam is characterized by a CFD value of at least 0.55psi at 50% deflection, at least 0.60psi at 50% deflection, at least 0.65psi at 50% deflection, at least 0.7psi at 50% deflection, or at least 0.75psi at 50% deflection as measured by ASTM D3574-08 test C. In certain embodiments, the high strength flexible TDI-based polyurethane foam is characterized by the reinforced foam having a CFD value of at least 0.7psi at 65% deflection as measured by ASTM D3574-08 test C. In certain embodiments, the high strength flexible TDI-based polyurethane foam is characterized by a CFD value of at least 0.75psi at 65% deflection, at least 0.80psi at 65% deflection, at least 0.85psi at 65% deflection, at least 0.9psi at 65% deflection, or at least 1psi at 65% deflection as measured by ASTM D3574-08 test C. In certain embodiments, the CFD values described above are for foam compositions having a density between about 2 and 2.6 pcf. In certain embodiments, the high strength flexible TDI-based polyurethane foam has a density of between about 2.2 and 2.6pcf or a density of about 2.4 pcf. In certain embodiments, the high strength flexible TDI-based polyurethane foam has a density between about 2 and 2.6pcf, and is further characterized in that it contains less than 10% filled polyol, less than 5% filled polyol, less than 3% filled polyol, less than 2% filled polyol, less than 1% filled polyol, or in that it is substantially free of filled polyol. In certain embodiments, the foam formulation described above is characterized by having comfort properties suitable for use in seat foams.

In certain embodiments, the present invention provides high strength flexible TDI-based polyurethane foam compositions having a combination of a density of less than about 4pcf and a CFD at 25% deflection of at least 0.8psi as measured by ASTM D3574-08 test C. In certain embodiments, the method is characterized in that the reinforcing foam formulation has a CFD value of at least 0.85psi at 25% deflection, at least 0.9psi at 25% deflection, at least 0.95psi at 25% deflection, or at least 1psi at 25% deflection. In certain embodiments, the method is characterized by a CFD value for a reinforced foam having a density of less than about 4pcf of at least 1psi at 50% deflection as measured by ASTM D3574-08 test C. In certain embodiments, the high strength foam composition is characterized by a reinforcing CFD value of at least 1.1psi at 50% deflection, at least 1.15psi at 50% deflection, at least 1.2psi at 50% deflection, at least 1.3psi at 50% deflection, or at least 1.4psi at 50% deflection.

In certain embodiments, the high strength flexible TDI-based foam composition is characterized by the foam having a combination of a density of less than about 4pcf and a CFD at 65% deflection of at least 1.4psi as measured by ASTM D3574-08 test C. In certain embodiments, the high strength foam composition is characterized by a CFD value of the foam of at least 1.5psi at 65% deflection, at least 1.6psi at 65% deflection, at least 1.7psi at 65% deflection, at least 1.8psi at 65% deflection, at least 1.9psi at 65% deflection, or at least 2psi at 65% deflection. In certain embodiments, the high strength flexible TDI-based foam composition has a density between about 3.2 and 3.8 pcf. In certain embodiments, the high strength flexible TDI-based foam composition has a density of between about 3.3 and 3.7pcf or a density of about 3.5 pcf. In certain embodiments, the high strength flexible TDI-based foam composition has a density between about 3.2 and 3.8pcf, and is further characterized in that it contains less than 10% filled polyol, less than 5% filled polyol, less than 3% filled polyol, less than 2% filled polyol, less than 1% filled polyol, or in that it is substantially free of filled polyol. In certain embodiments, the foam formulation described above is characterized by having comfort properties suitable for use in seat foams.

In certain embodiments, the present invention provides a high strength flexible MDI based polyurethane foam composition having a combination of a density of less than about 2.5 pounds per cubic foot (pcf) and a CFD at 25% deflection of at least 0.35psi as measured by ASTM D3574-08 test C. In certain embodiments, the method is characterized by the consolidated CFD value being at least 0.4psi at 25% deflection, at least 0.45psi at 25% deflection, or at least 0.5psi at 25% deflection. In certain embodiments, the high strength flexible MDI based polyurethane foam is characterized by a CFD value of at least 0.4psi at 50% deflection as measured by ASTM D3574-08 test C. In certain embodiments, the high strength flexible MDI based polyurethane foam is characterized by a CFD value of at least 0.45psi at 50% deflection, at least 0.50psi at 50% deflection, at least 0.55psi at 50% deflection, at least 0.6psi at 50% deflection, or at least 0.65psi at 50% deflection as measured by ASTM D3574-08 test C. In certain embodiments, the high strength flexible MDI based polyurethane foam is characterized by a CFD value of at least 0.7psi at 65% deflection as measured by ASTM D3574-08 test C. In certain embodiments, the high strength flexible MDI based polyurethane foam is characterized by a CFD value of at least 0.75psi at 65% deflection, at least 0.80psi at 65% deflection, at least 0.85psi at 65% deflection, at least 0.9psi at 65% deflection, or at least 1psi at 65% deflection as measured by ASTM D3574-08 test C. In certain embodiments, the high strength MDI-based foam has a density of between about 2 and 2.6 pcf. In certain embodiments, the high strength MDI-based foam has a density of between about 2.2 and 2.6pcf or a density of about 2.4 pcf. In certain embodiments, the high strength MDI based foams have a density between about 2 and 2.6pcf and are further characterized in that they contain less than 10% filled polyol, less than 5% filled polyol, less than 3% filled polyol, less than 2% filled polyol, less than 1% filled polyol, or in that they are substantially free of filled polyol. In certain embodiments, the foam formulation described above is characterized by having comfort properties suitable for use in seat foams.

In certain embodiments, the present invention provides high strength flexible MDI based polyurethane foam compositions having a combination of a density of less than about 4pcf and a CFD at 25% deflection of at least 0.8psi as measured by ASTM D3574-08 test C. In certain embodiments, the method is characterized in that the reinforcing foam formulation has a CFD value of at least 0.85psi at 25% deflection, at least 0.9psi at 25% deflection, at least 0.95psi at 25% deflection, or at least 1psi at 25% deflection. In certain embodiments, the method is characterized by a CFD value for a reinforced foam having a density of less than about 4pcf of at least 1psi at 50% deflection as measured by ASTM D3574-08 test C. In certain embodiments, the reinforced high strength foam composition is characterized by a CFD value of at least 1.1psi at 50% deflection, at least 1.2psi at 50% deflection, at least 1.4psi at 50% deflection, at least 1.5psi at 50% deflection, or at least 1.8psi at 50% deflection.

In certain embodiments, the high strength MDI-based foam composition is characterized by the foam having a combination of a density of less than about 4pcf and a CFD at 65% deflection of at least 1.4psi as measured by ASTM D3574-08 test C. In certain embodiments, the high strength foam composition is characterized by a CFD value of the foam of at least 1.5psi at 65% deflection, at least 1.6psi at 65% deflection, at least 1.7psi at 65% deflection, at least 1.8psi at 65% deflection, at least 1.9psi at 65% deflection, at least 2psi at 65% deflection, or at least 3psi at 65% deflection. In certain embodiments, the high strength MDI-based foam composition has a density of between about 3.2 and 3.8 pcf. In certain embodiments, the high strength MDI-based foam composition has a density of between about 3.3 and 3.7pcf or a density of about 3.5 pcf. In certain embodiments, the high strength MDI based foam composition has a density of between about 3.2 and 3.8pcf and is further characterized in that it contains less than 10% filled polyol, less than 5% filled polyol, less than 3% filled polyol, less than 2% filled polyol, less than 1% filled polyol, or in that it is substantially free of filled polyol. In certain embodiments, the foam formulation described above is characterized by having comfort properties suitable for use in seat foams.

In certain embodiments, the present invention provides high strength flexible polyurethane foam compositions (denoted as reinforced foam formulations) containing additives comprising polycarbonate polyols derived from the copolymerization of one or more epoxides and carbon dioxide, and characterized in that the tensile strength of the reinforced foam, as measured by ASTM D3574-08 test E, is higher than the tensile strength of a corresponding foam composition (denoted as reference foam formulation) formulated without added polycarbonate polyols. In certain embodiments, the aliphatic polycarbonate polyol is present in the B-side formulation in place of a portion of the one or more polyols in the reference foam. Preferably, this is achieved such that the-OH number of the B-side formulation for the reinforcing foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the high strength foam of the present invention is characterized in that the tensile strength of the fortified foam is at least 10% higher than the tensile strength of the reference foam formulation. In certain embodiments, the high strength foam is characterized in that the tensile strength of the fortified foam is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, or at least 100% higher than the tensile strength of the reference foam. In certain embodiments, the tensile strength of the fortified foam and the reference foam are normalized to the density of the foam prior to comparing them. In certain embodiments, the foam compositions of the present invention are characterized in that they have a density that is substantially the same as a reference foam composition to which they are compared.

In certain embodiments, the present invention provides high strength flexible polyurethane foam compositions containing additives comprising polycarbonate polyols derived from the copolymerization of one or more epoxides and carbon dioxide. In certain embodiments, the foam composition of the present invention is characterized by having a lower density than a corresponding foam composition formulated without the polycarbonate polyol additive (represented as a reference foam formulation), and further characterized by the tensile strength of the reinforced foam as determined by test E of astm d3574-08 being equal to or higher than the tensile strength of the reference foam. In certain embodiments, the composition is characterized by providing the additive in a B-side formulation from which the foam is produced by replacing a portion of one or more polyols in a reference formulation such that the-OH number of the B-side formulation used to reinforce the foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the polyurethane foam composition of the present invention is characterized in that the enhanced foam formulation has a density at least 10% lower than the density of the reference foam formulation. In certain embodiments, the reinforced polyurethane foam composition of the present invention is characterized in that the density of the reinforced foam formulation is at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% lower than the density of the reference foam. In certain embodiments, the inventive foam composition is characterized by a density that is at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% lower than the density of the reference foam, while the tensile strength of the reinforcing foam is at least equal to or at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 75%, or at least 100% higher than the tensile strength of the reference foam.

In certain embodiments, the present invention provides high strength flexible polyurethane foam compositions (denoted as reinforced foam formulations) containing additives comprising polycarbonate polyols derived from the copolymerization of one or more epoxides and carbon dioxide, and characterized in that the tear strength of the reinforced foam, as measured by ASTM D3574-08 test E, is higher than the tear strength of a corresponding foam composition (denoted as reference foam formulation) formulated without added polycarbonate polyols. In certain embodiments, the aliphatic polycarbonate polyol is present in the B-side formulation in place of a portion of the one or more polyols in the reference foam. Preferably, this is achieved such that the-OH number of the B-side formulation for the reinforcing foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the high strength foam of the present invention is characterized in that the tensile strength of the fortified foam is at least 10% higher than the tensile strength of the reference foam formulation. In certain embodiments, the high strength foam is characterized in that the tensile strength of the fortified foam is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, or at least 100% higher than the tensile strength of the reference foam. In certain embodiments, the tensile strength of the fortified foam and the reference foam are normalized to the density of the foam prior to comparing them. In certain embodiments, the foam compositions of the present invention are characterized in that they have a density that is substantially the same as a reference foam composition to which they are compared.

In certain embodiments, the present invention provides high strength flexible polyurethane foam compositions containing additives comprising polycarbonate polyols derived from the copolymerization of one or more epoxides and carbon dioxide. In certain embodiments, the foam composition of the present invention is characterized by having a density that is lower than a corresponding foam composition formulated without the polycarbonate polyol additive (denoted as a reference foam formulation), and further characterized by the tear strength of the reinforced foam as determined by test F of astm d3574-08 being equal to or higher than the tear strength of the reference foam. In certain embodiments, the composition is characterized by providing the additive in a B-side formulation from which the foam is produced by replacing a portion of one or more polyols in a reference formulation such that the-OH number of the B-side formulation used to reinforce the foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the polyurethane foam composition of the present invention is characterized in that the enhanced foam formulation has a density at least 10% lower than the density of the reference foam formulation. In certain embodiments, the reinforced polyurethane foam composition of the present invention is characterized in that the density of the reinforced foam formulation is at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% lower than the density of the reference foam. In certain embodiments, the inventive foam composition is characterized by a density that is at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% lower than the density of the reference foam, while the tear strength of the fortified foam is at least equal to or at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 75%, or at least 100% higher than the tensile strength of the reference foam.

B.Viscoelastic foam composition

Viscoelastic (VE) foams are aqueous foams typically produced using a mixture of a low molecular weight hydrophobic polyol, a high molecular weight polyol produced from propylene oxide and ethylene oxide, and a short molecular weight chain extender. These foams are typically produced at relatively low isocyanate indices which contribute to an open cell structure. To balance foaming rate and open cell morphology, polyols having high levels of hydrophilic ethylene oxide groups are used in the preparation of these foams and various surfactants. For the production of soft (compliant) foams, isocyanates such as TDI or mixtures of 4,4 '-and 2,4' -MDI are generally used in the production of VE foams. Calcium carbonate or other fillers may also be added to these formulations to increase density (and load bearing properties) and reduce tack.

In certain embodiments, the present invention provides novel VE foams characterized by at least a portion of the one or more polyols in the B-side formulation being made of CO₂And one or more epoxides. In certain embodiments, the VE foam compositions are further characterized in that they areContaining less or no inorganic filler than a comparative foam having similar viscoelastic properties but lacking the polycarbonate polyol additive. In certain embodiments, the polycarbonate polyol is present in an amount such that the final B-side composition contains from about 1 part to about 100 parts of polycarbonate polyol by weight based on 100 parts of polyether polyol. In certain embodiments, the polycarbonate polyol is present in an amount such that the polycarbonate polyol comprises about 5 parts, about 10 parts, about 20 parts, about 30 parts, about 40 parts, about 60 parts, about 80 parts, or about 100 parts based on 100 parts of the polyether polyol in the resulting B-side formulation. In certain embodiments, the aliphatic polycarbonate polyol comprises poly (propylene carbonate). In certain embodiments, the aliphatic polycarbonate polyol present comprises poly (ethylene carbonate). In certain embodiments, the aliphatic polycarbonate polyol present comprises poly (ethylene-co-propylene carbonate).

In certain embodiments, the high strength VE foam compositions of the present invention are characterized by a foam having a higher strength than a corresponding foam formulated without the polycarbonate polyol additive. In certain embodiments, the inventive foams are characterized by an enhancement in one or more properties selected from the group consisting of: tensile strength at break (measured according to ASTM D3574-08 test E); tear strength (measured according to ASTM D3574-08 test F); compressive Force Deflection (CFD) (measured according to ASTM D3574-08 test C); and tensile strength and elongation (measured according to ASTM D3574-08 test K) after dry heat aging at 140 ℃ for 22 hours.

In certain embodiments, the present invention provides a high strength VE foam composition (denoted as a reinforced foam formulation) comprising a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide, and characterized in that the reinforced foam has a Compressive Force Deflection (CFD) value (which is indicative of load bearing capacity) measured according to ASTM D3574-08 test C that is higher than the CFD value of a corresponding VE foam composition (denoted as a reference foam formulation) formulated without added polycarbonate polyol. In certain embodiments, the aliphatic polycarbonate polyol is present in the B-side formulation in place of a portion of the one or more polyols in the reference foam. Preferably, this is achieved such that the-OH number of the B-side formulation for the reinforcing foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the high strength foam of the present invention is characterized in that the CFD value of the fortified foam is at least 10% higher than the CFD value of the reference foam formulation. In certain embodiments, the high strength foam is characterized by a CFD value of the fortified foam that is at least 10% higher, at least 20% higher, at least 30% higher, at least 40% higher, at least 50% higher, or at least 100% higher than the CFD value of the reference foam. In certain embodiments, the CFD values of the fortified foam and the reference foam are normalized to the density of the foam prior to comparing them. In certain embodiments, the foam compositions of the present invention are characterized in that they have a density that is substantially the same as a reference foam composition to which they are compared.

In certain embodiments, the present invention provides a high strength VE foam composition (denoted as a reinforced foam formulation) comprising an additive comprising a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide, and characterized in that the tensile strength of the reinforced foam, measured according to ASTM D3574-08 test E, is higher than the tensile strength of a corresponding foam composition (denoted as a reference foam formulation) formulated without the added polycarbonate polyol. In certain embodiments, the aliphatic polycarbonate polyol is present in the B-side formulation in place of a portion of the one or more polyols in the reference foam. Preferably, this is achieved such that the-OH number of the B-side formulation for the reinforcing foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the high strength foam of the present invention is characterized in that the tensile strength of the fortified foam is at least 10% higher than the tensile strength of the reference foam formulation. In certain embodiments, the high strength foam is characterized in that the tensile strength of the fortified foam is at least 10% higher, at least 20% higher, at least 30% higher, at least 40% higher, at least 50% higher, or at least 100% higher than the tensile strength of the reference foam. In certain embodiments, the tensile strength of the fortified foam and the reference foam are normalized to the density of the foam prior to comparing them. In certain embodiments, the foam compositions of the present invention are characterized in that they have a density that is substantially the same as a reference foam composition to which they are compared.

In certain embodiments, the present invention provides a high strength VE foam composition (denoted as a reinforced foam formulation) comprising an additive comprising a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide, and characterized in that the tear strength of the reinforced foam, measured according to ASTM D3574-08 test E, is higher than the tensile strength of a corresponding foam composition (denoted as a reference foam formulation) formulated without the added polycarbonate polyol. In certain embodiments, the aliphatic polycarbonate polyol is present in the B-side formulation in place of a portion of the one or more polyols in the reference foam. Preferably, this is achieved such that the-OH number of the B-side formulation for the reinforcing foam is substantially the same as the-OH number of the B-side formulation of the reference foam formulation. In certain embodiments, the high strength foam of the present invention is characterized in that the tensile strength of the fortified foam is at least 10% higher than the tensile strength of the reference foam formulation. In certain embodiments, the high strength foam is characterized in that the tensile strength of the fortified foam is at least 10% higher, at least 20% higher, at least 30% higher, at least 40% higher, at least 50% higher, or at least 100% higher than the tensile strength of the reference foam. In certain embodiments, the tensile strength of the fortified foam and the reference foam are normalized to the density of the foam prior to comparing them. In certain embodiments, the foam compositions of the present invention are characterized in that they have a density that is substantially the same as a reference foam composition to which they are compared.

In certain embodiments, the present invention provides high strength VE foam compositions (denoted as fortified foam formulations) containing additives comprising polycarbonate polyols derived from the copolymerization of one or more epoxides and carbon dioxide, and characterized by increased energy absorption properties of the foam. In certain embodiments, this increase in energy absorption is indicated by an increase in hysteresis loss according to ASTM 3574-08, hysteresis procedure B. In certain embodiments, the VE foam of the present invention has greater hysteresis loss than a corresponding foam composition formulated without the added polycarbonate polyol (denoted as a reference foam formulation). In certain embodiments, the high strength foam of the present invention is characterized by a hysteresis loss at least 10% greater than that of a reference foam formulation. In certain embodiments, the high strength foam of the present invention is characterized in that its hysteresis loss is at least 20% higher, at least 30% higher, at least 40% higher, at least 50% higher, or at least 100% higher than that of the reference foam under the same conditions.

In certain embodiments, the viscoelastic foam composition of the present invention is characterized by having a reduced amount of inorganic filler.

C.Foams having novel physical properties

In another aspect, the present invention encompasses foam compositions having a combination of novel physical properties. In certain embodiments, the present invention provides a flexible polyurethane foam comprising the reaction product of a B-side mixture comprising essentially polyether polyol and an a-side mixture comprising one or more MDI or TDI, characterized in that the foam has the following combination:

less than 40kg/m of test A by ASTM D3574-08³(ii) a density of (d);

a CFD of greater than 1psi (or 3kPa) at 65% of test C by ASTM D3574-08; and

SAG factor between 2.0 and 3.0 (from ASTM D3574-08, test C is obtained by dividing CFD at 65% compression by CFD at 25% compression).

In certain embodiments, the foam of the present invention is characterized in that it has the following combination: less than 38kg/m of test A by ASTM D3574-08³Less than 36kg/m³Less than 34kg/m³Less than 32kg/m³Or less than 30kg/m³(iii) density and CFD at 65% of greater than 1.6psi and SAG factor of about 2.0 by ASTM D3574-08, test C.

In certain embodiments, the foam of the present invention is characterized in that it has the following combination: CFD at 65% of test C of greater than 0.8psi, greater than 1.0psi, greater than 1.2psi, greater than 1.4psi, greater than 1.6psi, greater than 1.8psi, or greater than 2.0psi by ASTM D3574-08, has a CFD of less than 40kg/m³And a comfort factor between 2 and 3.

In certain embodiments, the foam of the present invention is characterized in that it has the following combination: a CFD at 65% of test C of greater than 1psi, greater than 1.2psi, greater than 1.4psi, greater than 1.5psi, greater than 1.75psi, or greater than 2psi by ASTM D3574-08; having a weight of less than 38kg/m passing ASTM D3574-08, test A³Less than 36kg/m³Less than 34kg/m³Less than 32kg/m³Or less than 30kg/m³And a comfort factor between 2 and 3.

One method that is used today in the polyurethane foam art to increase the strength or CFD of flexible foams is to add a graft polyol to the B-side formulation. Graft polyols (also known as filled polyols or polymer polyols) contain finely divided styrene-acrylonitrile, acrylonitrile or Polyurea (PHD) polymer solids chemically grafted to a polyether backbone. They are used to increase the load bearing properties of low density High Resilience (HR) foams, and to increase the toughness of microcellular foams and cast elastomers. However, these materials add to the cost of the foam and sometimes result in a reduction in other foam properties or an increase in foam density or, as noted above, introduce unwanted VOCs into the finished product. In certain embodiments, the foams of the present invention are characterized in that they contain little or no graft polyol, in addition to the combination of physical properties described above.

In certain embodiments, the above-described foam compositions of the present invention are further characterized in that they contain less than 20% of a graft polyol additive. In certain embodiments, the above-described foam compositions of the present invention are further characterized in that they contain less than 10% of a graft polyol additive. In certain embodiments, the above-described foam compositions of the present invention are further characterized in that they contain less than 5% of a graft polyol additive. In certain embodiments, the above-described foam compositions of the present invention are further characterized in that they contain less than 3% of a graft polyol additive. In certain embodiments, the above-described foam compositions of the present invention are further characterized in that they contain less than 2% of a graft polyol additive. In certain embodiments, the above-described foam compositions of the present invention are further characterized in that they contain less than 1% of a graft polyol additive. In certain embodiments, the above-described foam compositions of the present invention are further characterized in that they are free of graft-type polyol additives.

In certain embodiments, such filled polyols are selected from: polyurea dispersion polyols (i.e., Poly Harnststoff Dispersion (PHD) polyols); polyurethane dispersion polyols (i.e., polyisocyanate-plus-polyol (PIPA); epoxy dispersion polyols; aminoplast dispersions, acrylic polyols, etc. are used to increase the load-bearing properties of low density High Resilience (HR) foams, as well as to increase the toughness of microcellular foams and cast elastomers.

In certain embodiments, the above-described foam compositions of the present invention are further characterized in that they contain less than 5% of a filled polyol additive. In certain embodiments, the seat foam compositions of the present invention described above are further characterized in that they contain less than 3% of a filled polyol additive. In certain embodiments, the seat foam compositions of the present invention described above are further characterized in that they contain less than 2% of a filled polyol additive. In certain embodiments, the seat foam compositions of the present invention described above are further characterized in that they contain less than 1% of a filled polyol additive. The seat foam compositions of the present invention described above are further characterized in that they are free of graft-type, filled or acrylic polyol additives.

While not necessarily explicitly described, the present invention encompasses other variations of the foam compositions described above that contain additional components typical of the formulation of the finished foam. The skilled artisan will readily appreciate these compositions based on common general knowledge in the art of polyurethane foam formulations in combination with the teachings and disclosures herein. Thus, while they are not specifically described in this specification, the present invention contemplates and encompasses compositions comprising additional reactive components or additives (e.g., catalysts, blowing agents, pigments, stabilizers, flame retardants, cell openers, surfactants, reactive diluents, antimicrobials, solvents, etc.) in the a-side and/or B-side formulations. Non-limiting examples of additives that can be used in the A-side and/or B-side mixtures of the foams of the present invention are described in appendix C entitled "additives" at the end of this specification.

Isocyanate-terminated prepolymers having utility as foam additives

In another aspect, the present invention encompasses isocyanate-terminated polyols obtained by reacting an excess of a polyisocyanate with any of the above-described aliphatic polycarbonate polyols. Such compositions may be incorporated into a-side formulations of polyurethane foam formulations to provide enhanced strength. Scheme 1 shows a representative example of how such materials can be made:

wherein the polycarbonate polyol represents any of those described above in appendix a or in the major and minor classes herein, the diisocyanate represents any reagent that can react with two alcohols or with two alcohols to form two urethane linkages, and wherein g is 0 or an integer up to about 10.

Preferably, g is small so that the Mn of the prepolymer remains relatively low and the material can be dissolved in a typical polyurethane a-side mixture without making it too viscous. In certain embodiments, g in the prepolymer composition has an average value of less than 10, less than 5, less than 4, less than 3, less than 2, or less than 1.

The prepolymers of the invention may also be obtained from higher functional polyols and/or higher functional isocyanates including those described in appendix a and appendix B appended hereto.

In another aspect, the present invention encompasses a composition comprising the reaction product between an isocyanate component and a polyol component, wherein the isocyanate component comprises from about 1 weight percent to about 20 weight percent of a polyol comprising CO₂An isocyanate-terminated prepolymer of a polyol obtained by copolymerization with one or more epoxides.

Examples

The invention is illustrated by the following examples. It is to be understood that the specific embodiments, materials, amounts, and procedures are to be construed broadly in accordance with the scope and spirit of the invention as set forth herein.

Example 1: high strength flexible foam

Described below are formulations of high strength flexible polyurethane foams according to the principles of the present invention. These materials are prepared using the aliphatic polycarbonate polyol additives defined herein. In particular, the aliphatic polycarbonate polyols hereinafter also referred to as "Novomer polyols" for use in the formulations hereinafter have the following properties:

performance of	58-103-C	74-276


			Acid value, mg KOH/g	0.28	0.51
Hydroxyl number, mg KOH/g	119	61.1
			Mn(GPC)	1,270	2,213
Mw(GPC)	1,370	2,443
			Polydispersity, Mw/Mn	1.07	1.06
Glass transition temperature (DSC), Tg	-5℃	-5.5℃
			Viscosity, cPs	4,990@80℃	-

Polyol 58-103-C is a linear 1270g/mol poly (propylene carbonate) polyol initiated by dipropylene glycol (a mixture of isomers), having a PDI of 1.06, more than 99% of-OH end groups and more than 99% of carbonate linkages (excluding ether linkages in dipropylene glycol). The polyol corresponds to the formula:

wherein n averages about 5.6 in the composition.

Polyol 74-276 is a linear 2200g/mol poly (propylene carbonate) polyol initiated with 425g/mol polypropylene glycol (mixture of isomers), having a PDI of 1.06, more than 99% of-OH end groups and more than 99% of carbonate linkages (excluding ether linkages in polypropylene glycol). The polyol corresponds to the formula:

wherein k averages about 6.8 and n averages about 8.7 in the composition.

The aim of this study was to determine CO₂The use of a basic poly (propylene carbonate) diol (PPC diol) as an additive in the moulding of High Resilience (HR) flexible polyurethane foams.

The effect of these PPC diols on load bearing and other properties of free rise and molded flexible foams was evaluated in comparison to HR flexible foams formulated with or without commercial graft polyols.

Experiment:

raw materials

The list of raw materials used in this evaluation is shown in table 1. All materials (including Novomer polyols) were used as received from the supplier.

In foaming experiments, formulations targeting high resilience flexible foams were used as reference. The formulation is based on a Poly-G85-29 ethylene oxide capped polyether triol (polyol). Lumulse POE 26 (ethoxylated glycerol) was used as reactive cell opener. Diethanolamine is used as cocatalyst and crosslinker.

Preparation and testing of the foams

Free-rise water-blown foams were prepared with 5%, 10%, 15%, 20% and 25% Novomer 58-103C and Novomer 74-276 polyol, respectively, which were compatible with Polymer-G85-29 polyol (tables 2-4). All foams were prepared at an isocyanate index of 90 using Mondur MRS-2 (2, 4' -MDI rich isocyanate) (tables 3-5).

Molded foams were prepared with 10% and 20% Novomer 58-103C. Reference molded foams were also prepared with or without the graft polyol specialflex NC-701.

Free rise foams were prepared using standard laboratory hand mixing procedures. Foaming profiles including cream time, gel time, rise time were measured for all foams. Immediately after the rise time, the foam was placed in an air circulating oven preheated to 80 ℃ for 30 minutes to complete the cure.

Molded foams were prepared using 12x12x2 inch size aluminum molds preheated to 69 ℃. The demold time was 4.5 minutes.

All foams were aged at room temperature for a minimum of one week prior to testing. The following properties were measured according to ASTM D3574-08:

foam Density (test A)

Rebound resilience by ball (test H)

Tensile Strength at Break (test E)

Elongation at break (test E)

Tear Strength (test F)

CFD, compression force deflection (test C)

Hysteresis (procedure B-CFD hysteresis loss)

Dry (constant compression ratio) compression set (test D)

Wet (constant compression ratio) compression set (test D and humid heat ageing, test L)

Tensile Strength and elongation after Dry Heat ageing at 140 ℃ after 22 hours (modified Heat ageing test K)

Results

Reactivity of polyol

Polyurethane foams were prepared at 5%, 10%, 15%, 20% and 25% as a replacement for the conventional polyol Poly-G85-29 in molded HR flexible foam formulations. The introduction of PPC polyol 58-103-C polyol to the reference foam formulation as a simple (drop-in) replacement for Poly-G85-29 did not significantly affect the reaction profile (foaming profile) measured as cream time, gel time and rise time. However, the foam exhibited a closed cell structure and shrunk after preparation (table 3A). After adjusting the catalysis and increasing the amount of diethanolamine (reactive catalyst/crosslinker) from 1 to 2 parts by weight, stable foams with open-cell structure were obtained (tables 3A and 3B).

PPC polyol 74-276 polyol-based foams were prepared using the same catalytic package as used for Novomer 58-103C polyol-based foams. No significant difference in reactivity between the two polyols was observed (tables 3 and 4).

Apparent cell structure and density

The free-rise foams based on the Novomer polyol showed similar white color to the reference foams prepared with Poly-G85-29 polyol as the sole polyol and with 10% and 25% graft polyol Speciflex NC-701. The apparent cell structure of the foam with the Novomer polyol was uniform and similar to the reference foam.

The replacement of the reference polyol with 5% to 25% of the Novomer polyol did not significantly change the density of the free rise foam (tables 3 and 4).

Molded foams prepared with 10% and 20% of 58-103C PPC polyol had a uniform apparent cell structure and were similar to reference foams prepared with Poly-G85-29 polyol as the sole polyol and with 10% graft polyol Speciflex NC-701.

Physical properties of the foam

The reference free rise foam prepared with the graft polyol (Speciflex NC-701) also exhibited a somewhat lower resilience and a somewhat higher hysteresis than the reference foam prepared with the base polyol (Poly-G85-29) as the sole polyol (tables 3A and 5). Foams based on Novomer polyols showed a somewhat lower resilience and a somewhat higher hysteresis at the same load compared to foams based on graft polyols (tables 3B, 4 and 5).

All foams, including molded foams, prepared with the Novomer polyols exhibit relatively high resilience and can be classified as PU foams of High Resilience (HR).

In general, tensile strength increases with the incorporation of the Novomer polyol. The elongation did not change significantly with the introduction of the Novomer polyol (tables 3 and 4). The tensile strength and elongation of foams based on Novomer polyols were similar to those based on graft polyols under the same loading (tables 3-5). These results indicate that the strength (toughness) of the foam is increased by the incorporation of the Novomer polyol.

The tear strength measured on the foam prepared with the Novomer polyol was significantly higher compared to the reference foam prepared with the base polyol as the sole polyol (tables 3 and 4). The tear strength of the foams based on the Novomer polyols was somewhat higher compared to the reference foams prepared with the graft polyols (tables 3 to 5). These results also indicate that the strength (toughness) of the foam is increased by the incorporation of the Novomer polyol.

The free-rise foams based on the Novomer polyol exhibited significantly higher Compressive Force Deflection (CFD) at 25%, 50% and 65% deflection compared to the reference foam prepared with the base polyol as the sole polyol (tables 3 and 4; fig. 1-2), and slightly higher Compressive Force Deflection (CFD) at 25%, 50% and 65% deflection compared to the reference foam based on the graft polyol (tables 3-5; fig. 3). These results clearly show that the Novomer polyols improve the load bearing properties of the flexible foams. More importantly, the SAG factor was not affected by the incorporation of the Novomer polyol into the foam formulation (tables 3-5; FIGS. 4 and 5). Similar effects of the Novomer polyols on CFD performance were observed in the case of molded foams (table 6).

A slight decrease in tensile strength was observed in all foams tested for resistance to dry heat aging at 140 ℃ for 22 hours. However, no major difference in retention of properties was observed between the reference foam with and without graft polyol and the foam prepared with the Novomer polyol (tables 3-5).

Conclusion

The reactivity of the Novomer polyol was similar to that of the reference polyol Poly-G85-29 and the graft polyol Speciflex NC-701. However, in order to obtain an open cell structure, the amount of catalyst and diethanolamine (reactive catalyst/crosslinker) needs to be adjusted.

Free-rise foams prepared with 5% to 25% of Novomer polyols exhibit a uniform cell structure. The density and apparent cell structure of these foams are similar to the reference foams prepared with or without the graft polyol.

All foams prepared with 5% to 25% of Novomer polyols exhibit relatively high resilience and can be classified as High Resilience (HR) PU foams. All these foams exhibit a degree of compatibility with Chrysler materials conforming to the standards for "cellular, molded polyurethane High Resilience (HR) type seating applications": most performance reference foams specified by MS-DC-649 were similar in performance.

The tensile strength and tear strength properties of the foams prepared with the Novomer polyols were better compared to the reference foams. The retention of stress-strain properties by thermal aging is not affected by the incorporation of the Novomer polyol.

The results of the CFD measurements clearly show that the load bearing properties of free-rise foams and molded foams based on Novomer polyols are increased without affecting the SAG (comfort) factor.

Example 2: viscoelastic foam composition

Described below are formulations of viscoelastic polyurethane foams according to the principles of the present invention. These materials are prepared using the aliphatic polycarbonate polyol additives defined herein. In particular, the aliphatic polycarbonate polyols hereinafter are also referred to as "Novomer polyols" for use in the formulations hereinafter, which have the following properties:

wherein n averages about 5.6 in the composition.

Polyol 74-217 is a linear 810g/mol poly (propylene carbonate) polyol initiated with dipropylene glycol (a mixture of isomers) having a PDI of 1.13, greater than 99% of-OH end groups, and greater than 99% carbonate linkages (excluding ether linkages in dipropylene glycol). The polyol corresponds to the formula:

wherein n averages about 3.3 in the composition.

Polyol 74-277 is a linear 2400g/mol poly (propylene carbonate) polyol initiated with 600g/mol polypropylene glycol (mixture of isomers), having a PDI of 1.05, more than 99% of-OH end groups and more than 99% of carbonate linkages (excluding ether linkages in polypropylene glycol). The polyol corresponds to the formula:

wherein k averages about 10 and n averages about 9 in the composition.

The effect of PPC glycol on load bearing (CFD) and other properties of viscoelastic polyurethane foams was evaluated in this study. Foams were also prepared using a mixture of Novomer PPC polyols. Mondur MRS-2 with a high 2,4' -MDI content was used as isocyanate in the preparation of the foams. The performance of the viscoelastic foam prepared with the NOVOMER polyol was similar to that of the reference molding formulation prepared with the conventional polyol.

Raw materials

The list of raw materials used in this evaluation is shown in table 1B. All materials (including Novomer polyols) were used as received.

Preparation and testing of the foams

Free rise water foams were prepared with 0%, 10% and 20% Novomer 58-103C, Novomer 74-217 and Novomer 74-277 polyols instead of the petroleum-based commercial polyol. VE foams were also prepared using a mixture of three Novomer polyols at levels up to 30% and 45% instead of the petroleum-based commercial polyol (tables 2B-5B). Also using CaCO₃Reference VE foams and VE foams based on Novomer polyols were prepared as fillers (table 2B-5B).

In the present example, most of the VE foams were made using Mondur at an isocyanate index of 70^TMMRS-2, which is a 2,4' -MDI rich isocyanate (Table 2B-5B). Based on three of 30% and 45%Foams of mixtures of Novomer polyols were also prepared at an isocyanate index of 80 (table 5B).

Free rise foams were prepared using standard laboratory hand mixing procedures. Foaming profiles including cream time, gel time and rise time were measured for all foams. Immediately after the rise time, the foam was placed in an air circulating oven preheated to 70 ℃ for 60 minutes to complete the cure.

After a minimum of 7 days of aging, the selected foams were fully characterized according to ASTM D3574-08 as follows:

-foam density (test A),

rebound resilience by ball rebound (test H),

tensile strength at break (test E),

elongation at break (test E),

tear strength (test F),

CFD, compressive force deflection (test C),

hysteresis (procedure B-CFD hysteresis loss),

dry (constant compression ratio) compression set (test D),

The recovery time was measured on an Instron Tester using an internal protocol. The following measurement parameters were used:

sample size: 2"x 2" x 1"

Indenter foot area: 64mm²

Velocity: 500mm/min

Indentation: 80 percent of

Retention time: 60 seconds

The recovery time was measured according to the following protocol: the test sample is placed on the support plate. The indentor foot is brought into contact with the sample. The sample was rapidly pressed down at a speed of 500mm/min for 80% of its initial thickness and held for 60 seconds. After a 60 second dwell time, the ram was returned to 0% deflection at 500mm/min and a stopwatch was started immediately upon initiation of the upward movement of the ram. The stop watch was stopped when the print of the presser foot was not visible and the time was recorded. The process was repeated on 2 additional samples and the average time was calculated.

The glass transition temperature was measured by the following method:

DSC (DSC Q10 from TA instruments) under nitrogen atmosphere at a heating rate of 20 ℃ per minute, a temperature rate between-80 ℃ and +200 ℃.

DMA (DMA 2980 from TA Instrument) under nitrogen atmosphere at a heating rate of 3 ℃ per minute, at a temperature rate between-80 ℃ and +130 ℃.

Results

Molded VE foam formulations are based on three different commercial polyether triols: Poly-G30-240, Poly-G76-120, and Poly-G85-34 having equivalent weights of 236, 468, and 1603, respectively, (Table 1B-5B). Ethoxylated glycerol Lumulse POE 26 having an equivalent weight of 416 was used as the open cell polyol (tables 1B-5B). Diethylene glycol (DEG) was used as the chain extender. Dabco 33LV and Niax A-1 were used as catalysts. The Dabco 33LV catalyst promotes the gelling reaction (reaction of isocyanate with polyol) and the blowing reaction (reaction of isocyanate with water). Niax A-1 is a blowing catalyst.

The reactivity of the PU system was not significantly affected after easy replacement of any commercial polyol (tables 2B-4B) including the open cell polyol (table 2B) with the Novomer polyols 10% and 20%. The reactivity of the PU system was not significantly affected after a simple replacement of the commercial polyol with a mixture of three Novomer polyols of 30% and 45% (table 5B). No catalytic conditioning was required to obtain open-cell foams with Novomer polyols (tables 2B-5B).

VE foams based on Novomer polyols exhibited a similar white color as the reference foam. The apparent cell structure of the foam with the Novomer polyol was uniform and similar to the reference foam.

Physical properties of the foam

Compressive Force Deflection (CFD) at 25%, 50% and 65% deflection was increased by the introduction of Novomer polyols (table 2B-5B and fig. 6, 10, 12 and 15). The CFD values normalized to density clearly show that the foams with Novomer polyols have a higher CFD (better load bearing performance) compared to the reference foams (tables 2B-5B and fig. 7, 10, 13 and 16). The CFD curves are shown in fig. 6-19.

Hysteresis loss independent of foam density also increased with the introduction of the Novomer polyol (tables 2B-5B and fig. 8, 11, 14 and 17), indicating that the Novomer polyol-based foams absorbed more energy than the reference foams. In general, hysteresis loss is a more reliable measure of energy absorption than rebound, as measured by the sphere rebound method. All foams prepared in this study exhibited very low resilience of 1% or less (tables 2B-5B).

The tensile strength (fig. 6-20) and tear strength (fig. 20-23) of VE foam were increased by introducing Novomer polyol 58-103-C as a replacement for a similar equivalent weight Poly-G76-120 polyol, both with and without calcium carbonate filler (compare formulations 1 and 2 with formulations 4 and 5 in table 2B). The measured tensile strength and tear strength are consistent with the CFD performance of these foams.

The increase in tensile and tear strength properties was particularly high in foams prepared with a proportional mixture of three Novomer polyols replacing the three commercial base polyols by 30% and 45% (compare formulations 1 and 2 with formulations 3 and 4 in table 5B). As expected, the tensile strength and tear strength in foams based on mixtures of Novomer polyols increased more with increasing isocyanate index from 70 to 80 (compare formulations 3 and 4 with formulations 5 and 6 in table 5B).

In most of the foams tested, the elongation at break is much higher than the elongation at maximum load (% strain). To maintain consistency, the elongation at maximum load was recorded as the elongation. Without exception, all foams exhibited elongations greater than 100% (tables 2B-5B).

The recovery time of foams prepared using only Novomer polyol after being pressed 80% of their original thickness was not significantly affected (tables 2B-4B). However, foams prepared with a proportional mixture of three Novomer polyols replacing the commercial base polyol at 30% and 45% levels showed a substantial increase in recovery time compared to the reference foam (table 5). This is consistent with the hysteresis values of these foams (table 5B).

Dry compression set and wet compression set were measured on a selected number of foams. In all foams containing up to 30% of Novomer polyol based on total polyol, both dry compression set and wet compression set were relatively lower and similar to the reference foam (tables 2B-5B).

DMA and DSC results

DMA and DSC curves of the selected foams are shown in FIGS. 18-23. The transitions (transitions) in the DMA and DSC curves are summarized in the table of the next page.

The reference foam (REF-3, formulation #1 in tables 2-5) exhibited a Tg of-46 deg.C, which corresponds to the first maximum in loss modulus measured by DMA (FIG. 18 a; see Table 1C). Tan δ is broad in peak and shows a low height of maximum at 35 ℃. In general, the area under the Tan δ peak relates to the energy absorption performance; a larger area should relate to higher energy absorption properties. Foams with low Tg and high area under the Tan delta curve are considered desirable for memory foams.

Foams based on 20% Novomer 74-217 polyol (formulation #4 in Table 3B) exhibited a similar Tg as measured by DMA to the reference foam (see Table 1C). The Tg measured by DSC was also similar to the reference foam (table 1C). The Tan delta maximum measured on the foam incorporating 20% of the Novomer 74-217 polyol is at a slightly higher temperature than the reference foam. However, the Tan δ peak is significantly higher and the area under the peak is significantly larger compared to the reference foam, indicating a higher energy absorption capacity. These data correlate very well with the hysteresis measurements. The hysteresis loss of the Novomer foam was 62%, while the hysteresis loss of the reference foam was 36% (formulations #1 and #4 in table 3B).

The foam based on 18% Novomer 58-103-C polyol (formulation #3 in Table 2B-2) exhibited a significantly higher Tg than the reference foam as measured by DMA (FIGS. 18a and 19; see also above). The shift in Tg measured by DMA can be attributed to the fact that the polyether polyol with a high equivalent weight of 1603 is replaced by a relatively low equivalent weight (471) of Novomer polyol (formulations #1 and #3 in table 2B-2). However, in the case of the Novomer foam, the Tg measured by DSC was detected at a slightly lower temperature than the reference foam (FIGS. 21 and 22; see also the above table).

The Tan delta maximum for this Novomer foam was at 30 ℃ close to the reference foam. The area under the Tan delta peak is higher than the reference foam, indicating a higher energy absorption capacity (fig. 18 and 19). These results are also consistent with the hysteresis measured on the two foams (formulations #1 and #3 in table 2B).

A20% Novomer 74-277 polyol based foam (formulation #4 in Table 4B) exhibited a relatively low Tg as measured by DMA (-33.49 ℃) and a broad and high Tan delta peak at 40 ℃. Both Tg and Tan δ maxima are slightly shifted to higher temperatures compared to the reference foam (fig. 18 and 19, table 1C). The energy absorption performance measured by DMA correlates very well with the hysteresis result. This foam exhibited significantly higher hysteresis than the reference foam (formulations #1 and #4 in table 4).

The foam prepared by using a 30% mixture of 3 different Novomer polyols (formulation #5 in table 5B) exhibited a low Tg as determined by DMA close to that of the reference foam. The Tan delta peak is broad and high with a maximum at 50 ℃ indicating a significantly higher energy absorption capacity than the reference foam (fig. 18 and 20 a; table 1C). The foam hysteresis value was high (73%), while that of the reference foam was 36% (formulations #1 and #5 in table 5B).

The foam prepared by using a 45% mixture of 3 different Novomer polyols (formulation #6 in table 5B) exhibited a relatively higher Tg than the reference foam and other foams prepared with the Novomer polyols (fig. 18-20, table 1C). Tan δ maximum is at 56 ℃, which is significantly higher than other foams. The Tan delta peak height, indicating a large energy absorption capacity, is consistent with a hysteresis loss of 83% (formulation #6 in table 5B).

Based on DMA measurements, it can be concluded that the Novomer polyols impart improved energy absorption properties to the foam, which are desirable properties for viscoelastic foams.

Conclusion

The reactivity of the Novomer polyols in the VE formulations was similar to that of the reference polyol used in this study. The reactivity of the PU system was not significantly affected after 10% and 20% facile replacement of any commercial polyol including open cell polyols used in the present invention. The reactivity of the PU system was not significantly affected after easy replacement of the commercial polyol with a mixture of three Novomer polyols, 30% and 45%. No catalytic tuning is required to obtain open-cell foams with Novomer polyols.

By introducing the Novomer polyol, the Compressive Force Deflection (CFD) of VE foam at 25%, 50% and 65% deflection was increased. The CFD values normalized to density clearly show that the foam with the Novomer polyol has a higher CFD (better load bearing properties) than the reference foam.

Hysteresis loss independent of foam density also increases with the introduction of the Novomer polyol, indicating that the Novomer polyol based foam absorbs more energy than the reference VE foam. All foams prepared in this study exhibited very low resilience of about 1% or less.

The tensile strength and tear strength of VE foam were increased by incorporating Novomer 58-103-C polyol as a replacement for a similar equivalent weight Poly-G76-120 polyol, both with and without calcium carbonate as a filler. The increase in tensile strength and tear strength properties is particularly high in foams prepared with a proportional mixture of three Novomer polyols replacing the three commercial polyols by 30% and 45%.

The increase in isocyanate index from 70 to 80 increases the tensile strength and tear strength in VE foams based on mixtures of Novomer polyols.

Elongation at break is much higher than elongation at maximum load (% strain). To maintain consistency, the elongation at maximum load was recorded as the elongation. Without exception, all VE foams exhibited elongations greater than 100%.

VE foams prepared with a proportional mixture of three Novomer polyols replacing the commercial base polyol at 30% and 45% levels showed a substantial increase in recovery time compared to the reference foam. This is consistent with the hysteresis values of these foams.

Dry compression set and wet compression set were measured on a selected number of VE foams. In all foams containing up to 30% of Novomer polyol based on total polyol, both dry compression set and wet compression set were relatively lower and similar to the reference foam.

Based on DMA measurements, it can be concluded that the Novomer polyols impart improved energy absorption properties to VE foam formulations, which is consistent with the hysteresis loss results. Higher energy absorption is a desirable feature for viscoelastic foams.

Example 3: TDI base chair foam

Described below are the formulations and properties of high strength TDI-based polyurethane foams made according to the principles of the present invention. These materials were prepared to evaluate their suitability for use in seat foam applications. TDI foams were prepared using the aliphatic polycarbonate polyol additives defined herein. In particular, the aliphatic polycarbonate polyols hereinafter are also referred to as "Novomer polyols" for use in the formulations hereinafter, which have the following properties:

polyol batch number	58-103-C	74-276	80-148	80-163


					Acid value, mg KOH/g	0.28	0.51	2.68	209
Hydroxyl number, mg KOH/g	119	61.1	111.7	64.9
					Mn(GPC)	1,270	2,213	1337	2205
Mw(GPC)	1,370	2,443	1453	2345
					Polydispersity, Mw/Mn	1.07	1.06	1.09	1.06
Glass transition temperature (DSC), Tg	-5℃	-5.5℃	6.0℃	-9.9℃

The structures of the polyols 58-103-C and 74-276 are shown in the previous examples above.

Polyol 80-163 is a linear 2250g/mol poly (propylene carbonate) polyol initiated with 600g/mol polypropylene glycol (mixture of isomers) having a PDI of 1.05, more than 99% of-OH end groups and more than 99% of carbonate linkages (excluding ether linkages in polypropylene glycol). The polyol corresponds to the formula:

wherein k averages about 9 and n averages about 7 in the composition.

Polyol 80-148 is a propylene glycol initiated linear poly (propylene carbonate) polyol and has 1340g/mol Mn, a PDI of 1.09, greater than 99% of-OH end groups, and greater than 99% of carbonate linkages. The polyol corresponds to the formula:

wherein n averages about 13 in the composition.

Raw materials

The list of starting materials used in this evaluation is shown in Table example 3-1a and example 3-1 b.

All materials (including Novomer polyols) were used as received from the supplier.

Solubility/compatibility of Novomer polyols with commercial polyether polyols

In the foaming experiments, formulations targeted at high resilience flexible polyurethane foams were used as reference. The formulation is based on a mixture of Poly-G85-29 ethylene oxide capped polyether triol (polyol) and catalytically active Voranol-Voractiv6340, a highly functional EO capped polyether polyol. Speciflex NC-701 was used as the grafted polyether polyol. Lumulse POE 26 (ethoxylated glycerol) was used as reactive cell opener. Diethanolamine is used as cocatalyst and crosslinker.

Preparation and testing of foams

Free-rise aqueous foams were prepared with 0%, 10% and 20% Speciflex NC-701 graft polyol at an isocyanate index of 90 (Table examples 3-2 to examples 3-5). Reference molded foams were prepared with 0%, 10%, 15%, 20% and 25% speciallex NC-701 graft polyol (table examples 3-6 to examples 3-10).

Free rise foams and molded foams were prepared with 10% and 20% Novomer PPC-2kd-PEOL polyol (Table examples 3-3 and examples 3-8). Molded foams were prepared at 20% with 80-163 polyol, targeting foam densities of 2.5 and 3.5pcf (Table 8A).

Due to limited compatibility with commercial polyols, free rise foams were prepared with 10% polyol 80-148 and molded foams were prepared with 10% and 15% polyol 80-148 (Table examples 3-5 and examples 3-10). Molded foams containing 15% of 80-148 polyol were prepared, targeting foam densities of 2.5 and 3.5pcf (Table examples 3-10).

Free-rise foams were prepared with 10%, 12.5% and 26.9% of polyol 74-276 (Table example 3-2) and with 10%, 12.5% and 16.7% of 58-103C polyol (Table example 3-4). Molded foams were prepared with 10% and 20% of each of the two polyols (Table examples 3-7 and examples 3-9) polyol 74-276 (Table examples 3-7).

In some cases, free rise and molded foams were prepared by grafting a mixture of polyether polyol and Novomer polyol with Speciflex NC-701 (Table examples 3-2 through 3-4, examples 3-7, examples 3-8B, and examples 3-9).

Free rise foams were prepared using standard laboratory hand mixing procedures. Foaming profiles including cream time, gel time and rise time were measured for all foams. Immediately after the rise time, the foam was placed in an air circulating oven preheated to 80 ℃ for 30 minutes to complete the cure.

Molded foams were prepared using 12x12x2 inch size aluminum molds preheated to 70 ℃. The demold time was 4.5 minutes.

All foams were aged at room temperature for a minimum of one week prior to testing. The molded foams were evaluated comprehensively. The following properties were measured according to ASTM D3574-08:

foam Density (test A)

Rebound resilience by ball (test H)

Tensile Strength at Break (test E)

Elongation at break (test E)

Tear Strength (test F)

CFD, compression force deflection (test C)

Hysteresis (procedure B-CFD hysteresis loss)

Dry (constant compression ratio) compression set (test D)

Flammability was measured as horizontal burn rate as per the modified internal method from ASTM D5132-04.

Results IV

Compatibility of polyols

After 24 hours, the Novomer PPC-2kd-PEOL polyol was compatible with an 50/50 blend of Poly-G85-29 polyol and Voranol6340 polyol at levels up to 25%.

After blending, the Novomer polyols 80-148 are immediately compatible with mixtures of these two commercial polyols at levels up to 15%. After 24 hours, the blend separated into a two-phase system.

Reactivity of polyol

The introduction of four different Novomer polyols as a simple replacement for Poly-G85-29 and Voranol Voractiv6340 to the reference foam formulation did not significantly affect the reaction profiles (foaming profiles) measured as cream time, gel time and rise time (table examples 3-2 to examples 3-5). No catalytic conditioning is required.

Apparent cell structure and density

The free-rise foams based on the Novomer polyol show a white colour similar to the reference foams prepared with or without the graft polyol Speciflex NC-701. The apparent cell structure of the foam with the Novomer polyol was uniform and similar to the reference foam.

The simple replacement of Poly-G85-29 polyol and Voranol Voractiv6340 polyol with Novomer polyol did not significantly change the density of the free rise foam (table examples 3-2 to examples 3-5).

The apparent cell structure of the molded foams prepared with the Novomer polyol was uniform and similar to the reference foam prepared with a mixture of Poly-G85-29 polyol and Voranol Voractiv6340 polyol and the reference foam prepared with graft polyol Speciflex NC-701.

Physical properties of the foam

In this study, free-rise foams were mostly prepared to evaluate epoxide-CO₂The reactivity of the base polyols and their effect on the foaming profile. The free-rise TDI foam showed significantly higher resilience than the MDI based HR foam prepared with the same level of Novomer polyol (example 1). MDI-based foams prepared with 10% and 25% Novomer polyol 74-276 exhibited 49% and 36% resiliency, respectively. TDI foams based on 10% and 26.9% of the same polyol showed 53% and 42% resilience. TDI foams prepared with 10% and 16.7% Novomer polyols 58-103 exhibited 55% and 45% resilience, respectively, and MDI foams prepared with 10% and 15% of the same polyol exhibited 43% and 39% resilience.

The reference free rise foam prepared with the graft polyol (Speciflex NC-701) also exhibited lower resilience than the reference foam prepared with the base polyether polyol.

The same effect on resilience was observed in molded foams for the graft polyols as for the Novomer polyols (Table examples 3-6 to examples 3-10). In all cases, with the incorporation of graft polyol and Novomer polyol, the resilience of the molded foam decreased somewhat and the hysteresis increased somewhat (Table examples 3-6 to examples 3-10). However, regardless of the type of Novomer polyol (table examples 3-6 to examples 3-10), the resilience is significantly higher and the hysteresis is significantly lower compared to the same level of MDI-based foam.

All molded TDI foams based on Novomer polyols exhibited hysteresis of less than 35% (tables 7-10, FIGS. 24 and 25) (with one exception) and were used with a 2pcf (32 kg/m)³) Minimum density requirement of type IV foam maximum specified by Chrysler material standard (fig. 33); the foam with 20% polyol 74-276 exhibited a hysteresis of 35.3% (see Table examples 3-7). All molded foams had a density of about 2.4pcf (38 kg/m)³)。

Based on hysteresis results, all foams prepared with Novomer polyols can be classified as High Resilience (HR) PU foams.

In general, tensile strength increases with the introduction of the Novomer polyol. Elongation did not change significantly with the introduction of the Novomer polyol (table examples 3-7 to examples 3-10). These results indicate that the strength (toughness) of the foam is increased by the incorporation of the Novomer polyol.

The tear strength measured on foams made with the Novomer polyol was significantly higher than the reference foams made with the base polyether polyols Poly-G85-29 and Voranol Voractiv6340 (Table examples 3-7 to examples 3-9). The tear strength of foams based on polyols 75-276, 80-163, and 58-103-C polyols was similar to the reference foams prepared with the graft polyols (Table examples 3-7 through examples 3-9). These results also indicate that the strength (toughness) of the foam is increased by the incorporation of the Novomer polyol.

All molded foams based on the Novomer polyol exhibited significantly higher Compressive Force Deflection (CFD) at 25%, 50% and 65% deflection compared to the reference foam prepared with the base polyol as the sole polyol, and similar or slightly higher CFD at 25%, 50% and 65% deflection compared to the reference foam based on the graft polyol (table examples 3-7 to examples 3-10, fig. 26-31). These results clearly show that the Novomer polyols improve the load bearing properties of the flexible foams. More importantly, the SAG factor was not significantly affected by the introduction of the Novomer polyol into the foam formulation (table examples 3-7 to examples 3-10, fig. 32).

Molded foams based on Novomer polyols had somewhat higher dry and wet compression set than the reference foams (Table examples 3-7 to examples 3-10). Molded foams prepared with the graft polyols also exhibited slightly higher compression set values than the reference foams prepared with the base polyether polyols (Table examples 3-6). However, all molded foams prepared with the Novomer polyol met the 25% maximum wet compression set requirement as defined by the Chrysler material standard for type IV foams (fig. 33).

Virtually all molded foams based on Novomer polyols meet the hysteresis loss, tear resistance and wet compression set requirements of the Chrysler material standard for type IV foams.

The flammability of the molded foam is not affected by the addition of the Novomer polyol. The burn rate of all molded foams based on the Novomer polyol was about 100mm/min, which is in the range of the reference foams prepared with and without graft polyol (Table examples 3-6, examples 3-7, examples 3-8A, examples 3-9 and examples 3-10). If desired, the flammability of the foam can be readily adjusted by adding small amounts of flame retardants.

All foams measured after dry aging at 140 ℃ for 22 hours retained the tensile strength properties well (Table examples 3-6, examples 3-7, examples 3-8A, examples 3-9 and examples 3-10). In some cases, no improvement in stress-strain performance with dry aging was observed in MDI foams (example 1). This can be attributed to the annealing effect of the TDI-based polymer network at elevated temperatures.

Foam properties prepared with NOVOMER polyol target density of 3.5pcf

The density of the above molded foam was about 2.4pcf (38 kg/m)³) This is in the range of type IV HR foams for seating applications according to Chrysler material standard MS-DC-649 (fig. 33). Two classes of targets were also prepared, 3.5pcf (56 kg/m)³) A molded foam of density of (a). Both foams, based on 20% polyol 74-176 (named 6B in Table examples 3-8A) and 15% polyol 80-148 (named 7B in Table examples 3-10), exhibited higher CFD performance and higher tensile and tear strength than the foams made at low density. More importantly, both foams appeared to be superiorLow hysteresis loss and lower wet and dry compression set (table examples 3-8A and examples 3-10).

Conclusion V

The simple substitution of Poly-G85-29 and Voranol Voractiv6340 with four different Novomer polyols introduced into the reference foam formulation did not significantly affect the reaction profile (foaming profile) measured as including cream time, gel time and rise time.

The simple replacement of Poly-G85-29 and Voranol Voractv 6340 polyols with Novomer polyols did not significantly alter the density and apparent cell structure of the free rise foams.

The apparent cell structure of the molded foams prepared with the Novomer polyol was uniform and similar to the reference foams prepared with and without the graft polyol.

All foams prepared with the Novomer polyols exhibit relatively high resilience and relatively low hysteresis loss and can therefore be classified as High Resilience (HR) PU foams.

The tensile strength and tear strength of the foams prepared with the Novomer polyols are somewhat superior to the reference foams.

The results of CFD measurements clearly show an increase in the load bearing properties of molded foams based on Novomer polyols without significant impact on the SAG (comfort) factor.

The foams based on Novomer polyols showed some increase in wet compression set and dry compression set compared to the reference foams. However, all molded foams prepared with the Novomer polyols met the 25% maximum wet compression set requirement as defined by the Chrysler material standard for type IV foams.

Virtually all molded foams based on Novomer polyols meet the Chrysler material standard for "cellular, molded polyurethane High Resilience (HR) type seating applications": hysteresis loss, tear resistance and wet compression set requirements as specified by MS-DC-649 (FIG. 33).

The flammability of the molded foam is not affected by the addition of the Novomer polyol.

Other embodiments

The foregoing is a description of certain non-limiting embodiments of the invention. Accordingly, it is to be understood that the embodiments of the invention herein described are merely illustrative of the application of the principles of the invention. References herein to details of the illustrated embodiments are not intended to limit the scope of the claims, which in themselves recite those features regarded as essential to the invention.

Appendix A aliphatic polycarbonate polyols

This section describes some aliphatic polycarbonate polyols having utility in the methods and compositions of the present invention. Aliphatic polycarbonate polyols are referred to herein as those resulting from the copolymerization of one or more epoxides and carbon dioxide. Examples of suitable polyols and methods of making the same are disclosed in PCT publication WO2010/028362, which is incorporated herein by reference in its entirety.

It is advantageous for many of the embodiments described herein that the aliphatic polycarbonate polyols used have a high percentage of reactive end groups. Such reactive end groups are typically hydroxyl groups, but if the polyol is treated to modify the chemistry of the end groups, other reactive functional groups may be present. Such a modifying material may be terminated with an amino group, a thiol group, an alkylene group, a carboxyl group, a silane, a phosphate derivative, an isocyanate group, or the like. For the purposes of the present invention, the term "aliphatic polycarbonate polyol" generally refers to an-OH terminated material, but does not exclude the incorporation of end-group modified compositions, unless otherwise indicated.

In certain embodiments, at least 90% of the terminal groups of the polycarbonate polyols used are reactive groups. In certain embodiments, at least 95%, at least 96%, at least 97%, or at least 98% of the end groups of the polycarbonate polyol used are reactive groups. In certain embodiments, greater than 99%, greater than 99.5%, greater than 99.7%, or greater than 99.8% of the end groups of the polycarbonate polyol used are reactive groups. In certain embodiments, greater than 99.9% of the end groups of the polycarbonate polyol used are reactive groups.

In certain embodiments, at least 90% of the terminal groups of the polycarbonate polyols used are-OH groups. In certain embodiments, at least 95%, at least 96%, at least 97%, or at least 98% of the end groups of the polycarbonate polyol used are-OH groups. In certain embodiments, greater than 99%, greater than 99.5%, greater than 99.7%, or greater than 99.8% of the end groups of the polycarbonate polyol used are-OH groups. In certain embodiments, greater than 99.9% of the terminal groups of the polycarbonate polyol used are-OH groups.

Another way to express the-OH end group content of a polyol composition is to report its OH number, as measured using methods well known in the art. In certain embodiments, the aliphatic polycarbonate polyols utilized in the present invention have an OH number greater than about 40. In certain embodiments, the aliphatic polycarbonate polyol has an OH number greater than about 50, greater than about 75, greater than about 100, or greater than about 120.

In certain embodiments, it is advantageous if the aliphatic polycarbonate polyol composition has a substantial proportion of primary hydroxyl end groups, as is normal for compositions comprising poly (ethylene carbonate), but for polyols resulting from the copolymerization of substituted epoxides, it is common for some or most of the chain ends to consist of secondary hydroxyl groups.

In certain embodiments, polycarbonate polyols having utility in the present invention contain a primary repeat unit having the structure:

wherein R is¹As defined above, and in the classes, subclasses, and examples herein.

In certain embodiments, the aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and ethylene oxide. In certain embodiments, the aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and propylene oxide. In certain embodiments, the aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and epoxycyclohexane. In certain embodiments, the aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and cyclopentane epoxide. In certain embodiments, the aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and 3-vinyl epoxycyclohexane.

In certain embodiments, the aliphatic polycarbonate chains comprise a terpolymer of carbon dioxide and ethylene oxide together with one or more additional epoxides selected from the group consisting of propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, cyclohexane oxide, 3-vinyl cyclohexene oxide, epichlorohydrin, glycidyl esters, glycidyl ethers, styrene oxide, and higher α -alkenes.

In certain embodiments, the aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and propylene oxide together with one or more additional epoxides selected from the group consisting of ethylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, cyclohexene oxide, 3-vinyl cyclohexene oxide, epichlorohydrin, glycidyl esters, glycidyl ethers, styrene oxide, and higher α -alkenes, hi certain embodiments, such terpolymers contain a majority of repeat units derived from propylene oxide and a lesser amount of repeat units derived from one or more additional epoxides.

In certain embodiments, aliphatic polycarbonate compositions having utility in the present invention have a number average molecular weight (M) in the range of from about 500g/mol to about 25,000g/mol_n)。

In certain embodiments, the aliphatic polycarbonate chains have a M of less than about 25,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M of less than about 10,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M of less than about 5,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M between about 500g/mol to about 15,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M between about 500g/mol to about 10,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M between about 500g/mol to about 5,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M between about 500g/mol to about 3,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M between about 500g/mol to about 2,500g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M between about 500g/mol to about 2,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M between about 500g/mol and about 1,500g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M between about 500g/mol to about 1,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M between about 1,000g/mol to about 5,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M between about 1,000g/mol to about 3,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have from about 5,000g/mol to about 10,000g/molM between mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M of about 5,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M of about 4,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M of about 3,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M of about 2,500g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M of about 2,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M of about 1,500g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M of about 1,000g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M of about 850g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M of about 750g/mol_n. In certain embodiments, the aliphatic polycarbonate chains have a M of about 500g/mol_n。

In certain embodiments, the aliphatic polycarbonate polyol used is characterized in that it has a narrow molecular weight distribution. This may be indicated by the polydispersity index (PDI) of the aliphatic polycarbonate polymer. In certain embodiments, the aliphatic polycarbonate composition has a PDI of less than 2. In certain embodiments, the aliphatic polycarbonate composition has a PDI of less than 1.8. In certain embodiments, the aliphatic polycarbonate composition has a PDI of less than 1.5. In certain embodiments, the aliphatic polycarbonate composition has a PDI of less than 1.4. In certain embodiments, the aliphatic polycarbonate composition has a PDI of between about 1.0 and 1.2. In certain embodiments, the aliphatic polycarbonate composition has a PDI of between about 1.0 and 1.1.

In certain embodiments, the aliphatic polycarbonate compositions of the present invention comprise substantially alternating polymers having a high percentage of carbonate linkages and a low content of ether linkages. In certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized by an average percentage of carbonate linkages in the composition of 85% or more. In certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized byThus, the average percentage of carbonate linkages in the composition is 90% or greater. In certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized by an average percentage of carbonate linkages in the composition of 91% or more. In certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized by an average percentage of carbonate linkages in the composition of 92% or more. In certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized by an average percentage of carbonate linkages in the composition of 93% or more. In certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized by an average percentage of carbonate linkages in the composition of 94% or more. In certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized by an average percentage of carbonate linkages in the composition of 95% or greater. In certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized by an average percentage of carbonate linkages in the composition of 96% or more. In certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized by an average percentage of carbonate linkages in the composition of 97% or more. In certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized by an average percentage of carbonate linkages in the composition of 98% or more. In certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized by an average percentage of carbonate linkages in the composition of 99% or more. In certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized by an average percentage of carbonate linkages in the composition of 99.5% or greater. In certain embodiments, the above percentages exclude ether linkages present in the polymerization initiator or chain transfer agent and refer to epoxide CO only₂Bonds formed during the copolymerization.

In certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized in that they are prepared from an epoxide CO₂The resulting polymer is substantially free of ether linkages within the polymer chain or within any polymerization initiator, chain transfer agent or end groups that may be present in the polymer. In thatIn certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized in that they contain, on average, less than one ether linkage per polymer chain in the composition. In certain embodiments, the aliphatic polycarbonate compositions of the present invention are characterized in that they are substantially free of ether linkages.

In certain embodiments, where the aliphatic polycarbonate is derived from a mono-substituted epoxide (e.g., such as propylene oxide, 1, 2-butylene oxide, epichlorohydrin, epoxidized α olefin, or a glycidyl derivative), the aliphatic polycarbonate is characterized by its stereoregularity.

In certain embodiments, the aliphatic polycarbonate polyols suitable for use in the present invention have a viscosity controlled within a particular range. The preferred range may depend on the particular application and may be controlled to be within the normal range for the particular application.

In certain embodiments, wherein the aliphatic polycarbonate polyol is used in the formulation of a rigid foam or thermoplastic composition, the polyol has a viscosity of less than about 30,000cps, as measured at a temperature of at least 20 ℃ but less than 70 ℃. In certain embodiments, such polyols have a viscosity of less than about 20,000cps, less than about 15,000cps, less than about 12,000cps, or less than about 10,000 cps. In certain embodiments, such polyols have a viscosity of between about 600 and about 30,000 cps. In certain embodiments, such polyols have a viscosity of between about 2,000 to about 20,000 cps. In certain embodiments, such polyols have a viscosity of between about 5,000 to about 15,000 cps.

In other embodiments, where the aliphatic polycarbonate polyol is used in the formulation of a flexible foam, the polyol has a viscosity of less than about 10,000cps, as measured at a temperature of at least 20 ℃ but less than 70 ℃. In certain embodiments, such polyols have a viscosity of less than about 8,000cps, less than about 6,000cps, less than about 3,000cps, or less than about 2,000 cps. In certain embodiments, such polyols have a viscosity of between about 1,000 to about 10,000 cps. In certain embodiments, such polyols have a viscosity of between about 1,000 to about 6,000 cps.

In certain embodiments, the polyol viscosity values described above represent viscosities as measured at 25 ℃. In certain embodiments, the above viscosity values represent viscosities as measured at 30 ℃, 40 ℃,50 ℃, 60 ℃ or 70 ℃.

In certain embodiments, the aliphatic polycarbonate polyols useful in the present invention have a Tg within a particular range. The desired Tg will vary with the application and can be controlled within a known normal range for a particular application. In certain embodiments, wherein a polyol is used in the formulation of the flexible foam composition, the polyol has a Tg of less than about 20 ℃. In certain embodiments, such polyols have a Tg of less than about 15 ℃, less than about 10 ℃, less than about 5 ℃, less than about 0 ℃, less than about-10 ℃, less than about-20 ℃, or less than about 40 ℃. In certain embodiments, such polyols have a Tg of between about-30 ℃ to about-20 ℃. In certain embodiments, such polyols have a Tg of between about-30 ℃ to about-20 ℃.

In certain embodiments, wherein the aliphatic polycarbonate polyol is used in the formulation of a rigid foam composition, the polyol has a Tg of greater than about-30 ℃. In certain embodiments, such polyols have a Tg of greater than about-20 ℃, greater than about-10 ℃, greater than about 0 ℃, greater than about 10 ℃, greater than about 15 ℃, or greater than about 25 ℃. In certain embodiments, such polyols have a Tg of between about-10 ℃ to about 30 ℃. In certain embodiments, such polyols have a Tg of between about 0 ℃ to about 20 ℃.

In certain embodiments, the compositions of the present invention comprise an aliphatic polycarbonate polyol having the following structure P1:

wherein the content of the first and second substances,

R¹、R²、R³and R⁴Independently at each occurrence in the polymer chain, selected from-H, fluorine, optionally substituted C_1-30Aliphatic radical and optionally substituted C_1-20Heteroaliphatic and optionally substituted C_6-10Aryl, wherein R¹、R²、R³And R⁴Any two or more of (a) may optionally form, together with intervening atoms, one or more optionally substituted rings optionally containing one or more heteroatoms;

y, at each occurrence, is independently — H or a site to which a moiety such as those described above containing another reactive end group is attached;

n, at each occurrence, is independently an integer from about 2 to about 100;

is a multivalent moiety; and is

x and y are each independently integers from 0 to 6, wherein the sum of x and y is between 2 and 6.

In certain embodiments, multivalent moieties are embedded within the aliphatic polycarbonate chainDerived from compounds having epoxide/CO generating capability₂Of two or more sites of copolymerizationA multifunctional chain transfer agent. In certain embodiments, such copolymerization is carried out in the presence of a multifunctional chain transfer agent, as exemplified in PCT publication WO/2010/028362.

In certain embodiments, the multifunctional chain transfer agent has the formula:

wherein each onex and y are as defined above and described in classes and subclasses herein.

In certain embodiments, the aliphatic polycarbonate chains in the polymer compositions of the present invention result from the copolymerization of one or more epoxides with carbon dioxide in the presence of such multifunctional chain transfer agents as shown in scheme 2.

Scheme 2

In certain embodiments, the aliphatic polycarbonate chains in the polymer composition of the present invention comprise chains having the following structure P2:

wherein each R¹、R²、R³、R⁴、Y、And n is as defined above and described in classes and subclasses herein.

In certain embodiments, wherein aliphaticThe polycarbonate chains have the structure P2,derived from a diol. In this caseDenotes the carbon-containing main chain of a diol adjacent toThe two oxygen atoms of (a) are derived from the-OH group of the diol. For example, if the multifunctional chain transfer agent is ethylene glycol, thenWill be-CH₂CH₂And P2 will have the following structure:

it will be apparent to those skilled in the art that this is true for the other polyfunctional chain transfer agents described herein-the structure of the chain transfer agent used and the resulting polyolThere is a relationship between the structures of (a).

In certain embodiments, whereinDerived from a diol comprising C_2-40A diol. In certain embodiments, the glycol is selected from: 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 2-dimethylpropane-1, 3-diol, 2-butyl-2-ethylpropane-1, 3-diol, 2-methyl-2, 4-pentanediol, 2-ethyl-1, 3-hexanediol, 2-methyl-1, 3-propanediol, 1, 5-hexanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, 1, 3-propanediol, 1, 2-butanediol, 2-dimethylpropane-1, 3-diol, 2-butanediol,2,2,4, 4-tetramethylcyclobutane-1, 3-diol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanediol, isosorbide, monoglycerides, monoethers of glycerol, monoesters of trimethylolpropane, monoethers of trimethylolpropane, diesters of pentaerythritol, diethers of pentaerythritol, and alkoxylated derivatives of any of these.

In certain embodiments, whereinDerived from a diol selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly (ethylene glycols) such as those having a number average molecular weight of 220 to about 2000g/mol, dipropylene glycol, tripropylene glycol, and higher poly (propylene glycols) such as those having a number average molecular weight of 234 to about 2000 g/mol.

In certain embodiments, whereinDerived from a diol comprising an alkoxylated derivative of a compound selected from a diacid, a diol or a hydroxy acid. In certain embodiments, the alkoxylated derivative comprises an ethoxylated or propoxylated compound.

In certain embodiments, whereinDerived from a diol comprising a polymeric diol. In certain embodiments, the polymeric glycol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polycarbonate polyols derived from glycols and phosgene (or its reactive equivalent); polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters, polyoxymethylene polymers, and alkoxylated analogs of any of these. In certain embodiments, the polymeric glycol has an average molecular weight of less than about 2000 g/mol.

At a certain pointIn some embodiments of the present invention, the substrate is,derived from polyols having more than two hydroxyl groups. In certain embodiments, the aliphatic polycarbonate chains in the polymer compositions of the present invention comprise aliphatic polycarbonate chains, wherein a portion thereofDerived from a triol. In certain embodiments, such aliphatic polycarbonate chains have the structure P3:

In certain embodiments, whereinDerived from a triol selected from: glycerol, 1,2, 4-butanetriol, 2- (hydroxymethyl) -1, 3-propanediol, hexanetriol, trimethylolpropane, trimethylolethane, trimethylolhexane, 1, 4-cyclohexane tricarbol alcohol, pentaerythritol monoesters, pentaerythritol monoethers, and alkoxylated analogs of any of these. In certain embodiments, the alkoxylated derivative comprises an ethoxylated or propoxylated compound.

In some embodiments of the present invention, the substrate is,alkoxylated derivatives derived from trifunctional carboxylic acids or trifunctional hydroxy acids. In certain embodiments, the alkoxylated derivative comprises an ethoxylated or propoxylated compound。

In certain embodiments, whereinDerived from a polymeric triol selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polyoxymethylene polymers, polycarbonate-copolyesters and alkoxylated analogues of any of these. In certain embodiments, the alkoxylated polymeric triols comprise ethoxylated or propoxylated compounds.

In some embodiments of the present invention, the substrate is,derived from a polyol having four hydroxyl groups. In certain embodiments, the aliphatic polycarbonate chains in the polymer compositions of the present invention comprise aliphatic polycarbonate chains, wherein a portion thereofDerived from a tetrol. In certain embodiments, the aliphatic polycarbonate chains in the polymer composition of the invention comprise chains having the structure P4:

In some embodiments of the present invention, the substrate is,derived from polyols having more than four hydroxyl groups. In some embodiments of the present invention, the substrate is,derived from a polyol having six hydroxyl groups. In certain embodiments, the polyol is dipentaerythritol (dipentaerithrotol) or an alkoxylated analog thereof. In certain embodiments, the polyol is sorbitol or an alkoxylated analog thereof. In certain embodiments, the aliphatic polycarbonate chains in the polymer composition of the present invention comprise chains having the following structure P5:

In certain embodiments, the aliphatic polycarbonates of the present invention comprise a combination of difunctional chains (e.g., polycarbonates of formula P2) in combination with higher functional chains (e.g., one or more polycarbonates of formula P3 through P5).

In some embodiments of the present invention, the substrate is,derived from a hydroxy acid. In certain embodiments, the aliphatic polycarbonate chains in the polymer composition of the invention comprise chains having the structure P6:

wherein each R¹、R²、R³、R⁴、Y、And n is as defined above and described in classes and subclasses herein. In this case, it is preferable that,represents the carbon-containing backbone of the hydroxy acid, adjacent toEsters and carbonate linkages of (A) are derived from-CO of hydroxy acids₂H groups and hydroxyl groups. For example, ifDerived from 3-hydroxypropionic acid, thenWill be-CH₂CH₂And P6 will have the following structure:

in some embodiments of the present invention, the substrate is,derived from optionally substituted C_2-40A hydroxy acid. In some embodiments of the present invention, the substrate is,derived from a polyester. In certain embodiments, such polyesters have a molecular weight of less than about 2000 g/mol.

In certain embodiments, the hydroxy acid is α -hydroxy acid in certain embodiments, the hydroxy acid is selected from the group consisting of glycolic acid, DL-lactic acid, D-lactic acid, L-lactic acid, citric acid, and mandelic acid.

In certain embodiments, the hydroxy acid is β -hydroxy acid in certain embodiments, the hydroxy acid is selected from the group consisting of 3-hydroxypropionic acid, DL 3-hydroxybutyric acid, D-3 hydroxybutyric acid, L-3-hydroxybutyric acid, DL-3-hydroxyvaleric acid, D-3-hydroxyvaleric acid, L-3-hydroxyvaleric acid, salicylic acid, and salicylic acid derivatives.

In certain embodiments, the hydroxy acid is α -omega hydroxy acid_3-20Aliphatic α -omega hydroxy acids and oligomeric esters.

In certain embodiments, the hydroxy acid is selected from:

in some embodiments of the present invention, the substrate is,derived from polycarboxylic acids. In certain embodiments, the aliphatic polycarbonate chains in the polymer composition of the invention comprise chains having the structure P7:

wherein each R¹、R²、R³、R⁴、Y、And n is as defined above and described in classes and subclasses herein, and y' is an integer from 1 to 5, inclusive.

In embodiments where the aliphatic polycarbonate chains have the structure P7,denotes the carbon-containing backbone (or covalent bond in the case of oxalic acid) of the polycarboxylic acid, adjacent toThe ester group of (A) is derived from the-CO of a polycarboxylic acid₂And (4) an H group. For example, ifDerived from succinic acid (HO)₂CCH₂CH₂CO₂H) Then, thenWill be-CH₂CH₂And P7 will have the following structure:

wherein each R¹、R²、R³、R⁴Y and n are as defined above and described in classes and subclasses herein.

In some embodiments of the present invention, the substrate is,derived from a dicarboxylic acid. In certain embodiments, the aliphatic polycarbonate chains in the polymer composition of the invention comprise chains having the structure P8:

in some embodiments of the present invention, the substrate is,selected from: phthalic acid, isophthalic acid, terephthalic acid, maleic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid.

In some embodiments of the present invention, the substrate is,selected from:

in certain embodiments, each of the structures hereinIndependently selected from:

wherein each R^xIndependently is an optionally substituted group selected from: c_2-20Aliphatic, C_2-20Heteroaliphatic, 3-to 14-membered carbocyclic ring, 6-to 10-membered aryl, 5-to 10-membered heteroaryl, and 3-to 12-membered heterocyclic ring.

wherein R is^xAs defined above and described in classes and subclasses herein.

In certain embodiments, the aliphatic polycarbonate chains comprise:

wherein each one-Y and n are as defined above and described in classes and subclasses herein. In some embodimentsIn this case, the aliphatic polycarbonate chain comprises

Wherein each-Y and n are as defined above and described in classes and subclasses herein.

In certain embodiments, the aliphatic polycarbonate chains comprise

Wherein each one-Y and n are as defined above and described in classes and subclasses herein.

In certain embodiments, the aliphatic polycarbonate chains comprise

Wherein each one-Y and n are as defined above and described inClasses and subclasses herein.

In certain embodiments, the aliphatic polycarbonate chains comprise

Each of which-Y、R^xAnd n is as defined above and described in classes and subclasses herein.

In certain embodiments, the aliphatic polycarbonate chains comprise

Wherein each-Y, R^xAnd n is as defined above and described in classes and subclasses herein.

In certain embodiments, the aliphatic polycarbonate chains comprise

Each of which-Y and n are as defined above and described in classes and subclasses herein; and each isIndependently represents a single bond or a double bond.

In certain embodiments, the aliphatic polycarbonate chains comprise

Wherein each of-Y,And n is as defined above and described in classes and subclasses herein.

In certain embodiments, the aliphatic polycarbonate chains comprise

Wherein each one R^xY and n are as defined above and described in classes and subclasses herein.

In certain embodiments, the aliphatic polycarbonate chains comprise

Each of which-Y and n are as defined above and described in classes and subclasses herein.

In certain embodiments, the aliphatic polycarbonate chains comprise

In certain embodiments, in the polycarbonates of structures P2a, P2c, P2d, P2f, P2h, P2j, P2l, P2l-a, P2n, P2P, and P2r,selected from: ethylene glycol, diethylene glycol, triethylene glycol, 1,3 propane diol, 1,4 butane diol, hexylene glycol, 1,6 hexane diol, propylene glycol, dipropylene glycol, tripropylene glycol, and alkoxylated derivatives of any of these.

For polycarbonates comprising repeat units derived from two or more epoxides, such as those represented by structures P2f through P2r described above, it is understood that the depicted structures may represent positional isomers or mixtures of regioisomers that are not explicitly described. For example, the polymer repeat units adjacent to either end of the polycarbonate chain may be derived from either of the two epoxides comprising the copolymer, or from only one of the two epoxides. Thus, while the polymer can be drawn with the particular repeat unit attached to the end group, the terminal repeat unit can be derived from either of the two epoxides and a given polymer composition can contain all possible mixtures in different ratios. The ratio of these end groups can be affected by several factors, including the ratio of the different epoxides used in the polymerization, the structure of the catalyst used, the reaction conditions (i.e., temperature, CO) used₂Pressure, etc.) and the time of addition of the reaction components. Similarly, while defined regioselections may be shown in the above figures for repeat units derived from substituted epoxides, in some cases, the polymer compositions will contain a mixture of regioisomers. The regioselectivity of a given polymerization can be affected by a number of factors, including the structure of the catalyst used and the reaction conditions employed. For purposes of illustration, this means that the composition represented by structure P2r above may contain a mixture of several compounds as shown in the following schematic. This schematic schematically shows isomers of polymer P2r, where the structure below the description of the chain shows that each regio and positional isomer is possible for the monomer units adjacent to the chain transfer agent and the end groups on each side of the polymer backbone. Each end group on the polymer may be independently selected from the groups shown on the left or right, including chain transfer agents and bothThe central portion of the polymer of each adjacent monomer unit may be independently selected from the groups shown. In certain embodiments, the polymer composition comprises a mixture of all possible combinations of these. In other embodiments, the polymer composition is enriched in one or more of these.

In certain embodiments, the aliphatic polycarbonate polyol is selected from Q1, Q2, Q3, Q4, Q5, Q6, and mixtures of any two or more of these.

Wherein t is an integer of 1 to 12 inclusive, and R^tIndependently at each occurrence is-H or-CH₃。

In certain embodiments, the aliphatic polycarbonate polyol is selected from:

a poly (ethylene carbonate) of formula Q1 having a number average molecular weight between about 500g/mol and about 3,000g/mol, a polydispersity index of less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

a poly (ethylene carbonate) of formula Q1 having a number average molecular weight of about 500g/mol, a polydispersity index of less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

a poly (ethylene carbonate) of formula Q1 having a number average molecular weight of about 1,000g/mol, a polydispersity index of less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

a poly (ethylene carbonate) of formula Q1 having a number average molecular weight of about 2,000g/mol, a polydispersity index of less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

a poly (ethylene carbonate) of formula Q1 having a number average molecular weight of about 3,000g/mol, a polydispersity index of less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

poly (propylene carbonate) of formula Q2 having a number average molecular weight of about 500g/mol to about 3,000g/mol, a polydispersity index of less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

poly (propylene carbonate) of formula Q2 having a number average molecular weight of about 500g/mol, a polydispersity index of less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

poly (propylene carbonate) of formula Q2 having a number average molecular weight of about 1000g/mol, a polydispersity index of less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

poly (propylene carbonate) of formula Q2 having a number average molecular weight of about 2,000g/mol, a polydispersity index of less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

poly (propylene carbonate) of formula Q2 having a number average molecular weight of about 3,000g/mol, a polydispersity index of less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

poly (ethylene-co-propylene carbonate) of formula Q3 having a number average molecular weight between about 500g/mol and about 3,000g/mol, a polydispersity index of less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

poly (ethylene-co-propylene carbonate) of formula Q3 having a number average molecular weight of about 500g/mol, a polydispersity index of less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

poly (ethylene-co-propylene carbonate) of formula Q3 having a number average molecular weight of about 1,000g/mol, a polydispersity index of less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

poly (ethylene-co-propylene carbonate) of formula Q3 having a number average molecular weight of about 2,000g/mol (e.g., n averages between about 10 to about 11), a polydispersity index of less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

poly (ethylene-co-propylene carbonate) of formula Q3 having a number average molecular weight of about 3,000g/mol, a polydispersity index of less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

poly (ethylene carbonate) of formula Q4 having a number average molecular weight of between about 500g/mol and about 3,000g/mol (e.g., between about 4 and about 16 per n), a polydispersity index of less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

a poly (ethylene carbonate) of formula Q4 having a number average molecular weight of about 500g/mol, a polydispersity index of less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

a poly (ethylene carbonate) of formula Q4 having a number average molecular weight of about 1,000g/mol, a polydispersity index of less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

a poly (ethylene carbonate) of formula Q4 having a number average molecular weight of about 2,000g/mol, a polydispersity index of less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

a poly (ethylene carbonate) of formula Q4 having a number average molecular weight of about 3,000g/mol, a polydispersity index of less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups.

Poly (propylene carbonate) of formula Q5 having a number average molecular weight between about 500g/mol and about 3,000g/mol, a polydispersity index of less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

poly (propylene carbonate) of formula Q5 having a number average molecular weight of about 500g/mol, a polydispersity index of less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

poly (propylene carbonate) of formula Q5 having a number average molecular weight of about 1,000g/mol, a polydispersity index of less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

poly (propylene carbonate) of formula Q5 having a number average molecular weight of about 2,000g/mol, a polydispersity index of less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

poly (propylene carbonate) of formula Q5 having a number average molecular weight of about 3,000g/mol, a polydispersity index of less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

poly (ethylene-co-propylene carbonate) of formula Q6 having a number average molecular weight between about 500g/mol and about 3,000g/mol, a polydispersity index of less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

poly (ethylene-co-propylene carbonate) of formula Q6 having a number average molecular weight of about 500g/mol, a polydispersity index of less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

poly (ethylene-co-propylene carbonate) of formula Q6 having a number average molecular weight of about 1,000g/mol, a polydispersity index of less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups;

poly (ethylene-co-propylene carbonate) of formula Q6 having a number average molecular weight of about 2,000g/mol (e.g., n averages between about 10 to about 11), a polydispersity index of less than about 1.25, at least 90% carbonate linkages, and at least 98% -OH end groups; and

poly (ethylene-co-propylene carbonate) of formula Q6 having a number average molecular weight of about 3,000g/mol, a polydispersity index of less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups.

In certain embodiments, an embedded chain transfer agentAre moieties derived from polymeric diols or higher polyols. In certain embodiments, such polymeric alcohols are polyether or polyester polyols. In some embodiments of the present invention, the substrate is,is a compound containing ethylene glycol or propylene glycol repeating units (-OCH)₂CH₂-O-or-OCH₂CH(CH₃) O-) or combinations of these. In some embodiments of the present invention, the substrate is,is a polyester polyol comprising the reaction product of a diol and a diacid, or a material resulting from the ring-opening polymerization of a lactone.

In certain embodiments, whereinComprising a polyether diol, the aliphatic polycarbonate polyol having the structure Q7:

wherein the content of the first and second substances,

R^qindependently at each occurrence in the polymer chain is-H or-CH₃；

R^ais-H or-CH₃；

q and q' are independently integers from about 2 to about 40; and is

And n is as defined above and in the examples and implementations herein.

In certain embodiments, the aliphatic polycarbonate polyol is selected from:

wherein each R^a、R^qQ, q', and n are as defined above and described in classes and subclasses herein.

In certain embodiments, wherein the aliphatic polycarbonate polyol comprises a compound conforming to structure Q7, in partDerived from commercially available polyether polyols such as those typically used in formulating polyurethane foam compositions.

In certain embodiments, whereinComprising a polyester diol, the aliphatic polycarbonate polyol having the structure Q8:

wherein the content of the first and second substances,

c is independently at each occurrence in the polymer chain an integer from 0 to 6;

d is independently at each occurrence in the polymer chain an integer from 1 to 11; and is

Each R^qN, q and q' are as defined above and are described in classes and subclasses herein.

In certain embodiments, the aliphatic polycarbonate polyol is selected from:

wherein each n and q is as defined above and described in classes and subclasses herein.

In certain embodiments, wherein the aliphatic polycarbonate polyol comprises a compound conforming to structure Q8, in partDerived from commercially available polyester polyols such as those typically used in formulating polyurethane foam compositions.

Appendix B isocyanate reagent

This section describes some polyisocyanates having utility in the methods and compositions of the present invention. The compositions of the present invention comprise an isocyanate reagent or reaction product thereof. The purpose of these isocyanate reagents is to react with the reactive end groups on the aliphatic polycarbonate polyols to form high molecular weight structures by chain extension and/or crosslinking.

The art of polyurethane synthesis is well advanced and a variety of isocyanates and related polyurethane precursors are known in the art and are commercially available. While this section of this specification describes isocyanates suitable for use in certain embodiments of the present invention, it is understood that the use of alternative isocyanates, along with the teachings of the present disclosure, to formulate additional compositions of matter within the scope of the present invention is within the ability of those skilled in the art of polyurethane formulation. A description of suitable isocyanate compounds and related methods can be found inChemistry and Technology of Polyols for PolyurethanesIonescu, Mihail 2005(ISBN 978-1-84735-.

In certain embodiments, the isocyanate reagent comprises two or more isocyanate groups per molecule. In certain embodiments, the isocyanate reagent is a diisocyanate. In other embodiments, the isocyanate reagent is a higher polyisocyanate such as triisocyanate, tetraisocyanate, isocyanate polymer or oligomer, and the like. In certain embodiments, the isocyanate agent is an aliphatic polyisocyanate or a derivative or oligomer of an aliphatic polyisocyanate. In other embodiments, the isocyanate is an aromatic polyisocyanate or a derivative or oligomer of an aromatic polyisocyanate. In certain embodiments, the composition may comprise a mixture of any two or more of the above types of isocyanates.

In certain embodiments, the isocyanate component used to formulate the novel materials of the present invention has a functionality of 2 or more. In certain embodiments, the isocyanate component of the materials of the present invention comprises a mixture of diisocyanates and higher isocyanates formulated to achieve a particular functionality for a given application. In certain embodiments, where the present composition is a flexible foam or a flexible elastomer, the isocyanate used has a functionality of about 2. In certain embodiments, such isocyanates have a functionality of between about 2 and about 2.7. In certain embodiments, such isocyanates have a functionality of between about 2 and about 2.5. In certain embodiments, such isocyanates have a functionality of between about 2 and about 2.3. In certain embodiments, such isocyanates have a functionality of between about 2 and about 2.2.

In other embodiments, where the composition of the present invention is a rigid foam or a thermoplastic, the isocyanate used has a functionality of greater than 2. In certain embodiments, such isocyanates have a functionality of between about 2.3 and about 4. In certain embodiments, such isocyanates have a functionality of between about 2.5 and about 3.5. In certain embodiments, such isocyanates have a functionality of between about 2.6 and about 3.1. In certain embodiments, such isocyanates have a functionality of about 3.

In certain embodiments, the isocyanate reagent is selected from: 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), 4' -methylene-bis (cyclohexyl isocyanate) (H)₁₂MDI), 2, 4-Tolylene Diisocyanate (TDI), 2, 6-Tolylene Diisocyanate (TDI), diphenylmethane-4, 4 '-diisocyanate (MDI), diphenylmethane-2, 4' -diisocyanateEsters (MDI), Xylylene Diisocyanate (XDI), 1, 3-bis (isocyanatomethyl) cyclohexane (H6-XDI), 2, 4-trimethylhexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate (TMDI), m-tetramethylxylylene diisocyanate (TMXDI), p-tetramethylxylylene diisocyanate (TMXDI), isocyanatomethyl-1, 8-octane diisocyanate (TIN), triphenylmethane-4, 4' triisocyanate, tris (p-isocyanatomethyl) thiosulfate, 1, 3-bis (isocyanatomethyl) benzene, 1, 4-tetramethylene diisocyanate, trimethylhexane diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 4-cyclohexyl diisocyanate, lysine diisocyanate, and mixtures of any two or more of these.

Isocyanates suitable for use in certain embodiments of the present invention are commercially available under various trade names. Examples of suitable commercially available isocyanates include materials sold under the following trade names:(Bayer MaterialScience)、(Perstorp)、(Takeda)、(Evonik)、(Bayer Material Science)、(Bayer Material Science)、Mondur(Bayer Material Science)、Suprasec(Huntsman Inc.)、(BASF)、Trixene(Baxenden)、(Benasedo)、(Sapici) and(BASF). Each of these trade names covers a wide variety of isocyanate materials available in various grades and formulations. The selection of suitable commercially available isocyanate materials as reagents to produce polyurethane compositions for particular applications is within the ability of those skilled in the art of polyurethane technology using the teachings and disclosures of the present patent application along with the information provided in the product data sheets provided by the suppliers above.

Additional isocyanates suitable for use in certain embodiments of the present invention are under the trade name(BASF). In certain embodiments, the isocyanate is selected from the materials shown in table 1:

TABLE 1

Other isocyanates suitable for use in certain embodiments of the present invention are under the trade name from Bayer Material ScienceAnd (5) selling. In certain embodiments, the isocyanate is selected from the materials shown in table 2:

TABLE 2

Additional isocyanates suitable for use in certain embodiments of the present invention are under the trade name(Perstorp). In certain embodiments, the isocyanate is selected from the materials shown in table 3:

TABLE 3

Other isocyanates suitable for use in certain embodiments of the present invention are under the trade name from Bayer Material ScienceAnd (5) selling. In certain embodiments, the isocyanate is selected from the materials shown in table 4:

TABLE 4

Appendix C additives

As noted above, in some embodiments, the methods and compositions of the present invention comprise a so-called B-side mixture comprising one or more aliphatic polycarbonate polyols. To produce the foam, the B-side mixture is reacted with an A-side mixture containing one or more polyisocyanates (or precursors of polyisocyanates). Typically, one or both of the a-side mixture and B-side mixture will contain different kinds of additional components and additives. In certain embodiments, the B-side mixture from which any of the foams of the present invention are produced comprises one or more additional polyols and/or one or more additives. In certain embodiments, the additive is selected from: solvents, water, catalysts, surfactants, blowing agents, colorants, UV stabilizers, flame retardants, antimicrobial agents, plasticizers, cell opening agents, antistatic compositions, compatibilizers, and the like. In certain embodiments, the B-side mixture comprises additional reactive small molecules such as amines, water, alcohols, thiols, or carboxylic acids that participate in the bonding reaction with the isocyanate.

A. Additional polyols

In certain embodiments, the B-side mixture of the present invention comprises an aliphatic polycarbonate polyol as described above in combination with one or more additional polyols, such as those conventionally used in polyurethane foam compositions. In embodiments where additional polyols are present, they may comprise up to about 95 weight percent of the total polyol content, with the remainder of the polyol mixture being comprised of one or more of the aliphatic polycarbonate polyols described in section I above and in the examples and embodiments herein.

In embodiments where the B-side mixture of the present invention comprises or is derived from a mixture of one or more aliphatic polycarbonate polyols and one or more additional polyols, the additional polyols are selected from polyether polyols, polyester polyols, polystyrene polyols, polyether-carbonate polyols, polyether-ester carbonates and mixtures of any two or more of these. In certain embodiments, the B-side mixture of the present invention comprises or is derived from a mixture of one or more aliphatic polycarbonate polyols as described herein and one or more other polyols selected from materials commercially available under the following trade names:(Dow)、(Dow)、(Dow)、(Shell)、(Bayer Material Science)、(Bayer MaterialScience)、(Bayer Material Science) and(Bayer MaterialScience)。

in certain embodiments, the B-side mixture of the present invention comprises a mixture comprising a polyether polyol in combination with one or more aliphatic polycarbonate polyols as described herein. In certain embodiments, such polyether polyols are characterized as having an Mn of from about 500 to about 10,000 g/mol. In certain embodiments, such polyether polyols have an Mn of from about 500 to about 5,000 g/mol. In certain embodiments, the polyether polyol comprises polyethylene glycol. In certain embodiments, the polyether polyol comprises polypropylene glycol.

Polyether polyols which may be present include those which can be obtained by known processes, for example polyether polyols can be produced by anionic polymerization with alkali metal hydroxides such as sodium or potassium hydroxide or alkali metal alcoholates (such as sodium methylate, sodium ethylate, potassium ethylate or potassium isopropylate) as catalyst and with addition of at least one initiator molecule containing 2 to 8, preferably 3 to 8, active hydrogens or by cationic polymerization with lewis acids such as antimony pentachloride, boron trifluoride etherate or the like or bleaching clay as catalyst with one or more olefin oxides having 2 to 4 carbons in the olefin group. Any suitable alkylene oxide may be used such as 1, 3-propylene oxide, 1, 2-butylene oxide and 2, 3-butylene oxide, pentane oxide, styrene oxide and preferably ethylene oxide and propylene oxide and mixtures of these oxides. The polyalkylene polyether polyols may be prepared from other starting materials, such as tetrahydrofuran and alkylene oxide-tetrahydrofuran mixtures; epihalohydrins such as epichlorohydrin; and aralkylene oxides such as styrene oxide. The polyalkylene polyether polyols may have primary or secondary hydroxyl groups, preferably secondary hydroxyl groups generated by the addition of propylene oxide to the initiator, since these groups react relatively slowly. Polyether polyols include polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polytetramethylene glycol, block copolymers such as polyoxypropylene glycol and polyoxyethylene glycol, poly-l, 2-oxybutylene and polyoxyethylene glycol, poly-l, 4-tetramethylene and polyoxyethylene glycol, and copolymer glycols prepared from blends or sequential additions of two or more olefin oxides. The polyalkylene polyether polyols may be prepared by any known process, such as, for example, the process disclosed by Wurtz, Encyclopedia of Chemical Technology, volume 7, page 257-262, Interscience publishers, Inc. (1951) or in U.S. Pat. No.1,922,459. Polyethers include alkylene oxide adducts of polyhydric alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1, 2-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, hydroquinone, resorcinol glycerol, 1,1, 1-trimethylol-propane, 1,1, 1-trimethylolethane, pentaerythritol, 1,2, 6-hexanetriol, a-methyl glucoside, sucrose, and sorbitol. The term "polyol" also includes compounds derived from phenol such as 2, 2-bis (4-hydroxyphenol) -propane, commonly referred to as bisphenol a. Particularly preferred in the polyol composition is at least one polyol starting with a compound having at least two primary or secondary amine groups, a polyol having 4 or more hydroxyl groups such as sucrose, or an initiator mixture using a polyol having at least 4 hydroxyl groups and a compound having at least two primary or secondary amine groups. Suitable organic amine initiators that may be condensed with the olefin oxide include aromatic amines-such as aniline, N-alkyl phenylene-diamines, 2,4' -, 2' -and 4,4' -methylenedianiline, 2, 6-or 2, 4-toluenediamine, ortho-chloroaniline, para-aminoaniline, 1, 5-diaminonaphthalene, methylenedianiline, various condensation products of aniline and formaldehyde, and isomeric diaminotoluenes; and aliphatic amines such as mono-, di-, and trialkanolamines, ethylenediamine, propylenediamine, diethylenetriamine, methylamine, triisopropanolamine, 1, 3-diaminopropane, 1, 3-diaminobutane, and 1, 4-diaminobutane. Preferred amines include monoethanolamine, ortho-toluenediamine, ethylenediamine (ethylene diamines) and propylenediamine (propylenediamine). Yet another class of aromatic polyether polyols contemplated for use in the present invention are Mannich-based polyols (an olefin oxide adduct of phenol/formaldehyde/alkanolamine resin), commonly referred to as "Mannich" polyols such as those disclosed in U.S. patent nos. 4,883,826; 4,939,182, and 5,120,815.

In embodiments where additional polyols are present, they comprise a total polyol content of from about 5 weight percent to about 95 weight percent, with the remainder of the polyol mixture consisting of one or more aliphatic polycarbonate polyols described in section I above and in the examples and specific embodiments herein. In certain embodiments, up to about 75 weight percent of the total polyol content of the B-side mixture is aliphatic polycarbonate polyol. In certain embodiments, up to about 50 weight percent of the total polyol content of the B-side mixture is aliphatic polycarbonate polyol. In certain embodiments, up to about 40 weight percent, up to about 30 weight percent, up to about 25 weight percent, up to about 20 weight percent, up to about 15 weight percent, or up to about 10 weight percent of the total polyol content of the B-side mixture is aliphatic polycarbonate polyol. In certain embodiments, at least about 5 weight percent of the total polyol content of the B-side mixture is aliphatic polycarbonate polyol. In certain embodiments, at least about 10 weight percent of the total polyol content of the B-side mixture is aliphatic polycarbonate polyol. In certain embodiments, at least about 15 weight percent, at least about 20 weight percent, at least about 25 weight percent, at least about 40 weight percent, or at least about 50 weight percent of the total polyol content of the B-side mixture is an aliphatic polycarbonate polyol.

B. Catalyst and process for preparing same

In certain embodiments, the B-side mixture contains one or more catalysts for the reaction of the polyol (and water, if present) with the polyisocyanate. Any suitable urethane catalyst may be used, including tertiary amine compounds and organometallic compounds. Exemplary tertiary amine compounds include triethylenediamine, N-methylmorpholine, N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, tetramethylethylenediamine, 1-methyl-4-dimethylaminoethylpiperazine, 3-methoxy-N-dimethylpropylamine, N-ethylmorpholine, diethylethanolamine, N-cocomorpholine (N-cocorophylline), N-dimethyl-N ', N' -dimethylisopropylpropylenediamine, N, n-diethyl-3-diethylaminopropylamindimethylbenzylamine, 1, 8-diazabicycloundec-7-ene (DBU), 1, 4-diazabicyclo [2.2.2] octane (DABCO) Triazabicyclodecene (TBD) and N-Methyltriazabicyclodecene (MTBD). Exemplary organometallic catalysts include organomercury, organolead, organoiron, and organotin catalysts, with organotin catalysts being preferred. Suitable tin catalysts include stannous chloride, tin salts of carboxylic acids such as dibutyltin dilaurate, and other organometallic compounds such as those disclosed in U.S. Pat. No.2,846,408, and others. Catalysts for the trimerization of polyisocyanates (to produce polyisocyanurates), such as alkali metal alkoxides, may also optionally be used herein. Such catalysts are used in amounts that measurably increase the rate of polyurethane or polyisocyanurate formation.

In certain embodiments, wherein the B-side mixture of the present invention comprises a catalyst, the catalyst comprises a tin-based material. In certain embodiments, the tin catalyst included in the B-side mixture is selected from: dibutyltin dilaurate, dibutylbis (laurylthio) stannate, dibutyltin bis (isooctylmercaptoacetate) and dibutyltin bis (isooctylmaleate), tin octoate, and mixtures of any two or more of these.

In certain embodiments, the catalyst included in the B-side mixture comprises a tertiary amine. In certain embodiments, the catalyst included in the B-side mixture is selected from: DABCO, pentamethyldipropylenetriamine, bis (dimethylaminoethyl ether), pentamethyldiethylenetriamine, DBU phenate, dimethylcyclohexylamine, 2,4, 6-tris (N, N-dimethylaminomethyl) phenol (DMT-30), 1,3, 5-tris (3-dimethylaminopropyl) hexahydro-s-triazine, ammonium salts, and combinations or formulations of any of these.

Typical amounts of catalyst in the B-side mixture are from 0.001 to 10 parts catalyst per 100 parts by weight total polyol. In certain embodiments, the catalyst level in the formulation, when used, ranges between about 0.001pph (per hundred parts by weight) and about 3pph, based on the amount of polyol present in the B-side mixture. In certain embodiments, the catalyst level ranges between about 0.05pph and about 1pph or between about 0.1pph and about 0.5 pph.

C. Foaming agent

In certain embodiments, the B-side mixture of the present invention contains a blowing agent. The blowing agent may be a chemical blowing agent (typically a reaction with the A-side component to release CO)₂Or molecules of other volatile compounds) or it may be a physical blowing agent (typically molecules with a low boiling point that evaporate during foam formation). Many blowing agents are known in the art and can be applied to the B-side compositions of the present invention according to conventional methods. The selection of blowing agent and the amount added can be a matter of routine experimentation.

In certain embodiments, the blowing agent comprises a chemical blowing agent. In certain embodiments, the water is present as a blowing agent. Water acts as a blowing agent by reacting with a portion of the isocyanate in the a-side mixture to produce carbon dioxide gas. Similarly, formic acid may be included as a blowing agent. Formic acid acts as a blowing agent by reacting with a portion of the isocyanate to produce carbon dioxide and carbon monoxide gas.

In certain embodiments, water is present in the B-side composition in an amount of from 0.5 to 20 parts per 100 parts by weight of polyol. In certain embodiments, water is present in the B-side composition at about 1 to 10 parts, about 2 to 8 parts, or about 4 to 6 parts per 100 parts by weight of the polyol. In certain embodiments, it is advantageous not to exceed 2 parts water, not to exceed 1.5 parts water, or not to exceed 0.75 parts water. In certain embodiments, the absence of water is advantageous.

In certain embodiments, formic acid is present in the B-side composition in an amount of from 0.5 to 20 parts per 100 parts by weight of polyol. In certain embodiments, formic acid is present in the B-side composition at about 1 to 10 parts, about 2 to 8 parts, or about 4 to 6 parts per 100 parts by weight of the polyol.

In certain embodiments, a physical blowing agent may be used. Suitable physical blowing agents include hydrocarbons, fluorine-containing organic molecular hydrocarbons, chlorocarbon compounds, acetone, methyl formate, and carbon dioxide. In some embodiments, the fluorine-containing organic molecule comprises a perfluoro compound, a chlorofluorocarbon, a hydrochlorofluorocarbon, and a hydrofluorocarbon. Suitable hydrofluoroalkanes are C_1-4Compounds including difluoromethane (R-32), 1,1,1, 2-tetrafluoroethane (R-134a), 1, 1-difluoroethane (R-152a), difluorochloroethane (R-142b), trifluoromethane (R-23), heptafluoropropane (R-227a), hexafluoropropane (R136), 1,1, 1-trifluoroethane (R-133), fluoroethane (R-161), 1,1,1,2, 2-pentafluoropropane (R-245fa), pentafluoropropene (R212 2125a), 1,1,1, 3-tetrafluoropropane, tetrafluoropropene (R-2134a), 1,1,2,3, 3-pentafluoropropane, and 1,1,1,3, 3-pentafluoron-butane.

In certain embodiments, when a hydrofluorocarbon blowing agent is present in the B-side mixture, it is selected from: tetrafluoroethane (R-134a), pentafluoropropane (R-245fa) and pentafluorobutane (R-365).

Suitable hydrocarbons for use as blowing agents include non-halogenated hydrocarbons such as butane, isobutane, 2, 3-dimethylbutane, n-and isopentane isomers, hexane isomers, heptane isomers and cycloalkanes (including cyclopentane, cyclohexane and cycloheptane). Preferred hydrocarbons for use as blowing agents include cyclopentane, especially n-pentane and isopentane. In certain embodiments, the B-side composition comprises a physical blowing agent selected from the group consisting of: tetrafluoroethane (R-134a), pentafluoropropane (R-245fa), pentafluorobutane (R-365), cyclopentane, n-pentane and isopentane.

In certain embodiments where a physical blowing agent is present, it is used in the B-side composition in an amount of from about 1 to about 20 parts per 100 parts by weight of polyol. In certain embodiments, the physical blowing agent is present in the B-side composition at 2 to 15 parts or 4 to 10 parts per 100 parts by weight of polyol.

D. Reactive small molecules

In certain embodiments, the B-side mixture of the present invention includes one or more small molecules reactive with isocyanates. In certain embodiments, the reactive small molecules included in the B-side mixtures of the present invention comprise organic molecules having one or more functional groups selected from the group consisting of alcohols, amines, carboxylic acids, thiols, and combinations of any two or more of these. In some embodiments, the non-polymeric small molecule has a molecular weight of less than 1,000g/mol or less than 1,500 g/mol.

In certain embodiments, the B-side mixture of the present invention comprises one or more alcohols. In certain embodiments, the B-side mixture comprises a polyol.

In certain embodiments, the reactive small molecule included in the B-side mixture of the present invention comprises a diol. In certain embodiments, the glycol comprises C_2-40A diol. In certain embodiments, the glycol is selected from: 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 2-dimethylpropane-1, 3-diol, 2-butyl-2-ethylpropane-1, 3-diol, 2-methyl-2, 4-pentanediol, 2-ethyl-1, 3-hexanediol, 2-methyl-1, 3-propanediol, 1, 5-hexanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, 2,4, 4-tetramethylcyclobutane-1, 3-diol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanediethanol, isosorbide, monoglycerides, monoethers of glycerol, trimethylolpropane monoesters, trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritol diethers, and alkoxylated derivatives of any of these.

In certain embodiments, the reactive small molecule included in the B-side mixture of the present invention comprises a diol selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly (ethylene glycols) such as those having a number average molecular weight of 220 to about 2000g/mol, dipropylene glycol, tripropylene glycol, and higher poly (propylene glycols) such as those having a number average molecular weight of 234 to about 2000 g/mol.

In certain embodiments, the reactive small molecules included in the B-side mixtures of the present invention comprise alkoxylated derivatives of compounds selected from: a diacid, a diol, or a hydroxy acid. In certain embodiments, the alkoxylated derivative comprises an ethoxylated or propoxylated compound.

In certain embodiments, the reactive small molecules included in the B-side mixtures of the present invention comprise polymeric diols. In certain embodiments, the polymeric glycol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether-polycarbonates, polycarbonate-copolyesters, and alkoxylated analogs of any of these. In certain embodiments, the polymeric glycol has an average molecular weight of less than about 2000 g/mol.

In some embodiments, the reactive small molecules included in the B-side mixtures of the present invention comprise triols or higher polyols. In certain embodiments, the reactive small molecule is selected from: glycerol, 1,2, 4-butanetriol, 2- (hydroxymethyl) -1, 3-propanediol, hexanetriol, trimethylolpropane, trimethylolethane, trimethylolhexane, 1, 4-cyclohexane tricarbol alcohol, pentaerythritol monoesters, pentaerythritol monoethers, and alkoxylated analogs of any of these. In certain embodiments, the alkoxylated derivative comprises an ethoxylated or propoxylated compound.

In some embodiments, the reactive small molecule comprises a polyol having four to six hydroxyl groups. In certain embodiments, the co-reactant comprises dipentaerythritol or an alkoxylated analog thereof. In certain embodiments, the co-reactant comprises sorbitol or an alkoxylated analog thereof.

In certain embodiments, the reactive small molecule comprises a compound having the general formula (HO)_xQ(COOH)_yWherein Q is a hydroxyl-carboxylic acid containing 1 to 12 carbon atomsA straight or branched chain hydrocarbon group, and x and y are each an integer of 1 to 3. In certain embodiments, the co-reactant comprises a diol carboxylic acid. In certain embodiments, the co-reactant comprises a bis (hydroxyalkyl) alkanoic acid. In certain embodiments, the co-reactant comprises a bis (hydroxymethyl) alkanoic acid. In certain embodiments, the diol carboxylic acid is selected from the group consisting of 2,2 bis- (hydroxymethyl) -propionic acid (dimethylolpropionic acid, DMPA), 2 bis (hydroxymethyl) butanoic acid (dimethylolbutanoic acid; DMBA), dihydroxysuccinic acid (tartaric acid), and 4,4' -bis (hydroxyphenyl) pentanoic acid. In certain embodiments, the co-reactant comprises an N, N-bis (2-hydroxyalkyl) carboxylic acid.

In certain embodiments, the amino diol is selected from the group consisting of Diethanolamine (DEA), N-Methyldiethanolamine (MDEA), N-ethyldiethanolamine (EDEA), N-Butyldiethanolamine (BDEA), N-bis (hydroxyethyl) - α -aminopyridine, dipropanolamine, Diisopropanolamine (DIPA), N-methyldiisopropanolamine, diisopropanol-p-toluidine, N-bis (hydroxyethyl) -3-chloroaniline, 3-diethylaminopropane-1, 2-diol, 3-dimethylaminopropane-1, 2-diol, and N-hydroxyethylpiperidine.

In certain embodiments, the reactive small molecule is selected from: inorganic or organic polyamines having an average of about 2 or more primary and/or secondary amine groups, polyols, ureas, and combinations of any two or more of these. In certain embodiments, the reactive small molecule is selected from: diethylenetriamine (DETA), Ethylenediamine (EDA), m-xylylenediamine (MXDA), aminoethylethanolamine (AEEA), 2-methylpentanediamine, and the like, as well as mixtures thereof. Also suitable for practicing the invention are propylenediamine, butylenediamine, hexylenediamine, cyclohexanediamine, phenylenediamine, tolylenediamine, 3-dichlorobenzidine, 4' -methylene-bis- (2-chloroaniline), 3-dichloro-4, 4-diaminodiphenylmethane and sulfonated primary and/or secondary amines. In certain embodiments, the reactive small molecule is selected from: hydrazine, substituted hydrazines, hydrazine reaction products, and the like, and mixtures thereof. In certain embodiments, the reactive small molecule is a polyol, including those having from 2 to 12 carbon atoms, preferably from 2 to 8 carbon atoms, such as ethylene glycol, diethylene glycol, neopentyl glycol, butanediol, hexanediol, and the like, and mixtures thereof. Suitable ureas include urea and its derivatives, and the like, and mixtures thereof.

In certain embodiments, the reactive small molecule containing at least one basic nitrogen atom is selected from the group consisting of: mono-, di-or polyalkoxylated aliphatic, cycloaliphatic, aromatic or heterocyclic primary amines, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, N-isopropyldiethanolamine, N-butyldiethanolamine, N-isobutyldiethanolamine, N-oleyldiethanolamine, N-stearyldiethanolamine, ethoxylated coconut oil fatty amines, N-allyldiethanolamine, N-methyldiisopropanolamine, N-ethyldiisopropanolamine, N-propyldiisopropanolamine, N-butyldiisopropanolamine, cyclohexyldiisopropanolamine, N-diethoxyaniline, N-diethoxytoluidine, N-diethoxy-1-aminopyridine, N '-diethoxypiperazine, N' -diethoxypiperazine, N-methyldiethanolamine, N-butyldiethanolamine, N-stearyldiethanolamine, dimethyl-bis-ethoxyhydrazine, N ' -bis- (2-hydroxyethyl) -N, N ' -diethylhexahydrop-phenylenediamine, N-12-hydroxyethylpiperazine, polyalkoxylated amines, propoxylated methyldiethanolamine, N-methyl-N, N-bis-3-aminopropylamine, N- (3-aminopropyl) -N, N ' -dimethylethylenediamine, N- (3-aminopropyl) -N-methylethanolamine, N ' -bis- (3-aminopropyl) -N, N ' -dimethylethylenediamine, N ' -bis- (3-aminopropyl) -piperazine, N- (2-aminoethyl) -piperazine, N-hydroxyethylamine, N-N ' -bis- (3-aminopropyl) -piperazine, N- (2-aminopropyl) -piperazine, N-hydroxyethylamine, N-bis- (3-aminopropyl) -piperazine, n, N '-dioxyethyl propane diamine, 2, 6-diaminopyridine, diethanol aminoacetamide, diethanol aminopropionamide, N-dioxyethyl phenyl thiosemicarbazide, N-dioxyethyl methyl semicarbazide, p' -bis-aminomethyl dibenzyl methylamine, 2, 6-diaminopyridine, 2-dimethylaminomethyl-2-methylpropane 1, 3-diol. In certain embodiments, the chain extender is a compound containing two amino groups. In certain embodiments, the chain extender is selected from: ethylenediamine, 1, 6-hexamethylenediamine and 1, 5-diamino-1-methyl-pentane.

E. Additive agent

In addition to the above components, the a-side or B-side mixtures of the present invention may optionally contain various additives as known in the art of polyurethane foam technology. Such additives may include, but are not limited to, compatibilizers, colorants, surfactants, flame retardants, antistatic compounds, antimicrobial agents, UV stabilizers, plasticizers, and cell openers.

-a colorant

In certain embodiments, the B-side mixture of the present invention comprises one or more suitable colorants. Many foam products are color coded during manufacture to identify product grades, hide yellowing, or to prepare consumer products. The historical method of coloring foams is by mixing in conventional pigments or dyes. Typical inorganic colorants include titanium dioxide, iron oxide, and chromium oxide. Organic pigments originate from azo/diazo dyes, phthalocyanines and dioxazines and also from carbon black. Typical problems encountered with these colorants include high viscosity, tendency to wear (abrasive tendencies), foam instability, foam scorch, color migration, and a limited range of available colors. Research advances in the development of polyol-binding colorants are described in:

Miley,J.W.；Moore,P.D.“Reactive Polymeric Colorants For Polyurethane”,Proceedings Of The SPI-26th Annual Technical Conference；Technomic:Lancaster,Pa.,1981；83-86.

Moore,P.D.；Miley,J.W.；Bates,S.H.；“New Uses For Highly Miscible LiquidPolymeric Colorants In The Manufacture of Colored Urethane Systems”；Proceedings of the SPI-27th Annual Technical/Marketing Conference；Technomic:Lancaster,Pa.,1982；255-261.

Bates,S.H.；Miley,J.W.“Polyol-Bound Colorants Solve Polyurethane ColorProblems”；Proceedings Of The SPI-30th Annual Technical/Marketing Conference；Technomic:Lancaster,Pa.,1986；160-165

vielee, r.c.; haney, t.v. "Polyurethanes"; in harvesting of Plastics; webber, T.G. eds, Wiley-Interscience, New York,1979,191-204.

UV stabilizers

In certain embodiments, the B-side mixture of the present invention comprises one or more suitable UV stabilizers. Polyurethanes based on aromatic isocyanates will generally turn dark-toned yellow when aged by exposure to light. A review of the polyurethane efflorescence phenomena is shown in: davis, a.; sims, d.weather Of Polymers; applied Science, London,1983, 222-. Yellowing is not an issue for most foam applications. Photoprotective agents such as hydroxybenzotriazoles, zinc dibutylthiocarbamate, 2, 6-di-tert-butylcatechol, hydroxybenzophenones, hindered amines and phosphites have been used to improve the light stability of polyurethanes. Colored pigments have also been successfully used.

-flame retardants

In certain embodiments, the B-side mixture of the present invention comprises one or more suitable flame retardants. Low density, open cell, flexible polyurethane foams have a large surface area and high permeability to air and therefore will burn given sufficient application of a source of ignition and oxygen. Flame retardants are often added to reduce flammability. The flame retardant selected for any particular foam is often dependent upon the intended service application for the foam and the attendant flammability testing protocol governing that application. Flammability aspects that may be affected by the additive include initial flammability, burn rate, and smoke release.

The most widely used flame retardants are chlorinated phosphates, chlorinated paraffins and melamine powders. These and many other compositions are available from specific chemical suppliers. An overview of the present subject matter has been given in: kuryla, w.c.; papa, a.j.flameretardance of Polymeric Materials, volume 3; marcel Dekker New York,1975, 1-133.

-bacteriostatic agents

Under certain conditions of warmth and high humidity, polyurethane foams are vulnerable to attack by microorganisms. When this becomes a problem, additives against bacteria, yeast or fungi are added to the foam during manufacture. In certain embodiments, the B-side mixture of the present invention comprises one or more suitable bacteriostatic agents.

-plasticizers

In certain embodiments, the B-side mixture of the present invention comprises one or more suitable plasticizers. Non-reactive liquids have been used to soften foams or reduce viscosity for improved processing. The softening effect can be compensated by using a lower equivalent weight of polyol in order to obtain a highly crosslinked polymer structure. These materials increase foam density and often adversely affect physical properties.

-cell opener

In certain embodiments, the B-side mixture of the present invention comprises one or more suitable cell openers. In some polyurethane foams, a cell opener must be added to obtain a foam that does not shrink upon cooling. Known additives for inducing open cells include silicone-based defoamers, waxes, fine solids, liquid perfluorocarbons, paraffin oils, long chain fatty acids, and certain polyether polyols made using high concentrations of ethylene oxide.

Antistatic agents

In certain embodiments, the B-side mixture of the present invention comprises one or more suitable antistatic compounds. Some flexible foams are used in packaging, apparel, and other applications where it is desirable to minimize the antistatic properties of the foam in order to minimize static charge build-up. This has traditionally been achieved by the addition of ionizable metal salts, carboxylic acid salts, phosphoric acid esters and mixtures thereof. These agents function either by intrinsic conductivity or by absorbing moisture from the air. The net result required is an order of magnitude reduction in foam surface resistivity.

Compatibilizers

In certain embodiments, the B-side mixture of the present invention comprises one or more suitable compatibilizers. Compatibilizers are molecules that allow two or more immiscible components to polymerize together and produce a homogeneous liquid phase. Many such molecules are known to the polyurethane industry, and these include: amides, amines, hydrocarbon oils, phthalates, polytetramethylene glycols and ureas.

Certain embodiments

In certain embodiments, the invention may be described as the following clauses.

1. A method for increasing the load bearing properties of a polyurethane foam composition comprising the reaction product of a polyol component and a polyisocyanate component, the method comprising the step of incorporating into the polyol component a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide, wherein the polycarbonate polyol is added in an amount from about 2 weight percent to about 50 weight percent of all polyols present in the polyol component.

2. The method of clause 1, wherein the polyol component comprises one or more polyols selected from the group consisting of: polyether polyols, polyester polyols, aliphatic polyols, and mixtures of any two or more of these.

3. The method of clause 1, wherein the polyol component substantially comprises a polyether polyol.

4. The method of clause 1, wherein the polycarbonate polyol is added in an amount from about 5 weight percent to about 25 weight percent of all polyols present in the polyol component.

5. The method of clause 4, wherein the polycarbonate polyol is added in an amount from about 2 weight percent to about 10 weight percent of all polyols present in the polyol component.

6. The method of clause 4, wherein the polycarbonate polyol is added in an amount from about 10 weight percent to about 20 weight percent of all polyols present in the polyol component.

7. The method of clause 4, wherein the polycarbonate polyol is added in an amount from about 20 weight percent to about 30 weight percent of all polyols present in the polyol component.

8. The method of clause 4, wherein the polycarbonate polyol is added in an amount from about 30 weight percent to about 50 weight percent of all polyols present in the polyol component.

9. The method of clause 1, wherein the foam composition comprising the added polycarbonate polyol has a Compressive Force Deflection (CFD) value measured according to ASTM D3574 that is higher than the CFD value of a corresponding foam composition lacking the added polycarbonate polyol.

10. The method of clause 9, wherein the CFD value of the foam composition comprising the added polycarbonate polyol is at least 10%, at least 20%, at least 30%, at least 40%, or at least 50% higher than the CFD value of the corresponding foam composition lacking the added polycarbonate polyol.

11. The method of clause 10, wherein the CFD value of the foam comprising the added polycarbonate polyol is at least 20%, at least 30%, at least 40%, or at least 50% higher than the CFD value of the corresponding foam without the added polycarbonate polyol.

12. The method of any of clauses 9-11, wherein the CFD values are normalized for the densities of the foam compositions being compared.

13. The method of any of clauses 9-11, wherein the foam composition is formulated such that the foam composition comprising the added polycarbonate polyol and a corresponding foam composition lacking the added polycarbonate polyol have substantially the same density.

14. The method of clause 1, wherein the foam composition comprises a flexible polyurethane foam.

15. The method of clause 1, wherein the foam composition comprises a viscoelastic polyurethane foam.

16. The method of clause 1, wherein the foam composition comprises a rigid polyurethane foam.

17. The method of clause 1, wherein the foam composition comprising the added polycarbonate polyol has a density measured according to ASTM D3574 that is lower than the density of a corresponding foam composition lacking the added polycarbonate polyol, and wherein the foam composition comprising the added polycarbonate polyol has a Compressive Force Deflection (CFD) value measured according to ASTM D3574 that is higher than the CFD value of a corresponding foam composition lacking the added polycarbonate polyol.

18. The method of clause 18, wherein the density of the foam composition comprising the added polycarbonate polyol is at least 10% lower than the density of a corresponding foam composition lacking the added polycarbonate polyol.

19. The method of clause 18, wherein the density of the foam with the added polycarbonate polyol is at least 20% lower than the density of a corresponding foam without the added polycarbonate polyol.

20. The method of clause 19, wherein the density of the foam with the added polycarbonate polyol is at least 25%, at least 30%, at least 40%, or at least 50% higher than the density of a corresponding foam without the added polycarbonate polyol.

21. The method of any of clauses 17-19, wherein the CFD value of the foam composition comprising the added polycarbonate polyol is at least 10% higher than the CFD value of a corresponding foam composition lacking the added polycarbonate polyol.

22. The method of clause 21, wherein the CFD value of the foam comprising the added polycarbonate polyol is at least 20%, at least 30%, at least 40%, or at least 50% higher than the CFD value of the corresponding foam without the added polycarbonate polyol.

23. The method of clause 1, wherein the polycarbonate polyol contains a primary repeat unit having the structure:

24. The method of clause 23, wherein the polycarbonate polyol contains a primary repeat unit having the structure:

25. the method of clause 24, wherein R¹Independently at each occurrence in the polymer chain is-H or-CH₃。

26. The method of clause 25, wherein the polycarbonate polyol is characterized in that it has an Mn of between about 500g/mol to about 20,000 g/mol.

27. The method of clause 26, wherein the polycarbonate polyol is characterized in that it has an Mn of between about 1,000g/mol to about 5,000 g/mol.

28. The method of clause 26, wherein the polycarbonate polyol is characterized in that it has an Mn of between about 1,000g/mol to about 3,000 g/mol.

29. The method of clause 28, wherein the polycarbonate polyol is characterized as having an Mn of about 1,000g/mol, about 1,200g/mol, about 1,500g/mol, about 2,000g/mol, about 2,500g/mol, or about 3,000 g/mol.

30. The method of clause 25, wherein the aliphatic polycarbonate polyol is characterized in that greater than 98%, greater than 99%, or greater than 99.5% of the chain ends are isocyanate-reactive groups.

31. The method of clause 25, wherein the isocyanate-reactive chain ends contain an-OH group.

32. A polyurethane foam composition comprising the reaction product of a polyol component and a polyisocyanate component, wherein the polyol component comprises a polycarbonate polyol resulting from the copolymerization of one or more epoxides and carbon dioxide, wherein the polycarbonate polyol is present in an amount from about 2 weight percent to about 50 weight percent of all polyols present in the polyol component, and characterized in that the foam composition comprising the added polycarbonate polyol has a Compressive Force Deflection (CFD) value measured according to ASTM D3574 that is higher than the CFD value of a corresponding foam composition lacking the polycarbonate polyol.

33. The polyurethane foam composition of clause 32, wherein the polyol component comprises one or more polyols selected from the group consisting of: polyether polyols, polyester polyols, aliphatic polyols, and mixtures of any two or more of these.

34. The polyurethane foam composition of clause 32, wherein the polyol component substantially comprises a polyether polyol.

35. The polyurethane foam composition of clause 32, wherein the polycarbonate polyol is present in an amount from about 5 weight percent to about 25 weight percent of all polyols present in the polyol component.

36. The polyurethane foam composition of clause 32, wherein the polycarbonate polyol is present in an amount from about 2 weight percent to about 10 weight percent of all polyols present in the polyol component.

37. The polyurethane foam composition of clause 32, wherein the polycarbonate polyol is present in an amount from about 10 weight percent to about 20 weight percent of all polyols present in the polyol component.

38. The polyurethane foam composition of clause 32, wherein the polycarbonate polyol is present in an amount from about 20 weight percent to about 30 weight percent of all polyols present in the polyol component.

39. The polyurethane foam composition of clause 32, wherein the polycarbonate polyol is present in an amount from about 30 weight percent to about 50 weight percent of all polyols present in the polyol component.

40. The polyurethane foam composition of clause 32, wherein the CFD value of the foam composition comprising the polycarbonate polyol is at least 10% higher than the CFD value of the corresponding foam composition lacking the polycarbonate polyol.

41. The polyurethane foam composition of clause 40, wherein the CFD value of the foam with the polycarbonate polyol is at least 20%, at least 30%, at least 40%, or at least 50% higher than the CFD value of the corresponding foam without the polycarbonate polyol.

42. The polyurethane foam composition of clauses 40 or 41, wherein the CFD values are normalized against the densities of the foam compositions being compared.

43. The polyurethane foam composition of clauses 40 or 41, wherein the foam composition is formulated such that the foam composition comprising the added polycarbonate polyol and a corresponding foam composition lacking the added polycarbonate polyol have substantially the same density.

44. The polyurethane foam composition of clause 32, wherein the foam composition comprises a flexible polyurethane foam.

45. The polyurethane foam composition of clause 32, wherein the foam composition comprises a viscoelastic polyurethane foam.

46. The polyurethane foam composition of clause 32, wherein the foam composition comprises a rigid polyurethane foam.

47. The polyurethane foam composition of clause 32, wherein the foam composition comprising the polycarbonate polyol has a density measured according to ASTM D3574 that is lower than the density of a corresponding foam composition lacking the polycarbonate polyol.

48. The polyurethane foam composition of clause 47, wherein the density of the foam comprising the polycarbonate polyol is at least 10% lower than the density of a corresponding foam composition lacking the added polycarbonate polyol.

49. The polyurethane foam composition of clause 47, wherein the density of the foam with the added polycarbonate polyol is at least 20%, at least 30%, at least 40%, or at least 50% higher than the CFD value of the corresponding foam composition without the added polycarbonate polyol.

50. The polyurethane foam composition of clauses 47-49, wherein the measured CFD value is at least 10% higher than the CFD value of a corresponding foam composition lacking the polycarbonate polyol.

51. The polyurethane foam composition of clause 50, wherein the CFD value of the foam with the polycarbonate polyol is at least 20%, at least 30%, at least 40%, or at least 50% higher than the CFD value of the corresponding foam without the added polycarbonate polyol.

52. The polyurethane foam composition of clause 32, wherein the polycarbonate polyol contains a primary repeat unit having the structure:

53. The polyurethane foam composition of clause 32, wherein the polycarbonate polyol contains a primary repeat unit having the structure:

54. the polyurethane foam composition of clause 32, wherein R¹Independently at each occurrence in the polymer chain is-H or-CH₃。

55. The polyurethane foam composition of clause 54, wherein the polycarbonate polyol is characterized in that it has an Mn of between about 500g/mol to about 20,000 g/mol.

56. The polyurethane foam composition of clause 55, wherein the polycarbonate polyol is characterized in that it has an Mn of between about 1,000g/mol to about 5,000 g/mol.

57. The polyurethane foam composition of clause 55, wherein the polycarbonate polyol is characterized in that it has an Mn of between about 1,000g/mol to about 3,000 g/mol.

58. The polyurethane foam composition of clause 55, wherein the polycarbonate polyol is characterized in that it has an Mn of about 1,000g/mol, about 1,200g/mol, about 1,500g/mol, about 2,000g/mol, about 2,500g/mol, or about 3,000 g/mol.

59. The polyurethane foam composition of clause 55, wherein the polycarbonate polyol is characterized in that greater than 98%, greater than 99%, or greater than 99.5% of the chain ends are isocyanate-reactive groups.

60. The polyurethane foam composition of clause 59, wherein the isocyanate-reactive chain ends comprise-OH groups.

61. A seat foam comprising the reaction product between an isocyanate component and a polyol component, wherein the polyol component comprises from about 5 weight percent to about 20 weight percent of a polycarbonate polyol having a primary repeat unit of the structure:

wherein the content of the first and second substances,

R¹independently at each occurrence in the polymer chain is-H or-CH₃；

The polycarbonate polyol has an Mn between about 1,000g/mol to about 5,000 g/mol; and is

The polycarbonate polyols are characterized in that more than 99% of the chain ends are groups which are reactive toward isocyanates.

62. A viscoelastic foam article comprising the reaction product between an isocyanate component and a polyol component, wherein the polyol component comprises from about 5 weight percent to about 20 weight percent of a polycarbonate polyol having a primary repeat unit of the structure:

wherein the content of the first and second substances,

R¹independently at each occurrence in the polymer chain is-H or-CH₃；

Claims

1. A method for increasing the load bearing properties of a polyurethane foam composition comprising the reaction product of a polyol component and a polyisocyanate component, the method comprising the step of incorporating into the polyol component a polycarbonate polyol derived from the copolymerization of one or more epoxides and carbon dioxide, wherein the polycarbonate polyol is added in an amount from about 2 weight percent to about 50 weight percent, from about 5 weight percent to about 25 weight percent, from about 2 weight percent to about 10 weight percent, from about 10 weight percent to about 20 weight percent, from about 20 weight percent to about 30 weight percent, from about 30 weight percent to about 50 weight percent of all polyols present in the polyol component.