WO2024215452A1

WO2024215452A1 - Copolymer polyols and methods thereof

Info

Publication number: WO2024215452A1
Application number: PCT/US2024/020697
Authority: WO
Inventors: Anantha Narayana Iyer KRISHANAN; Lin TZU-PIN; Carlos R. LOPEZ-BARRON; Eryn LEE; Jonathan J. SCHAEFER; Matthew W. Holtcamp
Original assignee: ExxonMobil Technology and Engineering Co
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 2023-04-10
Filing date: 2024-03-20
Publication date: 2024-10-17
Anticipated expiration: 2025-10-10

Abstract

The present disclosure relates to copolymer polyols, polyurethanes made using copolymer polyols, and methods thereof. In some embodiments, a copolymer is represented by Formula (I), Formula (II), Formula. (Ill), or Formula (IX) wherein each of Q¹and Q² is independently hydrogen (A), (B) or (C); each instance of X is independently oxygen or sulfur; each instance of R^a and R^b is independently hydrogen, ether, hydrocarbyl, or substituted hydrocarbyl, wherein R^a and R^b may combine to form a five-membered, six-membered, or seven- membered ring; n is zero a. positive integer of about 1 to about 100; each of m and p is independently a positive integer of 1 to 100 (m may be zero); and each instance of R^c is independently alkylene, vinylene, ether, carbonyl -containing hydrocarbon, or alkanoate.

Description

TITLE: Copolymer Polyols and Methods Thereof

Inventors: Krishnan Iyer; Tzu-Pin Lin, Carlos R. Lopez-Barron, Eryn Lee, Jonathan J. Schaefer, Matthew W. Holtcamp

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of USSN 63/495, 196 filed April 10, 2023 and is incorporated by reference in its entirety.

FIELD

[0002] The present disclosure relates to copolymer polyols, polyurethanes made using copolymer polyols, and methods thereof.

BACKGROUND

[0003] Thermoplastic polyurethane elastomers (TPUs) are of industrial importance because of the excellent balance of mechanical properties and thermoplastic processability TPUs can be produced via the reaction of polyols (typically polyester or polyether homopolymer polyols), diisocyanate, and a short-chain diol (chain extenders). The hardness of a TPU is determined via the ratio of hard segment (reaction of chain extender with diisocyanate) to soft segment (reaction of polyol with diisocyanate).

[0004] The majority of polyols used for TPU include polyether polyols produced by the catalytic living ring opening polymerization of propylene oxide and/or ethylene oxide in the presence of multifunctional alcohols. Preparation of polyether carbonate polyols by catalytic reaction of alkylene oxides (epoxides), alcohol/alcohol and CO₂ has been studied for over 40 years. W02.003/014186 discloses DMC catalyzed polyether polyols with two different epoxides with alteration of the ratio of epoxides. W02008/058913 discloses flexible polyurethane foams using polyether-carbonate polyols prepared by DMC catalysis, where the polyether carbonate polyol have a block of pure epoxide units such as propylene oxide at chain ends. EP2714770 discloses DMC -catalyzed polyether carbonate polyols having a mixed block composed of two different epoxides in a molar ratio of 15/85 to 60/40

[0005] Nonetheless, current polyether carbonate polyols have substantial disadvantages in that exchanging a polyether polyol for a polyether carbonate polyol in a polyurethane formulation results in an overall formulation that has to be modified substantially to achieve good properties and processability. For example, plasticizers are added, but, in addition to hardness changes and regulatory pressures, plasticizers can bloom or be extracted from such compositions in which case the hardness of the composition can increase to an unacceptable level In addition, the current approach to producing soft TPUs less than 80 Shore A by reducing hard segment content produces tacky, poorly solidifying TPUs that exhibit sever shrinkage

[0006] Another kind of soft TPU is plasticizer-free soft TPU. However, the products with hardness of less than 60 Shore A are absent from the market despite a high demand because processes to form the TPUs are too expensive and/or the mechanical properties of such a TPU are not sufficient for market, demand.

[0007] Additionally, when polycarbonate polyol and polyether polyol are physically blended to produce polyurethanes, there is poor phase mixing and the TPUs produced have significantly reduced physical properties. Therefore, it is desirable to be able to replace or blend the polyether polyol and polycarbonate or polyether carbonate polyol for producing TPU with exceptional properties

[0008] Lastly, compression molding of TPUs would be valuable due to some advantageous properties provided by TPUs However, conventional polyurethanes can suffer from low temperature stability (due to high temperature provided by a compression molding process).

[0009] There is a need for producing block copolymers of polyols that reduce or eliminate challenges with TPU properties and processability.

[0010] References for citing in an Information Disclosure Statement (37 C.F.R. 1.97(h)): W02003/014186; W02008/058913; EP2714770; U.S. 2016/0122465.

SUMMARY

[0011] The present disclosure relates to copolymer polyols, polyurethanes made using copolymer polyols, and methods thereof.

[0012] In some embodiments, a copolymer is represented by Formula (I), Formula (II), Formula (III), or Formula (IX):

wherein: each of Q^l and Q² of Formula (II) is independently hydrogen

,

each of Q¹ and Q² of Formula (I) and (III) is independently hydrogen, -XH,

each instance of X is independently oxygen or sulfur; each instance of R^a and R^b is independently hydrogen, substituted or unsubstituted ether, or substituted or unsubstituted hydrocarbyl, wherein R^a and R^b may combine to form a substituted or un substituted five-membered, six-membered, or seven-membered ring; n is zero or a positive integer of about 1 to about 300; m is zero or a positive integer of about 1 to about 300; p is a positive integer of about 1 to about 300; q is zero or 1; each instance of R^c is independently substituted or unsubstituted alkylene, substituted or unsubstituted vinylene, substituted or unsubstituted ether, substituted or unsubstituted carbonylcontaining hydrocarbon, or substituted or unsubstituted alkanoate, wherein the copolymer of Formula (I), (II), (III), and (IX) is independently a block copolymer or random copolymer; and each instance of E is independently an oxygen, sulfur, or methylene (CH?)

[0013] In some embodiments, a method of forming a polyurethane includes introducing a catalyst with a copolymer of the present disclosure, a diisocyanate and a chain extender.

[0014] In some embodiments, a polyurethane includes di isocyanate units, chain extender units, and copolymer units, the copolymer units being copolymer polyol units of the present disclosure.

BRIEF DESCRIPTION GF THE DRAWINGS

[0015] FIG. 1 is a graph illustrating weight percentages of different units of copolymers, according to an embodiment.

[0016] FIG. 2 is a graph illustrating stress-strain curves obtained for PCL/PCHC-based TPUs according to tensile test (Method A), according to an embodiment.

[0017] FIG. 3 is a graph illustrating plots of shore A and glass transition temperature (Tg, °C) versus percentage of PCHC in polyol (PCL + PCHC), according to an embodiment.

[0018] FIG. 4 illustrates x-ray scattering images of AH 1590-17, illustrating the occurrence of strain-induced-crystallization, according to an embodiment.

[0019] FIG 5 illustrates AFM and SAXS images illustrating the bi-continuous structures in AH1590-17, according to an embodiment.

DETAILED DESCRIPTION

Definitions

[0020] For the purposes of the present disclosure and the claims thereto, the new numbering scheme for the Periodic Table Groups is used as described in Chemical and Engineering News, v.3(5), pg. 27 (1985). For example, a “group 4 metal” is an element from group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.

[0021] The terms “substituent,” “radical,” “group,” “substituent,” and “moiety” may be used interchangeably.

[0022] The term “heteroatom” refers to any group 13-17 element, excluding carbon. A heteroatom may include B, Si, Ge, Sn, N, P, As, O, S, Se, Te, F, Cl, Br, and I. The term “heteroatom” may include the aforementioned elements with hydrogens attached, such as BH, BH₂, S1H₂, OH, NH, NH₂, etc The term “substituted heteroatom” describes a heteroatom that has one or more of these hydrogen atoms replaced by a hydrocarbyl or substituted hydrocarbyl group(s).

[0023] The term “hydrocarbon” is a class of compounds consisting of the elements carbon (C) and hydrogen (H) only.

[0024] The term "hydrocarbyl " means a univalent group formed by removing a hydrogen atom from a hydrocarbon.

[0025] Unless otherwise indicated, (e.g., the definition of "substituted hydrocarbyl", "substituted aromatic", etc.), the term “substituted” means that at least one hydrogen atom has been replaced with at least one non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom containing group, such as halogen (such as Br, Cl, F or I) or at least one functional group such as -NR* ₂, -OR*, -SeR*, -TeR*, -PR* ₂, -AsR*2, -SbR*₂, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*₃, -PbR*₃, where each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join together to form a substituted or un substituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.

[0026] The term "substituted hydrocarbyl" means a hydrocarbyl radical in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one heteroatom (such as halogen, e.g., Br, Cl, F or I) or heteroatom-containing group (such as a functional group, e.g., - NR*2, -OR*, -SeR*, -TeR*, -PR*₂, -AsR*₂, -SbR*₂, -SR*, -BR*₂, -SiR*₃, -GeR*₃, -SnR*₃, - PbR*3, where each R* is independently a hydrocarbyl or halocarbyl radical, and two or more R* may join togetherto form a substituted or un substituted completely saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring. The term "hydrocarbyl substituted phenyl" means a phenyl group having 1, 2, 3, 4 or 5 hydrogen groups replaced by a hydrocarbyl or substituted hydrocarbyl group. For example, the "hydrocarbyl substituted phenyl" group can be represented by the formula:

where each of R^a, R^b, R^c, R^d, and R^e can be independently selected from hydrogen, C₁-C₄₀ hydrocarbyl or C₁-C₄₀ substituted hydrocarbyl, a heteroatom or a heteroatom -containing group (provided that at least one of R^a, R^b, R^c, R^d, and R^e is not H), or two or more of R^a, R^b, R^c, R^d, and R^e can be joined together to form a C4-C62 cyclic or polycyclic hydrocarbyl ring structure, or a combination thereof.

[0027] The term "non-halogenated” excludes Group 17 elements (e.g., F, Cl, Br, or I). For example, the term "non-halogenated substituted hydrocarbyl" means a substituted hydrocarbyl radical that does not comprise any Group 17 element.

[0028] The term "substituted aromatic," means an aromatic group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.

[0029] The term "substituted phenyl," mean a phenyl group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group

[0030] The term "tri-substituted borane" means a borane group having 3 hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.

[0031 ] The terms "tri-substituted phosphine" or “tertiary' phosphine” means a phosphine group having 3 hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group.

[0032] The term “substituted adamantyl” means an adamantyl group having 1 or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom or heteroatom containing group. The terms “alkoxy” and “alkoxide” mean an alkyl or aryl group bound to an oxygen atom, such as an alkyl ether or aryl ether group/radical connected to an oxygen atom and can include those where the alkyl/aryl group is a C₁ to C10 hydrocarbyl (also referred to as a hydrocarbyloxy group). The alkyl group may be straight chain, branched, or cyclic. The alkyl group may be saturated or unsaturated. Examples of suitable alkoxy radicals can include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, phenoxy.

[0033] The term "aryl" or "aryl group" means an aromatic ring and the substituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl, 4 -bromo-xylyl. Likewise, heteroaryl means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O, or S. As used herein, the term "aromatic" also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic; likewise the term aromatic also refers to substituted aromatics.

[0034] The term "arylalkyl" means an aryl group where a hydrogen has been replaced with an alkyl or substituted alkyl group. For example, 3,5'-di-tert-butyl-phenyl indenyl is an indene substituted with an arylalkyl group. When an arylalkyl group is a substituent on another group, it is bound to that group via the aryl.

[0035] The term "alkylaryl" means an alkyl group where a hydrogen has been replaced with an aryl or substituted aryl group For example, phenethyl indenyl is an indene substituted with an ethyl group bound to a benzene group. When an alkylaryl group is a substituent on another group, it is bound to that group via the alkyl.

[0036] The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has six ring atoms and tetrahydrofuran has 5 ring atoms.

[0037] A heterocyclic ring is a ring having a heteroatom in the ring structure as opposed to a heteroatom substituted ring where a hydrogen on a ring atom is replaced with a heteroatom. For example, tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom- substituted ring. Other examples of heterocycles may include pyridine, imidazole, and thiazole.

[0038] The terms “hydrocarbyl radical,” “hydrocarbyl group,” or “hydrocarbyl” may be used interchangeably and are defined to mean a group consisting of hydrogen and carbon atoms only. For example, a hydrocarbyl can be a C₁-C₁₀₀ radical that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic. Examples of such radicals may include, but are not limited to, alkyl groups such as methyl, ethyl, propyl (such as n-propyl, isopropyl, cyclopropyl), butyl (such as n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl), pentyl (such as iso-amyl, cyclopentyl) hexyl (such as cyclohexyl), octyl (such as cyclooctyl), nonyl, decyl (such as adamantyl), undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, or tricontyl, and and groups, such as phenyl, benzyl, and naphthyl.

[0039] The term “vinylene” or “1,2-di-substituted vinylene” means

(i) an olefin having the following formula:

(ii) an olefin having the follwing formula:

(iii) a mixture of (i) and (ii) at any proportion thereof, wherein R¹ and R² are each, independently, a hydrocarbyl group, such as saturated hydrocarbyl group such as alkyl group.

[0040] For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising a monomer (the monomer present in such polymer or copolymer is the polymerized form of the monomer). For example, when a copolymer is said to have a "caprolactone" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from caprolactone in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer. A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. A “copolymer” is a polymer having two or more mer units that are different from each other. A “terpolymer” is a polymer having three mer units that are different from each other. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like. “Different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. A "polylactone" is a polymer where the mer unit(s) in the polymer are derived from one or more lactones (where the lactone mer units may be ring opened) A "caprolactone polymer" or "caprolactone copolymer" is a polymer or copolymer comprising at least 50 mol% of one or more caprolactone derived units (such as caprolactone, decalactone, or methylcaprolactone).

[0041] As used herein. Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity index (PDI), is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g , Mw, Mn, Mz) are reported in units of g/mol (g mol^-1).

[0042] A “catalyst system” is a combination of at least one catalyst compound, an initiator, an optional co-activator, an optional chain transfer reagent, and an optional support material. The terms “catalyst compound” and “catalyst complex” are used interchangeably. A polymerization catalyst system is a catalyst system that can polymerize monomers to polymer. Furthermore, catalyst compounds represented by formulae herein embrace both neutral and ionic forms of the catalyst compounds and activators.

[0043] In the description herein, the catalyst may be described as a catalyst, catalyst compound, or a catalyst complex, and these terms are used interchangeably.

[0044] The following abbreviations may be used herein: Me is methyl, Et is ethyl, Bu is butyl, Oct is octyl, Ph is phenyl, Bz and Bn are benzyl (i.e., CH₂Ph), THF (also referred to as thf) is tetrahydrofuran, RT is room temperature (and is about 23°C unless otherwise indicated).

[0045] The term “diastereomers” are defined as non-mirror image, non-identical stereoisomers. They occur when two or more stereoisomers of a compound have different configurations at one or more (but not all) of the equivalent (related) stereocenters and are not mirror images of each other.

[0046] The present disclosure relates to copolymer polyols, polyurethanes made using copolymer polyols, and methods thereof.

[0047] In some embodiments, a copolymer is represented by Formula (I), Formula (II), Formula (III), or Formula (IX):

wherein: each of Q^l and Q² of Formula (II) is independently hydrogen,

each of Q¹ and Q² of Formula (I) and (III) is independently hydrogen, -XH,

each instance of X is independently oxygen or sulfur; each instance of R^a and R^b is independently hydrogen, substituted or unsubstituted ether, or substituted or unsubstituted hydrocarbyl, wherein R^a and R^b may combine to form a substituted or unsubstituted five-membered, six-membered, or seven -membered ring, n is zero or a positive integer of about 1 to about 300; m is zero or a positive integer of about 1 to about 300; p is a positive integer of about 1 to about 300, q is zero or 1; each instance of R^c is independently substituted or unsubstituted alkylene, substituted or unsubstituted vinylene, substituted or unsubstituted ether, substituted or unsubstituted carbonylcontaining hydrocarbon, or substituted or unsubstituted alkanoate, wherein the copolymer of Formula (I), (II), (III), and (IX) is independently a block copolymer or random copolymer; and each instance of E is independently an oxygen, sulfur, or methylene (CH₂).

[0048] In some embodiments, a method of forming a polyurethane includes introducing a catalyst with a copolymer of the present disclosure, a diisocyanate and a chain extender.

[0049] In some embodiments, a polyurethane includes di isocyanate units, chain extender units, and copolymer units, the copolymer units being copolymer polyol units of the present disclosure. [0050] Polyurethanes comprise three main units. Unit A: a. diisocyanate (such as methylene diphenyl diisocyanate MDI), Unit B: a chain extender (such as di-, tri-, or tetra-alcohol), and Unit C: a conventional polyol that is not derived from carbon dioxide (such as poly tetramethylene oxide PTMO, or polycaprolactone PCL).

[0051] Polyurethanes of the present disclosure can include Units A, B, optionally C, and at least one copolymer polyol unit selected from the group of Formula (IB), Formula (IIB), Formula (IIIB), or Formula (IXB):

wherein: each instance of X is independently oxygen or sulfur; each instance of R^a and R^b is independently hydrogen, substituted or unsubstituted ether, or substituted or unsubstituted hydrocarbyl, wherein R^a and R^b may combine to form a substituted or unsubstituted five-membered, six-membered, or seven-membered ring; n is zero or a positive integer of about 1 to about 300; m is zero or a positive integer of about 1 to about 300; p is a positive integer of about 1 to about 300, q is zero or 1; each instance of R^c is independently substituted or unsubstituted alkylene, substituted or unsubstituted vinylene, substituted or unsubstituted ether, substituted or unsubstituted carbonylcontaining hydrocarbon, or substituted or unsubstituted alkanoate, each instance of E is independently an oxygen, sulfur, or methylene (CH₂), wherein a wavy line indicates a point of bonding to another unit of the polyurethane, wherein the copolymer polyol unit is a block (b) copolymeric unit or a random (r) copolymeric unit.

[0052] In some embodiments, the introduction of copolymer polyol units of the present disclosure (e.g., of Formula (IB), (IIB), (IIIB), or (IXB)) (to form the new polyurethane) results in improved mechanical properties, lower Shore A values (softer polymers), and better oxidation resistance when compared to the conventional incumbent polyurethanes

[0053] Scheme 1 illustrates non-limiting examples of diisocyanate (Unit A), chain extender (Unit B), conventional polyol (unit C), and copolymer polyols of the present disclosure (Units D,

Scheme 1

Unit F example: Formula (XX):

(Formula (XX))

[0054] R^a and R^b of the copolymer polyols of Scheme 1 are defined as R^a and R^b of Formula (I), (II), (III), and (IX) above. Each of n, o, p, q, r, s, t, u, and v of Scheme 1 is independently a positive integer of about 1 to about 300, about 1 to about 100, such as about 1 to about 50, such as about 1 to about 25, such as about 1 to about 10, such as about 1 to about 5. In such embodiments of Scheme 1, the Units may include the following: include, but not limited to, methylene diphenyl diisocyanate (MDI),

1.4-diisocy anatobutan e (BDI ), 1 ,6-diisocyanatohexane, 1 ,3-diisocyanatomethylbenzene,

1.5-diisocyanatonaphthalene, isophorone diisocyanate (IPDI), methylene bis-(4-cyciohexy]isocyanate) (HMDI), lysine methyl ester diisocyanate (LDI), glycolide-ethylene glycol -glycolide isocyanate.

[0056] Unit B (chain extender): a di-, tri-, tetra-, penta-alcohol, or a di-, tri-, tetra-, penta-amine. Examples include, but not limited to, 1 ,4-butane-diol, 1,1,1 -tri s(hydroxymetbyl)propane, pentaerythritol, 1,5-pentane-diol, 1,4-butanedi amine, ethylene diamine, diaminopropane, cyclohexane diphenylalanine.

[0057] Unit C (a conventional polyol): a conventional polyol is a polymer, featuring telechelic alcohol end-groups, that is not synthesized from copolymerization of carbon dioxide. Examples of a conventional polyol include a polyether such as poly tetramethylene oxide PTMO, a polyester such as polycaprolactone PCL, a polyolefin such as polyethylene PE or polybutadiene PBD.

[0058] Unit D (a polyalkylene carbonate PAC polyol or polyalkylene ether carbonate PAEC polyol): a polyalkylene carbonate polyol or polyalkylene ether carbonate polyol is a polymer featuring telechelic alcohol end-groups with a generic structure shown below. The polyol is derived from copolymerization of carbon dioxide and one epoxide. Examples can include polycyclohexene carbonate (PCHC), polyethyl glycidyl carbonate (PEGC), polybutylene carbonate (PBC), polypropylene carbonate (PPC). -

[0059] Unit E (a poiyaikylene carbonate FAC copolymer polyol or polyalkylene ether carbonate PAEC copolymer polyol): a polyalkylene carbonate copolymer polyol or polyalkylene ether carbonate copolymer polyol is a polymer featuring telechelic alcohol end-groups with a generic structure shown in Scheme 1. The copolymer polyol is derived from copolymerization of carbon dioxide and more than one epoxides.

[0060] Unit F (a Hock copolymer polyol of PAC or PAEC): a di-, tri- or multi-block copolymer comprising at least one block of PAC or PAEC. [0061] The term “hard segment” refers to the combined diisocyanate (Unit A) and chain extender (Unit B). For example, 20% hard segment (20% HS) means Units A and B sums up to

20 wt% of the total polyurethane weight

[0062] The term “soft segment” refers to the combined portions of polyols (Units C, D, E, and [0063] The present disclosure relates to copolymer polyols, polyurethanes made using copolymer polyols, and methods thereof.

[0064] In some embodiments, a copolymer is represented by Formula (I), Formula (II), or Formula (III):

wherein: each of Q¹ and Q² of Formula (II) is independently hydrogen,

each of Q¹ and Q² of Formula (I) and (III) is independently hydrogen, -XH,

each instance of X is independently oxygen or sulfur, each instance of R^a and R^b is independently hydrogen, substituted or unsubstituted ether, or substituted or unsubstituted hydrocarbyl, wherein R^a and R^b may combine to form a substituted or unsubstituted five-membered, six-membered, or seven-membered ring, n is zero or a positive integer of about 1 to about 300; m is zero or a positive integer of about 1 to about 300, p is a positive integer of about 1 to about 300; q is zero or 1; each instance of R^c is independently substituted or unsubstituted alkylene, substituted or unsubstituted vinylene, substituted or unsubstituted ether, substituted or unsubstituted carbonylcontaining hydrocarbon, or substituted or unsubstituted alkanoate; and each instance of E is independently an oxygen, sulfur, or methylene (CH₂), wherein the copolymer of Formula (I), (II), (III), and (IX) is independently a block copolymer or random copolymer.

[0065] In some embodiments, a method of forming a polyurethane includes introducing a catalyst with a copolymer of the present disclosure, a diisocyanate and a chain extender

[0066] In some embodiments, a method of forming a polyurethane includes polymerizing Units A, B, C (PTMO), and D (PCHC) of Scheme 1.

[0067] In some embodiments, a method of forming a polyurethane includes polymerizing Units A, B, C (PCI .), and I) (PCHC) of Scheme 1 .

[0068] In some embodiments, a method of forming a polyurethane includes polymerizing Units A, B, C (PTMO), and D (PEGC) of Scheme 1 [0069] In some embodiments, a method of forming a polyurethane includes polymerizing Units A, B, C (PCL), and D (PEGC) of Scheme 1 .

[0070] In some embodiments, a method of forming a polyurethane includes polymerizing Units A, B, C ( PCL), and I) (PBC) of Scheme 1.

[0071] In some embodiments, a method of forming a polyurethane includes polymerizing Units A, B, C (PCL), and D (PPC) of Scheme 1,

[0072] In some embodiments, a method of forming a polyurethane includes polymerizing Units A, B, and one D (PBO) of Scheme 1 ,

[0073] In some embodiments, a method of forming a polyurethane includes polymerizing Units A, B, and one D (PEGC) of Scheme 1

[0074] In some embodiments, a method of forming a polyurethane includes polymerizing Units A, B, and two D (PCHC and PBC) of Scheme 1.

[0075] In some embodiments, a method of forming a polyurethane polymerizing Units A, B, and two D (PCHC and PEGC) of Scheme 1.

[0076] In some embodiments, a method of forming a polyurethane includes polymerizing Units A, B, C (PCL), and E (PCHC and PBC) of Scheme 1.

[0077] In some embodiments, a method of forming a polyurethane includes polymerizing Units A, B, C (PCL), and E (PCHC and PEGC) of Scheme 1.

[0078] In some embodiments, a method of forming a polyurethane includes polymerizing Units A, B, and one F wherein F is a triblock copolymer polyol of PCHC-PCL-PCHC of Scheme 1.

[0079] In some embodiments, a polyurethane includes di isocyanate units, chain extender units, and copolymer units, the copolymer units being copolymer polyol units of the present disclosure. [0080] It has been discovered that TPUs having improved properties can be obtained by forming the TPU from a CO₂/epoxy -derived polyol. The CO₂/epoxy-derived polyol is further derived from a polymeric diol (e.g., one or more of polyether polyols, polycaprolactone polyols, polycarbonate polyols, or polyester polyols) and can have low poly dispersity and good processability for producing the TPU having improved properties. For example, triblock copolymers made via CO₂/epoxy and polymeric diol can have low molecular weights, narrow and monomodal molecular weight distributions (MWDs), high thermal stability, and hydroxyl end group functionality. Use of copolymer polyols of the present disclosure (e.g., to form polyurethanes) provide improved properties for soft polyurethanes, e.g., Shore A hardness less than 90. In addition, use of copolymer polyols of the present disclosure reduces or eliminates the need for producing physical blends of conventional polyols with the new copolymer polyols of the present disclosure. The reduction/elimination of such physical mixing and phase separation provides TPUs having excellent properties.

[0081] TPUs of the present disclosure can be produced in a one-step reaction by polymerization of: i) linear polyol, ii) organic diisocyanate, and iii) glycol chain extender (e.g , butanediol).

[0082] The composition of a tri block linear polyol can be independently selected from polyether, polycaprolactone, polylactone, polyalkylene carbonate (polycarbonate), or polyester, with molecular weight ranging of about 500 g/mol to about 80,000 g/mol.

[0083] Another advantage of polyols of the present disclosure is their ability to reduce hard segment ratio for producing soft TPUs without the challenges of sticking to a mold and tackiness. Although TPUs of the present disclosure can be soft, the TPUs have little tendency to stick to molds. Accordingly, TPUs of the present disclosure are advantageous for injection molding applications. Moreover, TPUs molded into articles can have good low-temperature properties and good mechanical properties, and do not harden substantially at low temperature, such as lower than -10°C. Such TPUs can be produced with hard segment content about 30% or less, such as about 20% or less, such as about 15% or less. In addition, TPUs of the present disclosure can be transparent, whereas comparative polyurethanes were found to be translucent (e.g., immediately or over time) making TPUs of the present disclosure useful for a wide variety of end use applications.

Polymerization Processes to Form Copolymer Polyols

[0084] In embodiments herein, polymerization processes to form copolymer polyols include one or more epoxide monomers, one or more of CO₂, COS, or CS₂, one or more polymeric diols, and optional chain extenders are contacted with one or more catalyst compositions, to form oxygen containing polymers, such as polyalkylene carbonates, polyalkylene ether carbonates, or polyether. Scheme 2

[0085] For Formulas (I), (II), (III), and (IX), each instance of X is independently oxygen or

X sulfur. Each of Q¹ and Q² is independently hydrogen, -XH,

Each of R^a and R^b is independently hydrogen, ether, hydrocarbyl, or substituted hydrocarbyl. such as, but not limited to, alkyl, aryl, arylalkyd, alkydaryl, alkenyl, alkynyl, and cycloalkyl. R³ and R^:1 may combine to form a five-membered, six-membered, or seven-membered cycloalkyl or aryl ring. In some embodiments, R^a and R^b combine to form a cyclopentyl, cyclohexyl, or cycloheptyl ring.

[0086] In some embodiments, R^a and R^b can be independently an alkyl, substituted alkyl, aryl, or substituted aryl group, such as a C₁ to C₅₀ (such as C₂ to C₃₀. such as C₃ to C₂₀) alkyl, C1 to C₅₀ (such as (C₂ to C₃₀, such as C₃ to C₂₀) substituted alkyl, C₅ to C₅₀ (such as C₆ to C₃₀. such as C_{6 t}o C₂₀) aryl, or C₅ to C₅₀ (such as C₆ to C₃₀, such as C₆ to C₂₀) substituted aryl group. In some embodiments, R^a and R” are independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl.

[0087] Each of R^a and R^b can independently be based on the epoxide monomer starting material (as described in more detail below) used to form the polymeric diol. For example, R^a and R^b can combine to form a cyclohexyl ring, n is zero or a positive integer (e.g., about 1 to about 300, such as about 1 to about 100, such as about 10 to about 70, such as about 15 to about 50, such as about 15 to about 25, alternatively about 25 to about 50). Each of p and m is independently a positive integer (e.g., about 1 to about 300, such as about 1 to about 100, such as about 10 to about 70, such as about 15 to about 50, such as about 15 to about 25, alternatively about 25 to about 50). m may be zero. Each instance of “X-R^c” is independently a monomeric unit of alkyl, vinylene, ether, carbonyl-containing alkyl, or alkanoate (such as lactone or other ester). R^c is independently alkyl, vinylene, ether, carbonyl-containing alkyl, or alkanoate.

[0088] In some embodiments, IV is alkylene, vinylene, ether, carbonyl-containing

each instance of X is independently oxygen or sulfur and n’ is a positive integer (e.g., about 1 to about 10, such as about 4 to about 8).

[0089] In embodiments herein, a polymeric diol is contacted with one or more epoxide monomers, one or more of CO₂, COS, and CS₂, and one or more catalyst compositions, to form copolymers, such as random copolymers, gradient copolymers, or block copolymers.

[0090] An embodiment relates to a method to produce polymers comprising: contacting a catalyst composition represented by the Formula (la) or (lb) (as shown below) with one or more epoxide monomers, one or more of CO₂, CO_S, or CS₂, a polymeric diol, and optional chain extenders to obtain a copolymer polyol of the present disclosure.

Copolymer Polyol Properties

[0091] Copolymer polyols provided by the present disclosure can have, for example, about 10 wt% to about 80 wt% of a polymeric diol content, such as about 30 wt% to about 50 wt%, such as about 35 wt% to about 50 wt%, or about 40 wt% to about 50 wt% of a polymeric diol, where wt% is based on the total weight of the copolymer polyol

[0092] Copolymer polyols of the present disclosure can have an Mw of about 500 g/mol to about 50,000 g/mol (such as about 1,000 g/mol to about 10,000 g/mol, such as about 1,500 g/mol to about 5,000 g/mol), as determined by gel permeation chromatography (GPC).

[0093] Copolymer polyols of the present disclosure can have an Mn of about 500 g/mol to about 45,000 g/mol (such as about 900 g/mol to about 9,000 g/mol, such as about 1,300 g/mol to about 4,500 g/mol), as determined by GPC.

[0094] Copolymer polyols of the present disclosure can have an Mw/Mn value of greater than about 1 to about 40 (alternately about 1.01 to about 20, alternately about 1 1 to about 10, alternately about 1.1 to about 2, about 1.2 to about 1.8, alternately about 1.3 to about 1.6), as determined by GPC.

[0095] Copolymer polyols of the present disclosure can have thermal stability of about 140°C to about 240°C (such as about 150°C to about 220°C, such as about 190°C to about 210°C) as determined by ASTM E1131 .

Epoxide Monomers

[0096] Epoxide monomers useful herein include epoxides, substituted epoxides, and isomers thereof. Examples of epoxides include, but are not limited to, cyclohexene oxide, cyclopentene oxide, methyl cyclohexene oxide, dimethyl cyclohexene oxide, ethyl cyclohexene oxide, vinyl cyclohexene oxide, vinyl cyclohexene dioxide, limonene oxide, limonene dioxide, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, pentene oxide, hexene oxide, heptane oxide, octene oxide, epichlorohydrin, glycidyl methyl ether, glycidyl ethyl ether, glycidyl n-butyl ether, glycidyl isobutyl ether, glycidyl allyl ether, glycidyl 2-ethylhexyl ether, glycidyl benzyl ether, glycidyl phenyl ether, norbornene oxide.

[0097] Exemplary epoxide monomers include cyclohexene oxide and vinyl cyclohexene oxide and their respective homologs and derivatives Optional Chain Extenders

[0098] In general, a chain extender allows the polymerization to produce additional polymer chains. Chain extenders can be used to produce additional polymer chains. Chain extenders can also be used to control the molecular weights. Chain extenders useful with the cataly st complexes can include alcohols (such as di-alcohols), carboxylic acids (such as dicarboxylic acids), carboxylates, or thio groups.

Polymeric Diols as Chain Extenders

[0099] A polymeric diol can be, for example, a polyester diol, a polyether diol, a polycarbonate diol, a polycaprolactone diol, or a combination thereof. A polymeric diol may be selected from any of the chemical classes of polymeric polyols used in polyurethane formulations.

[00100] A polymeric diol can be characterized by a number average molecular weight (Mn), for example, of about 250 g/mol to about 10,000 g/mol, of about 500 g/mol to about 9,000 g/mol, of about 1,000 g/mol to about 8,000 g/mol, or of about 2,000 g/mol to about 6,000 g/mol.

[00101] Polymeric diols can include hydroxyl terminal groups with at least one oxycarbonyl linkage and can include about 5 carbon atoms to about 20 carbon atoms. Suitable polymeric diols include polyesters, polyesteramides, polycarbonates, and polycaprolactones. A polymeric diol can include aliphatic polycarbonate diols, having, for example a molecular weight of about 500 g/mol to about 2,000 g/mol or about 500 g/mol to about 1,000 g/mol.

[00192] A polymeric diol can be a polyether diol. Polyether diols can include those having the structure:

where m can be an integer from 1 to 10, and n can be an integer from 5 to 50 or from 4 to 45. Suitable polyether diols include polytetrahydrofuran (poly(tetramethylene ether) glycol or polyltetram ethylene oxide)), where m is 4. Commercially available examples of polyether diols include Terathane® polyether glycols (Invista), which are blends of linear diols in which the hydroxyl groups are separated by repeating tetramethylene ether groups such as HO — ( — CH₂ — CH₂ — CH₂ — CH₂ — O)_n — H where 11 can be, for example, an integer from 4 to 45. A Terathane® poly ether glycol can be Terathane® 1000 (n averages 14), Terathane® 2000 (11 averages 27), Terathane® 2900 (polytetramethylene ether glycol, PTMEG), Terathane® 650 or a combination of any of the foregoing. Such polyether glycols have a molecular weight of about 950 g/mol to about 1,050 g/mol, of about 1,900 g/mol to about 2,100 g/mol, and of about 625 g/mol to about 675 g/mol, respectively. Other Terathane® polyether glycols may be used.

[00103] Suitable polyether glycols are also available from BASF under the tradename PolyTHF®.

[00104] In some embodiments, a polyether diol can have a weight average molecular weight of about 250 g/mol to less than about 2,900 g/mol. For example, a polyether diol can have a weight average molecular weight of about 300 g/mol to about 2,700 g/mol, of about 500 g/mol to about 2,500 g/mol, of about 650 g/mol to about 2,000 g/mol, of about 1 ,000 g/mol to about 1,800 g/mol, or about 1,000 g/mol to about 1,400 g/mol.

[00105] More than one type of polyether diol can be used. A polymeric diol can include a combination of polyether polyols having several different weight average molecular weights. A composition can include a mixture of polyether diols having several different glass transition temperatures. A polymeric diol can include a combination of different types of polymeric diols such as, for example, a combination of polyether diols and polyester diols

[00106] Examples of polymeric diols can include polyester glycols, polycaprolactone diols, polycarbonate diols and combinations thereof Polyester glycols can include the esterification products of one or more dicarboxylic acids having from four to ten carbon atoms, such as adipic acid, succinic acid, or sebacic acid, with one or more low molecular weight glycols having from two to ten carbon atoms, such as ethylene glycol, propylene glycol, di ethylene glycol, 1,4- butanediol, neopentyl glycol, 1,6-hexanediol, and 1,10-decanediol. Examples of suitable poly caprolactone diols include those prepared by condensing caprolactone in the presence of difunctional active hydrogen material such as water or low molecular weight glycols, for example ethylene glycol and propylene glycol. Examples of suitable polycaprolactone diols include commercially available materials designated as the CAPA® series from Solvay Chemical; such as CAPA® 2047A and CAPA® 2077A, and the polycaprolactone TONE® series from Dow Chemical, such as TONE® 0201, TONE® 0210, TONE® 0230, and TONE® 0241. A polycaprolactone diol can have a weight average molecular weight (Mn) of, for example, about 500 g/mol to about 2,000 g/mol, or about 500 g/mol to about 1,000 g/mol. Polyester diols include those included within the Desmophen® and Baycoll® product lines available from Covestro.

[00107] Examples of suitable polycarbonate diols include aliphatic polycarbonate diols, for example those based upon alkylene glycols, ether glycols, alicyclic glycols or combinations thereof The alkylene groups for preparing the polycarbonate diol can include about 5 to about 10 carbon atoms and can be straight chain, cycloalkylene, or combinations thereof. Examples of such alkylene groups include hexylene, octylene, decylene, cyclohexylene and cyclohexyl dimethyl ene. Suitable polycarbonate polyols can be prepared, for example, by reacting a hydroxy terminated alkylene glycol with a dialkyl carbonate, such as methyl, ethyl, n-propyl or n-butyl carbonate, or di aryl carbonate, such as diphenyl or dinaphthyl carbonate, or by reacting of a hydroxy -terminated alkylene diol with phosgene or bischloroformate, in a manner well-known to those skilled in the art. Examples of such polycarbonate diols include those commercially available as Ravecarb™ 107 from Enichem S.p.A. (Polimeri Europa), and polyhexylene carbonate diols, about 1000 number average molecular weight (Mn), such as 13410-1733 polycarbonate diol prepared from hexanediol, available from Stahl. Examples of other suitable polycarbonate diols that are commercially available include KM10-1122,

KM10-1667 (prepared from a 50/50 weight percent mixture of cyclohexane dimethanol and hexanediol) (commercially available from Stahl U.S.A. Inc.) and Desmophen® 2020E (Bayer Corp).

[00108] Examples of suitable polycarbonate diols also include polycarbonate-polyester diols Suitable polymeric diols include polycarbonate diols and polycarbonate-polyester diols such as Desmophen® C available from Covestro.

[00109] Polymeric diols can include dimer acid-based poly ester diols. For example, dimer acidbased diols can include Priplast™ dimer fatty acid-based polyester diols available from Croda Polymers & Coatings.

[00110] In some embodiments, polyol can be a powder, which helps with introducing the polyol into an extruder to promote the polymerization.

Polymerization Conditions for Forming Copolymer Polyols

[00111] Polymerization processes of the present disclosure can be carried out in any manner known in the art. Any suspension, homogeneous, bulk, or solution polymerization process known in the art can be used Such processes can be run in a batch, semi-batch, or continuous mode. Homogeneous polymerization processes are typically useful, such as homogeneous polymerization process where at least about 90 wt% of the product is soluble in the reaction media.) A bulk homogeneous process is also useful, such as a process where monomer concentration in all feeds to the reactor is 70 volume % or more. Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts typically found with the monomer).

[00112] A solution polymerization is a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends. A solution polymerization is typically homogeneous A homogeneous polymerization is one where polymer product is dissolved in the polymerization medium, such as about 80 wt% or more, about 90 wt.% or more or about 100% of polymer product is dissolved in the reaction medium. Such systems are preferably not turbid as described in Oliveira, J V. C , et al. (2000), Ind. Eng. Chem. Res., v.29, pg. 4627.

[00113] A bulk polymerization means a polymerization process in which the monomers and/or comonomers being polymerized are used as a solvent or diluent using little or no inert solvent as a solvent or diluent. A small fraction of inert solvent might be used as a carrier for catalyst and scavenger. A bulk polymerization system typically contains less than about 25 wt% of inert solvent or diluent, such as less than about 10 wt%, less than about 1 wt%, or about 0 wt%.

[00114] Suitable diluents/solvents for polymerization include inert liquids. Examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (Isopar™ fluids); perhalogenated hydrocarbons, such as perfluorinated C_4-10 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. In some embodiments, aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In another embodiment, the solvent is not aromatic, such as aromatics are present in the solvent at less than 1 wt%, such as less than 0.5 wt%, such as less than 0 wt% based upon the weight of the solvents. Suitable diluents/solvents for polymerization also include polar, heteroatom containing liquids such as tetrahydrofuran, dichloromethane, dimethoxy ethane.

[00115] In some embodiments, the feed concentration of the monomers and comonomers for the polymerization is 60 vol% solvent or less, such as 40 vol% or less, such as 20 vol% or less, based on the total volume of the feedstream, or no solvent. In some embodiments, the polymerization is run in a bulk process.

[00116] Polymerizations can be run at any temperature and/or pressure suitable to obtain the desired polymers (copolymer polyols). Typical temperatures and/or pressures include a temperature in the range of about 0°C to about 300°C, such as about 20°C to about 200°C, such as about 35°C to about 150°C, such as about 40°C to about 130°C, such as about 45°C to about 120°C; and at a pressure in the range of about 0.35 MPa to about 10 MPa, such as about 0.45 MPa to about 6 MPa, such as about 0.5 MPa to about 4 MPa.

[00117] In a typical polymerization, the run time of the reaction is up to 4,320 minutes, such as in the range of from about 3 minutes to about 1,440 minutes, such as from about 10 minutes to about 240 minutes.

[00118] Catalyst complexes described herein may be used to prepare random copolymers. In alternate embodiments, the catalyst complexes described herein may be used to prepare block copolymers, typically diblock and triblock copolymers. This may be done by sequential monomer addition to the same catalyst complexes or by sequential polymerization reactions with different catalysts. This may also be done by sequential monomer addition to multiple catalyst complexes or addition of new catalyst complexes and monomer in the same or different reaction zones.

[00119] The catalysts of the present disclosure can be introduced at a polymerization process which enables the copolymerization of the polymeric diol with epoxides/CO₂, COS, CS₂. The epoxide can be introduced before, after, or simultaneously with the CO₂, COS, CS₂.

[00120] In some embodiments, a polymerization reaction for catalyst composition represented by Formula (la) or (lb):

1) is conducted at temperatures of about 0°C to about 300°C (such as about 20°C to about 200°C, such as about 35°C to about 150°C, such as about 40°C to about 130%’);

2) is conducted at a pressure of atmospheric pressure up to about 10 MPa (such as about 0.35 to about 10 MPa, such as about 0.45 to about 6 MPa, such as about 0.5 to about 4 MPa);

3) is conducted in solvent, or may be conducted in neat epoxides (without or with added solvents such as dichloromethane or toluene);

4) the polymerization reaction is to be formed under an inert atmosphere such as nitrogen or argon;

5) occurs in one reaction zone; and

6) has a turnover number for the catalyst composition of about 100 or more, (such as at least about 200, such as at least about 500, such as at least about 5,000).

[00121] In some embodiments, the catalyst composition used in the polymerization includes no more than one catalyst complex. A "reaction zone” also referred to as a "polymerization zone" is a vessel where polymerization takes place, for example a batch reactor. When multiple reactors are used in either series or parallel configuration, each reactor is considered as a separate polymerization zone. For a multi-stage polymerization in both a batch reactor and a continuous reactor, each polymerization stage is considered as a separate polymerization zone In some embodiments, the polymerization occurs in one reaction zone. Room temperature is about 23°C unless otherwise noted.

[00122] Other additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, reducing agents, oxidizing agents, hydrogen, silanes, or chain transfer agents such as alcohols, polyols, amines, or carboxylic acids.

Catalysts

[00123] Catalysts of Formula (la) or (lb) or combinations thereof can catalyze the polymerization of one or more epoxides, one or more of CO₂, COS, and CS2, and polymeric diol. Phosphine-Borane Catalyst Complexes

[00124] Embodiments described herein relate to tertiary pnictogen-boranes catalyst complexes represented by the Formula (la).

[00125] Exemplary embodiments described herein relate to a tertiary' phosphine-borane catalyst complex represented by the Formula (la):

(la) wherein:

B* is a group 13 element, such as boron or aluminum, such as boron;

P constitutes a tertiary phosphine moiety wherein P is covalently bonded to Y, R³, and R⁴, and P is not directly bonded to more than two nitrogen atoms; each of R¹, R², R³, and R⁴ is independently a hydrocarbyl, a non-halogenated substituted hydrocarbyl group, or a heteroatom-containing group, each of R¹, R², R³, and R⁴ can optionally be a tri-substituted borane or tri-substituted phosphine moiety, R¹ and R², R³ and R⁴, R¹ and Y, R³ and Y, R¹ and R³, and R¹ and R² and R³ are optionally fused to form cyclic or multi cyclic rings; and

Y is a non-halogenated linking group having about 1 to about 50 non-hydrogen atoms, such as about 2 to about 40 non-hydrogen atoms, such as 3 to 10 non-hydrogen atoms, such as a trimethylene, a tetramethylene, a pentamethylene, a hexamethylene, a heptamethylene, an octamethylene,

In some embodiments of Formula (la), R¹, R², R³, R⁴, and Y do not have a Group 2. to 12 metal. In some embodiments of Formula (la), R¹, R², R³, R⁴, and Y do not have a Group 3 to 11 transition metal.

[00126] In some embodiments, no phosphorus atom is directly bond to more than two nitrogen atoms.

[00127] In some embodiments of Formula (la), R³ and/or R⁴ is a secondary alkyl, a tertiary’ alkyl, or R³ and R⁴ are fused to form cyclic or multi cyclic rings.

[00128] In some embodiments of Formula (la), R¹ , R², R³, and R⁴ are hydrocarbons that contain 0, 1 , or 2 B* moieties, and 0, 1 , or 2 P moieties.

[00129] In some embodiments of Formula (la), R¹, R², R ⁴, and R⁴ contain heteroatoms to form heteroatom-C or heteroatom -P or heteroatom-B* bonds.

[00130] In some embodiments of Formula (la), each R^!, R², R³, and R⁴ is independently an alkyl, substituted alkyl, aryl, or substituted aryl group, such as a C₁ to C₅₀ (such as C₂ to C₃₀. such as C₃ to C₂₀) alkyl, C₁ to C₅₀ (such as C₂ to C₃₀, such as C₃ to C₂₀) substituted alkyl, C₅ to C₅₀ (such as C₅ to C₃₀. such as C₅ to C₂₀) aryl, or C₅ to C₅₀ (such as C₆ to C₃₀. such as C₆ to C₂₀) substituted aryl group,

[00131] Alternately, in some embodiments of Formula (la), R¹, R², R³, and R⁴ are independently selected from methyl, ethyl, propyl, butyl, pentyl, neopentyl, adaraantyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, norbornyl, substituted norbornyl and isomers thereof.

[00132] In some embodiments of Formula (la), one or more of R¹ and R², R³ and R⁴, R¹ and Y, R³ and Y, R¹ and R³, and R¹ and R² and R³ are fused and may form saturated or aromatic cyclic or multi cyclic groups.

[00133] In some embodiments of Formula (la), one or more of R¹, R², R³, and R⁴ includes one or more catalyst compositions selected form the group consisting of catalyst compositions represented by the Formula (la).

[00134] In some embodiments of Formula (la), each Y is independently a hydrocarbyl group, or substituted hydrocarbyl group, a Group containing 14, 15, 16, or 17 heteroatom, or a substituted Group 13, 14, 15, 16, or 17 heteroatom (such as a silyl group, a substituted silyl group, oxygen group, sulfur group, nitrogen group or phosphine group) such as an alkyl, substituted alkyl, aryl, or substituted aryl group, such as a C₁ to C₅₀ (such as C₂ to C₃₀. such as C₃ to C ₃₀ alkyl. C₁ to C₅₀ (such as C₂ to C₃₀, such as C₃ to C₂₀) substituted alkyl, C₅ to C₅₀ (such as C₆ to C₃₀. such as C* to C₂₀) aryl, or C₅ to C₅₀ (such as C₆ to C₃₀, such as C₆ to C₂₀) substituted aiyl group.

[00135] Alternately, in some embodiments of Formula (la), each Y is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenylene, substituted phenylene (such as 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,8- naphthalene, methylphenylene and dimethylphenylene), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, norbornyl, substituted norbornyl and isomers thereof.

[00136] In some embodiments of Formula (la), each Y is independently -O-, (-CH₂-)n, where n is 1 to 50, alternately n is 2 to 30, alternately n is 3 to 12 (alternately n is 1, e.g., -CH₂-), -CR_2-, -SilR₂- -GeR₂-, -NR-(where each R is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, norbornyl, or substituted norbornyl.

[00137] In some embodiments of Formula (la), Y is a bridging group containing at least one Group 13, 14, 15, 16, or 17 element, in particular boron or a Group 14, 15, 16, or 17 element. Examples of suitable bridging groups include

R*₂CCR*₂, R*₂CCR*₂CR*2, R*2CCR*₂CR*₂CR*2, R*C=CR*, R*C=CR*CR*₂,

R*₂CCR*=CR*CR*₂, R*C-CR*CR*-CR*, R*C-CR*CR*₂CR*₂, R*₂CSiR*₂, R*₂SiSiR*₂, R*₂SiOSiR*₂, R*₂CSiR*₂CR*₂, R*₂SiCR*₂SiR*₂, R*C=CR*SiR*₂, R*₂CGeR*₂, R*₂GeGeR*₂, R*₂CGeR*₂CR*₂, R*₂GeCR*₂GeR*₂, RMSiGeR*?, R*OCR*GeR*₂, R*B, R*₂C-BR*, R*₂C- BR*-CR*₂, R*₂C-O -CR*₂, R*₂CR*₂C-O-CR*₂CR*₂, R*₂C-0 -CR*₂CR*₂, R*₂C O CR*-CR*, R*₂C-S-CR*2, R*₂CR*₂C-S-CR*₂CR*₂, R*₂C-S-CR*₂CR*₂, R*₂C-S-CR*=CR*, R*₂C--Se-CR*₂, R*₂CR*₂C-Se~CR*₂CR*₂, R*₂C-Se-CR*₂CR*₂, R*₂C-Se-€R*=CR*, R*₂C- N~CR*, R*₂C-NR*-CR*₂, R*₂C-NR*-CR*₂CR*₂₎ R*₂C-NR*-CR*=CR*, R*₂CR*₂C-NR*- CR*₂CR*2, RM' P cr R*₂C- -PR*- CR*2, O, S, Se. Te, XR*. PR*, AsR*, SbR*, O-O, S-S, R*N-NR*, R*P-PR*, 0-S, O-NR*, O-PR*, S-NR*, S-PR*, and R*N-PR*, where R* is hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituent and optionally two or more adjacent R* may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. Some examples for the bridging group Y include

Me₂SiOSiMe₂, and PBu. In some embodiments, Y is represented by the formula ER^y ₂ or (ER^y ₂)₂, where E is C, Si, or Ge, and each R^y is, independently, hydrogen, halogen, C₁ to C₂₀ hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a

substituted hydrocarbyl, and two R^y can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system. In some embodiments, Y is abridging group comprising carbon or silicon, such as dialkylsilyl , such as Y is selected from

, cyclotrimethylenesilylene (Si(CH₂)₃), cyclopentamethylenesilylene (Si(CH₂)₅.) and cyclotetramethylenesilylene (Si(CH₂)₄).

[00138] For Complex 1, R³ and R² formed a fused ring with boron namely

9-Borabicy cl o(3.3 l)nonane, R³ = R^{4 :;}= tert-butyl, Y ==^: trimethylene.

[00139] For Complex 2, R¹ and R² formed a fused ring with boron namely

9-Borabicy cl o(3.3. l)nonane, R^{3 ::::} R⁴ tert-butyl, Y ^:::: pentamethylene.

[00140] For Complex 3, R³ and R² formed a fused ring with boron namely

9-Borabicyclo(3.3. 1)nonane, R³ R⁴ = 1-adamantyl, Y =^: pentamethylene

[00141] For Complex 4, R¹ and R² formed a fused ring with boron namely

9-Borabicyclo(3.3. l)nonane, R³ and R⁴ formed a fused ring with phosphine namely 9~phosphabicyclo(3.3.1)nonane, Y = pentamethylene.

[00142] Specific examples of catalyst complexes useful herein are shown below as Complexes 1-27:

[00143] Additional catalyst structures of Formula (la) include:

Pnictogenium-Borane Catalyst Complexes

[00144] Exemplary embodiments described herein relate to a tertiary pnictogenium-borane catalyst complex represented by the Formula (lb):

where Pn is a group 15 pnictogen element, such as nitrogen or phosphorus, such as phosphorus:

Pn⁺ constitutes a cationic tertiary' pnictogenium moiety wherein the pnictogen is covalently bonded to one hydrogen atom, as well as non-hydrogen Y, R³ and R ^: groups;

(the number of pnictogenium moieties, Pn+) x Z = T x Q_;

B* is a group 13 element, such as boron or aluminum, such as boron,

Z is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; where if Z is greater than 1, then the catalyst units are present individually or are bound together in linear, branched or cyclic groups; T is 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10, indicating the anionic charge of X;

Q is I, 2, 3, 4, 5, 6, 7, 8, 9, or 10, indicating the number of X present; each of R¹, R², R³ and R¹ is independently a hydrocarbyl group, a non -halogenated substituted hydrocarbyl, or a heteroatoni -containing group, and can optionally be a tri -substituted borane or cationic tertiary pnictogenium moiety;

Y is independently a linking group having about 1 to about 50 non-hydrogen atoms, such as about 2 to about 40 non-hydrogen atoms, such as about 3 to about 10 non-hydrogen atoms, such as a trimethylene, a tetramethylene, a pentamethylene, a hexamethylene, a heptamethylene, an octamethylene, -CH₂CH₂Si(Me2)-CH₂CH₂-, or -CH₂(C₆H₄)-CH₂-; and

X is independently a mono-anionic group, a multi-anionic group, or a combination thereof. [00145] In some embodiments of Formula (Ib), R¹, R², R³ R⁴, and Y do not have a Group 2 to 12 metal. In some embodiments of Formula (lb), R¹, R², R³, R⁴, and Y do not have a Group 3 to 11 transition metal.

[00146] In some embodiments of Formula (Ib), R¹, R², R³, and R⁴ are hydrocarbons that contain

0, 1 , or 2 B* moi eties, and 0, 1, or 2 Pn moiety, and 0, 1 , or 2 Pn+.

[00147] In some embodiments of Formula (lb), R¹, R², R³, and R⁴ contain heteroatoms to form heteroatom-C or heteroatora-Pn or heteroatom-B* bonds.

[00148] In some embodiments of Formula (Ib), each R¹, R², R³, and R⁴ is independently an alkyl, substituted alkyl, aryl, or substituted aryl group, such as a C₁ to C₅₀ (such as C₂ to C₃₀. such as C₃ to C₂₀) alkyl. C₁ to C₅₀ (such as C₂ to C₃₀, such as C₃ to C₂₀) substituted alkyl, C₅ to C₅₀ (such as C₆ to C₃₀. such as C₆ to C₂₀) aryl, or C₅ to C₅₀ (such as C₆ to C₃₀, such as C₆ to C₂₀) substituted aryl group.

[00149] Alternately, in some embodiments of Formula (Ib), R¹, R², R³, and R⁴ are independently selected from methyl, ethyl, propyl, butyl, pentyl, neopentyl, adamantyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methyl cyclohexyl, norbomyl, substituted norbornyl and isomers thereof.

[00150] In some embodiments of Formula (lb), one or more of R¹ and R², R³ and R⁴, R¹ and Y, R³ and Y, R¹ and R³, and R¹ and R² and R³ are fused and may form saturated or aromatic cyclic or multicyclic groups [00151] In some embodiments of Formula (lb), one or more of R^l, R², R³ and R⁴ includes one or more catalyst compositions seiected from catalyst compositions represented by the Formula (I). [00152] In some embodiments of Formula (lb), Y can be a linking group of formula ~(CH₂)n- wherein n = 3 - 8, such as n = 4 - 6, such as n = 5.

[00153] In some embodiments of Formula (lb), each Y is independently a hydrocarbyl group, or substituted hydrocarbyl group, a group containing 14, 15, 16, or 17 heteroatom, or a substituted group 13, 14, 15, 16, or 17 heteroatom (such as a silyl group, a substituted silyl group, oxygen group, sulfur group, nitrogen group or phosphine group) such as an alkyl, substituted alkyl, aryl, or substituted aryl group, such as a C₁ to C₅₀ (such as C₂ to C₃₀ such as C₃ to C₂₀) alkyl, C₁ to C₅₀ (such as C₂ to C₃₀, such as C₃ to C₂₀) substituted alkyl, C₅ to C₅₀ (such as C₆ to C₃₀, such as C₆ to C₂₀) aryl, or C₅ to C₅₀ (such as (Y to C₃₀, such as (Y to C₂₀ ) substituted aryl group.

[00154] Alternately, in some embodiments of Formula (lb), each Y is independently selected from methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, hepta decylene, octadecylene, nonadecylene, eicosylene, heneicosylene, docosylene, tricosylene, tetracosyl ene, pentacosylene, hexacosylene, heptacosyl ene, octacosylene, nonacosylene, triacontylene, phenylene, substituted phenylene (such as 1,2-phenylene, 1,3- phenylene, 1 ,4---phenylene, 1,8-naphthalene, methylphenylene and dimethylphenylene), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, norbornyl, substituted norbornyl, or isomers thereof.

[00155] In some embodiments of Formula (lb), each Y is independently -O-, (-CH₂-)n, where n is 1 to 50, alternately n is 2 to 30, alternately n is 3 to 12 (alternately n is 1, e.g., -CH₂-), -CR₂-, -SiR.₂-, -GeR₂-, -NR-(where each R is independently methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, substituted phenyl (such as methylphenyl and dimethylphenyl), benzyl, substituted benzyl (such as methylbenzyl), naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, norbornyl, or substituted norbornyl.

[00156] In some embodiments of Formula (lb), Y is a bridging group containing at least one Group 13, 14, 15, 16, or 17 element, in particular boron or a Group 14, 15, 16, or 17 element. Examples of suitable bridging groups include

R*₂CCR*₂, R*₂CCR*₂CR*₂, R*2CCR*₂CR*₂CR*₂, R*C=CR*, R*C=CR*CR*₂,

R*₂CCR*=CR*CR*₂, R*C-CR*CR*-CR*, R*C-CR*CR*₂CR*₂, R*₂CSiR*₂, R*₂SiSiR*₂, R*₂SiOSiR*₂, R*₂CSiR*₂CR*₂, R*₂SiCR*₂SiR*₂, R*C=CR*SiR*₂, R*₂CGeR*₂, R*₂GeGeR*₂, R*₂CGeR*₂CR*₂, R*₂GeCR*₂GeR*₂, R*₂SiGeR*₂, R*(>CR*GeR*₂, R*B, R*₂C-BR*, R*₂C- BR*-CR*₂, R*₂C-O -CR*₂, R*₂CR*₂C-O-CR*₂CR*₂, R*₂C-O -CR*₂CR*₂, R*₂C O CR*-CR*, R*₂C-S-CR*₂, R*₂CR*₂C-S-CR*₂CR*₂, R*₂C-S-CR*₂CR*₂, R*₂C-S-CR*-CR*, R*₂C--Se-CR*₂, R*₂CR*₂C-Se~CR*₂CR*₂, R*₂C-Se-CR*₂CR*₂, R*₂C-Se-CR*=CR*, R*₂C- N-CR*, R*₂C-NR*-CR*₂, R*₂C-NR*-CR*₂CR*₂₎ R*₂C-NR*-CR*=CR*, R*₂CR*₂C-NR*- CR*₂CR*₂, RM' P cr R*₂C- -PR*- CR*2, O, S, Se. Te, XR*. PR*, AsR*, SbR*, O-O, S-S, R*N-NR*, R*P-PR*, 0-S, O-NR*, O-PR*, S-NR*, S-PR*, and R*N-PR* where R* is hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl substituent and optionally two or more adjacent R* may join to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. Examples for the bridging group Y can include CH₂, CH₂CH₂, SiMe₂, SiPh₂, SiMePh, _Si(CH2)3: Si(CH ₂)₄ 0, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me₂SiOSiMe₂, and PBu. In some embodiments, Y is represented by the formula ER^y, or (ER^y ₂)₂, where E is C, Si, or Ge, and each R^y is, independently, hydrogen, halogen. C₁ to C₂₀ hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl) or a C₁ to C₂₀ substituted hydrocarbyl, and two R^y can form a cyclic structure including aromatic, partially saturated, or saturated cyclic or fused ring system. In some embodiments, Y is a bridging group comprising carbon or silicon, such as dialkyl silyl, such as Y is selected from CH₂, CH₂CH₂, ( (CH ₃ )₂’. SiMe₂, Me₂Si-SiMe₂, cyclotrimethylenesilylene (Si(CH₂)₃), cyclopentamethylenesilylene (Si(CH₂)₅.) and cyclotetramethylenesilylene (Si(CH₂)₄).

[00157] In some embodiments of Formula (lb), X is a mono- or multi-anionic (such as tri -anionic) group that acts as an initiator for the polymerization Alternately, each X is independently a halide, an alkoxide, aryloxide, a carboxylate, a carbonate, a sulfate, a phosphate, di-alkoxide, di-aryloxide, a di-carboxylate, a di-carbonate, a di -sulfate, a di-phosphate (such as a di-carboxylate) or tri-alkoxide, tri-aryl oxi de, a tri-carboxylate, a tri-carbonate, a tri-sulfate, a tri-phosphate (such as a tri-carboxylate), or a combination thereof. Alternately, each X is independently a dicarboxylate (such as Norbornene di -carboxylate). Additionally, X can contain one or more than one alcohol groups (-OH) and thiol groups (-SH). X can contain a group 13 to 17 heteroatom, such as B, Si, Ge, Sn, N, P, As, O, S, Se, Te, or the aforementioned elements with hydrogens attached, such as BH, BH₂, SiH₂, OH, NH, NH₂, etc. X can be a substituted heteroatom, e.g., a heteroatom that has one or more of these hydrogen atoms replaced by a hydrocarbyl or substituted hydrocarbyl group! s). X can be a substituted group 13 to 16 heteroatom, such as -O(R*), -OS(O)₂(R*), -OS(O)₂CF3, -S(R*), -N(R*)2, -NH ( R*), -P(R*)₂, -PH(R*), -Si ( R * )3„ -SiH(R*)₂, -SiH₂(R* ), -Ge(R*)₃, -B(R* )₂, -BH(R*) wherein R* is hydrocarbyl or substituted hydrocarbyl, such as, but not limited to, arylalkyd, alkylaryl, alkenyl, alkynyl, cycloalkyl, and the like, and wherein two or more adjacent R* may join together to form a cyclic or polycyclic structure.

[00158] For Complex 1, R¹ and R² formed a fused ring with boron namely

9-Borabicyclo(3.3.1)nonane, R³ = R⁴ = cyclohexyl, Y = pentamethylene, X = Br.

[00159] For Complex 2, R³ and 2² formed a fused ring with boron namely

9-Borabicyclo(3.3, l)nonane, R³ " R^{4 :::} tert-butyl, Y ~ pentamethylene, X = Br.

[00160] For Complex 3, R³ = R² =cyclohexyl, R³ = R⁴ = tert-butyl, Y = pentamethylene, X - Br.

[00161] For Complex 4, R³ and R² formed a fused ring with boron namely 9-Borabicyclo(3.3, l)nonane, R³ and R⁴ formed a fused ring with phosphine namely 9-phosphabicyclo(3.3.1)nonane, Y “ pentamethylene, X == Br.

[00162] For Complex 5, R¹ and R² formed a fused ring with boron namely 9-Borabicyclo(3.3.1 [nonane, R^{3 :=:} R⁴ = 1-adamantyl, Y = pentamethylene, X ^:=: Br.

[00163] Specific examples of catalyst complexes useful herein are shown below:

[00164] Additional catalyst structures of Formula (lb) include:

[00165] In some embodiments, two or more different catalyst complexes are present in the catalyst system used herein. In some embodiments, two or more different catalyst complexes are present in the reaction zone where the process(es) described herein occur. It is optional to use the same initiator for the compounds, however, two different initiators can be used in combination.

[00166] The two catalyst complexes may be used in any ratio. Molar ratios of (A) catalyst complex to (B) catalyst complex can fall within the range of ( A:B) about 1 : 1000 to about 1000: 1, alternatively about 1 : 100 to about 500: 1 , alternatively about 1 : 10 to about 200: 1 , alternatively about 1 : 1 to about 100: 1, and alternatively about 1 : 1 to about 75: 1, and alternatively about 5: 1 to about 50: 1. The particular ratio chosen will depend on the exact complex chosen, the method of initiation, and the end product desired. In a particular embodiment, when using the two catalysts, useful mole percents, based upon the molecular weight of the catalysts, are about 10% to about 99.9% A to about 0.1% to about 90% B, alternatively about 25% to about 99% A to about 0.5% to about 50% B, alternatively about 50% to about 99% A to about 1% to about 25% B, and alternatively about 75% to about 99% A to about 1% to about 10% B.

Initiators

[00167] In some embodiments of Formula (la) or (lb), X is a mono- or multi-anionic (such as tri-anionic) group that acts as an initiator for the polymerization. Alternately, each X is independently a halide, alkoxide, carboxylate, sulfate, triflate, phosphate, di-alkoxide, di-aryl oxide, a di-carboxylate, a di-carbonate, a di -sulfate, a di-phosphate (such as a di-carboxylate), or tri-alkoxide, tri -aryl oxi de, a tri-carboxylate, a tri-carbonate, a tri-sulfate, a triphosphate (such as a tri-carboxylate), or a combination thereof examples of mono-anionic initiators:

examples of multi-anionic initiators:

Co- Activators

[00168] Co-activators may be used with the catalyst complexes. A co-activator is usually a Lewis acid or a Lewis base that, by itself does not catalyze the polymerization of CO₂/epoxide/polymeric diol. A co-activator may be used in conjunction with an initiator in order to form an active catalyst complex In some embodiments a co-activator can be pre-mixed with the catalyst complex before introduction into a reaction zone or may be introduced separately into the reaction zone. Compounds which may be utilized as co-activators include, for example, phosphonium halide and bis(tripheny[phosphine)iminium halide, or triethyl borane, tricyclohexyl borane, tri-n-hexyl borane, l,8-diazabicyclo[5.4.0]undec-7-ene, etc.

Polyurethanes and Syntheses Thereof

[00169] A copolymer polyol from Units C, D, E, or F (or combinations thereof) of the present disclosure (e.g., of Formula (I), (II), (III), (IX), or combinations thereof) can be reacted with a diisocyanate and optionally a chain extender (such as a diol other than the copolymer polyol) to form a polyurethane prepolymer of the present disclosure Polyurethane

[00170] A polyurethane can be produced using a copolymer polyol of the present disclosure.

[00171] As to the method for producing the polyurethane of the present disclosure by using a copolymer polyol, known polyurethane forming reaction conditions usually employed to produce a polyurethane can be used.

[00172] For example, a copolymer polyol can be reacted with a poly isocyanate and an optional chain extender at a temperature ranging from ambient temperature to 200°C, whereby the polyurethane can be produced.

[00173] Alternatively, the copolymer polyol of the present disclosure is first reacted with an excess of polyisocyanate to produce a prepolymer having an isocyanate group at one or both termini of the prepolymer, and the polymerization degree is further increased using a chain extender, whereby the polyurethane can be produced.

Polyisocyanates

[00174] Suitable diisocyanates for preparing polyurethane prepolymers of the present disclosure can include aliphatic diisocyanates, alicyclic aliphatic diisocyanates, aromatic diisocyanates, and combinations of any of the foregoing.

[00175] A diisocyanate can include a rigid diisocyanate, a flexible diisocyanate, or a combination thereof. The terms rigid diisocyanate and flexible or soft diisocyanate are relative and refer to the conformational degrees of freedom of the molecule. A rigid or hard diisocyanate refers to a diisocyanate that has no or few conformational degrees of freedom. An example of a rigid diisocyanate is 4,4'-methylene dicyclohexyl diisocyanate (H₁₂MDI). A flexible diisocyanate has more conformational degrees of freedom than a rigid diisocyanate. An example of a flexible diisocyanate, compared to H12MDI, is isophorone diisocyanate (IPD1). Tetramethyl xylene diisocyanate (TMXDI) is another example of a soft diisocyanate. Both fl exible diisocyanates and rigid diisocyanates are included within the scope of the hard segment.

[00176] Flexible diisocyanates can be characterized by diisocyanates having a linear structure. Flexible diisocyanates generally include aliphatic diisocyanates. Examples of suitable flexible diisocyanates include 1,6-hexam ethylene diisocyanate, 1.5-diisocyanato-2-methylpentane, 1,6- diisocyanato-2,2,4-trimethylhexane, l,6-diisocyanato-2,4,4-trimethylhexane, 1,4- diisocyanatobutanone, tri-methyl-hexamethylene dii socyanate,

1 ,8-diisocyanatooctane, 1 , 12-diisocyanatododecane, 1 ,8-diiscyanto-2,4-dimethyloctane, and TMXDI. In TMXDI, the isocyanate is not bonded directly to the aromatic ring.

[00177] Flexible diisocyanates also include diisocyanates having a single aromatic or cycloaliphatic ring such as isophorone diisocyanate (IPDI), l,3-bis(isocyanato niethyl)cyclohexane, 1 ,4-bis(isocyanato methyl)cyciohexane, trans-l,4-cyclohexylene di isocyanate, and 2,4-diisocyanato-l -methyl cyclohexane.

[00178] A rigid diisocyanate can have a two aromatic or cycloalkane ring. Examples of rigid diisocyanates include 4,4-methylene dicyclohexyl diisocyanate, and bis(4-isocyanatocyclohexyl methane.

[00179] Suitable aliphatic diisocyanates for preparing polyurethane prepolymers provided by the present disclosure include, for example, isophorone diisocyanate (IPDI), tetramethyl xylene diisocyanate (TMXDI), 4,4'-methylene dicyclohexyl diisocyanate (H₁₂MDI), methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), 1,6-hexam ethylene diisocyanate (HDI), pentane, 1,5-diisocyanato-, and a combination of any of the foregoing.

[00180] Examples of other suitable aliphatic diisocyanates include l,5-diisocyanato-2- methylpentane, methyl -2, 6-diisocyanatohexanoate, bis(isocyanatomethyl)cyc1ohexane, 1 ,3-bis(isocyanatomethyl)cyclohexane, 2,2,4-trimethylhexane 1 ,6-dii socyanate,

2,4,4-trimethylhexane 1 ,6-dii socyanate, 2,5(6)-bis(isocyanatomethyl)cyclo[2.2.1.]heptane, 1,3,3- trimethyl-l-(isocyanatomethyl)-5-isocyanatocyclohexane, l,8-diisocyanato-2,4-dimethyloctane, octahydro-4, 7-methano- IH-indenedimethyl diisocyanate, and

1 ,1 ' -m et hy 1 enelris(4~i socy an atocy clohexane) .

[00181] Examples of suitable alicyclic aliphatic diisocyanates include isophorone diisocyanate (IPDI), 1,4-cyclohexyl diisocyanate (CHDI), methylcyclohexane diisocyanate, bi s(i socy anatom ethyl )cy cl ohexane, bi s(i socy anatocyclohexy1)m ethane, bis(isocyanatocyclohexyl)-2,2-propane, bis(i socy anatocy clohexyl)-1 ,2-ethane,

2-isocyanatometbyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-i socyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-3-(3-i socyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane, and 2- isocyanatomethy1-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane. [00182] Other examples of suitable alicyclic diisocyanates for preparing polyurethane prepolymers provided by the present disclosure include 2,2,4-trim ethylhexamethylene diisocyanate (TMDI), 1,6-hexam ethylene diisocyanate (HDI), l,l'-methylene-bis-(4- isocyanatocyclohexane), 4,4'-methylene-bis-(cyclohexyl diisocyanate) (4,4-methylene dicyclohexyl diisocyanate (H12MDI)), hydrogenated toluene diisocyanate, 4,4’-isopropylidene-bis-(cyclohexyl isocyanate), 1,4-cyclohexyl diisocyanate (CHDI), 4,4'-dicyclohexylmethane diisocyanate (Desmodur® W), and 3-isocyanato methyl-3,5,5- trimethyl cyclohexyl di isocyanate (IPDI). Mixtures and combinations of these diisocyanates can also be employed

[00183] Compositions prepared using acyclic and alicyclic aliphatic diisocyanates may exhibit greater stability relative to compositions prepared using other di isocyanates when exposed to ultraviolet (UV) light.

[00184] Examples of suitable aromatic diisocyanates in which the isocyanate groups are not bonded directly to the aromatic ring include bis(isocyanatoethyl)benzene, a,a,a',a'- tetramethy 1 xy 1 en e di i socy anate, 1 , 3 -bi s( 1 -i socy anato- 1 -methyl ethy 1 )b enzen e, bis(isocyanatobutyl)benzene, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether, bis(isocyanatoethyl)phthalate, and

2 , 5 -di ( i socy anatom ethy I )furan .

[00185] Suitable aromatic diisocyanates having isocyanate groups bonded directly to the aromatic ring include, for example, phenylene diisocyanate, ethylphenylene diisocyanate, isopropylphenylene diisocyanate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, naphthalene diisocyanate, methylnaphthalene diisocyanate, biphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, bis(3-methyl-4- isocyanatophenyl)methane, bi s(i socyanatophenyl)ethylene, 3 ,3 '-di methoxy-biphenyl-4,4'- diisocyanate, diphenylether diisocyanate, bi s(isocyanatophenylether)ethyleneglycol, bis(isocyanatophenylether)-l,3-propyleneglycol, benzophenone diisocyanate, carbazole di isocyanate, ethylcarbazole diisocyanate, dichlorocarbazole diisocyanate, 4,4 '-di phenylmethane diisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluene diisocyanate. [00186] Other examples of suitable aromatic diisocyanates include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,6-toluene diisocyanate (2,6-TDI), 2,4-toluene diisocyanate (2,4- TDI), a blend of 2,4-TDI and 2,6-TDI, 1,5-diisocyanato naphthalene, diphenyl oxide 4,4’- diisocyanate, 4,4'-methylenediphenyl diisocyanate (4,4-MDI),

2,4'-methylenediphenyl diisocyanate (2,4-MDI), 2,2'-diisocyanatodiphenylmethane (2,2-MDI), diphenylmethane diisocyanate (MDI), 3,3’-dimethyl-4,4'-biphenylene isocyanate, 3,3'- dimethoxy-4,4'-biphenylene diisocyanate, l-[(2,4-diisocyanatophenyl)methyl]-3-isocyanato-2- m ethyl benzene, 2,4,6-triisopropyl-m-phenylene diisocyanate, and a combination of any of the foregoing.

[00187] A suitable diisocyanate can have a molecular weight, for example, of about 150 g/mol to about 600 g/mol, such as about 100 g/mol to about 1 ,000 g/mol, or about 300 g/mol to about 1,000 g/mol. The reactants for preparing a polyurethane can include a ratio of isocyanate functional groups to hydroxyl groups, for example, about 1 to about 5, about 1 to about 3, alternatively about 2 to about 5, or about 2 to about 3, or 1 to about 1, or 1.1 to about 1. A diisocyanate can be a single type of diisocyanate or can be a combination of different types of diisocyanates. A diisocyanate can be a combination of a single type of diisocyanate having diisocyanates with different molecular weights.

Optional Chain Extender

[00188] A chain extender used at the time of producing the polyurethane of the present disclosure in the case of producing the later-described prepolymer having an isocyanate group is a low-molecular- weight compound having at least two active hydrogens reacting with an isocyanate group and usually includes a discrete alcohol, a polyol, a polyamine, etc.

[00189] In the polyurethane forming reaction at the time of producing the polyurethane, the copolymer polyol (or combination of multiple copolymer polyols) of the present di sclosure maybe used, if desired, in combination with another polyol (as a chain extender). The polyol other than the copolymer polyol (or combination thereof) of the present disclosure is not particularly limited as long as it is a polyol that can be used for the production of a polyurethane, and examples thereof include a polyether polyol, a polyester polyol, a polycaprolactone polyol, and a polycarbonate polyol (e.g., as described above) other than the copolymer polyol (or combination thereof) of the present disclosure. The weight ratio of the copolymer polyol (or combination thereof) to the total weight of copolymer polyol (or combination thereof) of the present disclosure and another polyol can be 70% or more, such as 90% or more.

[00190] Some examples thereof include linear diols such as ethylene glycol,

1.3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol,

1.9-nonanediol, 1,10-decanediol and 1 ,12 -dodecanediol; branched chain-containing diols such as

2 -methyl- 1,3-propanediol, 2,2-dimethyl-l,3-propanediol, 2, 2-di ethyl- 1,3-propanediol,

2 -methyl -2-propyl- 1,3 -propanediol, 2,4-heptanediol, 1 ,4-dimethylolhexane, 2-ethyl- 1 ,3- hexanediol, 2,2,4-trimethyl-l,3-pentanediol, 2 -methyl- 1,8-octanediol, 2-butyl-2-ethyl-l ,3- propanediol and dimer diol; ether group-containing diols such as diethylene glycol and propylene glycol; alicyclic structure-containing diols such as 1,4-cyclohexanediol,

1.4-cyclohexanedimethanol and 1,4-dihydroxyethylcyclohexane; aromatic group-containing diols such as xylylene glycol, 1,4-dihydroxy ethylbenzene and 4,4'-methyienebis(hydroxyethylbenzene); polyols such as glycerin, trimethylolpropane and pentaerythritol; 1,1,1 -Tri s(hydroxymethyl)propane, hydroxyamines such as

N-methylethanolamine and N-ethylethanolamine; polyamines such as ethylenediamine, 1 ,3-diaminopropane, hexamethylenediamine, tri ethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2 -hydroxy ethylpropylenedi amine, di-2- hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine,

2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine,

4,4'-diphenylmethanediamine, niethylenebis(o-chloroaniline), xylylenediamine, diphenyldiamine, tolyl en ediamine, hydrazine, piperazine and N,N’-diaminopiperazine; and water. One of these chain extenders may be used alone, or two or more thereof may be used in combination. Among these, in view of preferable balance of physical properties of the polyurethane obtained and mass availability at low cost in industry’, 1,4-butanediol (also referred to as 1,4BD), 1,5-pentanediol, 1,6-hexanediol, 1 ,8-octanediol, 1,9-nonanediol,

1.10-decanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, ethyIen ediamine,

1 ,3-diaminopropane, isophoronediamine, and

4,4'-diaminodicyclohexylmethane may be used.

Chain Terminator

[00191] At the time of producing the polyurethane, a chain terminator having one active hydrogen group may be used, if desired, for the purpose of controlling the molecular weight of the pol yurethan e obtain ed [00192] Examples of the chain terminator include aliphatic monools having one hydroxyl group, such as methanol, ethanol, propanol, butanol and hexanol, and aliphatic monoamines having one amino group, such as diethylamine, dibutylamine, n-butylamine, monoethanolamine, diethanolamine and morpholine

[00193] One of these chain terminators may be used alone, or two or more thereof may be used in combination.

Catalyst

[00194] In the polyurethane forming reaction at the time of producing the polyurethane, a known urethane polymerization catalyst typified, for example, by an amine-based catalyst such as triethylamine, N-ethylmorpholine and triethylenediamine, and an organic metal salt of a tin-based compound, such as tri methyltin laurate, dibutyltin di laurate, dioctyltin dilaurate and dioctyltin dineodecanoate, or a titanium-based compound, etc. may be used. One catalyst may be used alone, or two or more catalysts may be used in combination.

Solvent

[00195] In the polyurethane forming reaction at the time of producing the polyurethane of the present disclosure, a solvent may be used.

[00196] Example solvents can include an amide-based solvent such as dimethylformamide, di ethylformamide, dimethylacetamide and N-methylpyrrolidone; a sulfoxide-based solvent such as dimethyl sulfoxide; a ketone-based solvent such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone, an ether-based solvent such as tetrahydrofuran and dioxane; an ester-based solvent such as methyl acetate, ethyl acetate and butyl acetate; and an aromatic hydrocarbon-based solvent such as toluene and xylene. One of these solvents may be used alone, or two or more thereof may be used as a mixed solvent.

[00197] Among these organic solvents, examples are methyl ethyl ketone, ethyl acetate, toluene, dimethylformamide, dimethyl acetamide, N-methylpyrrolidone, dimethyl sulfoxide, etc. [00198] In addition, a polyurethane in the form of an aqueous dispersion liquid may also be produced from a polyurethane composition in which the copolymer polyol, a polydiisocyanate, and the above-described chain extender are blended.

Production Method of Polyurethane

[00199] As the method for producing the polyurethane of the present disclosure by using the above-described reaction reagents, a production method employed experimentally or industrially in general may be used.

[00200] Examples thereof include a method where the copolymer polyol, a polyisocyanate, a chain extender, and optionally another polyol are mixed and reacted (hereinafter, sometimes referred to as “one-step method”), and a method where the copolymer polyol of the present disclosure, a polyisocyanate, and optionally another polyol are first reacted to prepare a prepolymer having an isocyanate group at both ends and the prepolymer is reacted with a chain extender (hereinafter, referred to as “two-step method”).

[00201] The two-step method involves a process of previously reacting the copolymer polyol of the present disclosure and optional other polyol with one equivalent or more of poly isocyanate to prepare an intermediate terminated by an isocyanate at both ends, which is a moiety corresponding to the soft segment of a polyurethane. In this way, -when a prepolymer is once prepared and then reacted with a chain extender, the molecular weight of the soft segment moiety may be easily adjusted, and this method is useful in the case where phase separation of a soft segment and a hard segment can be achieved. Nonetheless, even a one-step method of forming polyurethane of the present disclosure can also achieve improved (reduced or eliminated) phase separation of a soft segment and a hard segment while rendering an additional polyol merely optional. This is so because of the improved properties provided by copolymer polyols of the present disclosure.

One- Step Method

[00292] A one-step method is a method of performing the polyurethane formation reaction by charging the copolymer polyol (or combinations thereof), optionally another polyol, a polyisocyanate and optional chain extender en bloc.

[00203] The amount of the polyisocyanate used in the one-step method is not particularly limited, but when the sum of the total number of hydroxyl groups in the copolymer polyol of the present disclosure and optional other polyol, the number of hydroxyl groups of the chain extender and the number of amino groups is assumed to be 1 equivalent, the lower limit can be about 0.7 equivalents, such as about 0.8 equivalents, such as about 0.9 equivalents, such as about 0.95 equivalents, and the upper limit can be about 3 equivalents, such as about 2 equivalents, such as about 1.5 equivalents, such as about 1.1 equivalents.

[00204] The amount of the chain extender used is not particularly limited, but when the number obtained by subtracting the number of isocyanate groups in the poly isocyanate from the total number of hydroxyl groups in the copolymer polyol and optional other polyol is assumed to be about 1 equivalent, the lower limit may be about 0.7 equivalents, such as about 0.8 equivalents, such as about 0.9 equivalents, such as about 0.95 equivalents, and the upper limit can be about 3 equivalents, such as about 2 equivalents, such as about 1.5 equivalents, such as about 1.1 equivalents.

Two-Step Method

[00205] The two-step method is also called a prepolymer method and can include the following parameters:

(a) a method where the copolymer polyol, optional other polyol and an excess of polyisocyanate are reacted in a reaction equivalent ratio of polyisocyanate/(copolymer polyol and optional other polyol) of more than 1 to 10 to produce a prepolymer having an isocyanate group at both molecular chain terminals and a chain extender is added thereto to produce a polyurethane, and/or

(b) a method where a polyisocyanate, an excess of the copolymer polyol and optional other polyol are previously reacted in a reaction equivalent ratio of polyisocyanate/(copolymer polyol and optional other polyol) of about 0.1 to less than about 1 to produce a prepolymer having a hydroxyl group at both molecular chain terminals and an isocyanate group-temiinated polyisocyanate as a chain extender is reacted therewith to produce a polyurethane.

[00206] The two-step method can be performed without a solvent or in the presence of a solvent. [00207] The polyurethane production by the two-step method can be performed by any one method of the following (1) to (3):

(1) a polyisocyanate, the copolymer polyol and optional other polyol are first reacted directly without using a solvent to synthesize a prepolymer and the prepolymer is used as it is for a chain extension reaction,

(2) a prepolymer is synthesized by the method of (1), then dissolved in a solvent and used for the subsequent chain extension reaction, and

(3) a polyisocyanate, the copolymer polyol and optional other polyol are reacted by using a solvent from the beginning and thereafter, a chain extension reaction is performed. [00298] In the case of the method of (1 ), at the time of chain extension reaction, a polyurethane is obtained in the form of coexisting with a solvent, for example, by a method of dissolving a chain extender in a solvent or simultaneously dissolving the prepolymer and a chain extender in a solvent.

[00209] The amount of the polyisocyanate used in the method (a) of the two-step method is not particularly limited, but when the total number of hydroxyl groups in the copolymer polyol and optional other polyol is assumed to be 1 equivalent, in terms of the number of isocyanate groups, the lower limit can be more than about 1 equivalent, such as about 1.2 equivalents, such as about 1.5 equivalents, and the upper limit can be about 10 equivalents, such as about 5 equivalents, such as about 3 equivalents.

[00210] The amount of the chain extender used is not particularly limited, but when the number of isocyanat.es contained in the prepolymer is assumed to be about 1 equivalent, the lower limit can be about 0. 1 equivalents, such as about 0.5 equivalents, such as about 0.8 equivalents, and the upper limit can be about 5 equivalents, such as about 3 equivalents, such as about 2 equivalents.

[00211] At the time of the above-described chain extension reaction, monofunctional organic amines or alcohols may be allowed to coexist for the purpose of adjusting the molecular weight

[00212] The amount of the polyisocyanate used when preparing a hydroxyl group-terminated prepolymer in the method (b) of the two-step method is not particularly limited, but when the total number of hydroxyl groups in the copolymer polyol and optional other polyol is assumed to be I equivalent, in terms of the number of isocyanate groups, the lower limit can be about 0.1 equivalents, such as about 0.5 equivalents, such as about 0.7 equivalents, and the upper limit can be about 0.99 equivalents, such as about 0.98 equivalents, such as about 0.97 equivalents.

[00213] The amount of the chain extender used is not particularly limited, but when the total number of hydroxyl groups in the copolymer polyol and optional other polyol used for the prepolymer is assumed to be about 1 equivalent, in terms of the total equivalent including the equivalent of the isocyanate group used for the prepolymer, the lower limit can be about 0.7 equivalents, such as about 0.8 equivalents, such as about 0.9 equivalents, and the upper limit can be less than about 1 equivalent, such as about 0.99 equivalents, such as about 0.98 equivalents.

[00214] At the time of the above-described chain extension reaction, monofunctional organic amines or alcohols may be allowed to be present for the purpose of adjusting the molecular weight. [00215] The chain extension reaction is usually performed at 0°C to 250°C, but the temperature varies depending on the amount of solvent, the reactivity of raw material used, the reaction equipment, etc. and is not particularly limited.

[00216] In the chain extension reaction, a catalyst, a stabilizer, etc. may also be added, if desired.

[00217] The catalyst includes, for example, compounds such as triethylamine, tributylamine, dibutyltin dilaurate, stannous octoate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid and sulfonic acid, and one compound may be used alone, or two or more compounds may be used in combination. The stabilizer includes, for example, compounds such as 2,6-dibutyl-4- m ethyl phenol, disteaiy 1 thiodipropionate, N,N'-di-2-naphthyl-l ,4-phenylenedi amine and tris(dinonylphenyl)phosphite, and one compound may be used alone, or two or more compounds may be used in combination. Here, in the case where the chain extender is a compound having high reactivity, such as short-chain aliphatic amine, the reaction may be performed without addition of a catalvst.

Polyurethanes and Polyurethane Properties

[00218] A polyurethene of the present includes polyisocyanate units (such as diisocyanate units), copolymer polyol units, optional chain extender (c.g,, other polyol), and end groups (e.g., hydrogen atoms, one at each terminus of the polyurethane).

[00219] In some embodiments, the copolymer polyol units are represented by Formula (IB), Formula (IIB), Formula (IIIB), or (IXB):

wherein: each instance of X is independently oxygen or sulfur; each instance of R^a and R^b is independently hydrogen, substituted or unsubstituted ether, or substituted or unsubstituted hydrocarbyi, wherein R^a and R^b may combine to form a substituted or unsubstituted five-membered, six-membered, or seven -membered ring; n is zero or a positive integer of about 1 to about 300; m is zero or a positive integer of about 1 to about 300; p is a positive integer of about 1 to about 300; q is zero or 1; each instance of R^c is independently substituted or unsubstituted alkylene, substituted or unsubstituted vinylene, substituted or unsubstituted ether, substituted or unsubstituted carbonylcontaining hydrocarbon, or substituted or unsubstituted alkanoate, each instance of E is independently an oxygen, sulfur, or methylene (CH₂), wherein a wavy line indicates a point of bonding to another unit of the polyurethane, wherein the copolymer polyol unit is a block (b) copolymeric unit or a random (r) copolymeric polyol unit.

[00220] In some embodiments, R^a and R^b can be independently an alkyl, substituted alkyl, aryl, or substituted aryl group, such as a C₁ to C₅₀ (such as C₂ to C₃₀. such as C₃ to C₂₀) alkyl, C₁ to C₅₀ (such as C₂ to C₃₀. such as C₃ to C₂₀) substituted alkyl, C₅ to C₅₀ (such as C₆ to C₃₀. such as C₆ to C₂₀) aryl, or C₅ to C₅₀ (such as C₆ to C₃₀, such as C₆ to C₂₀) substituted aryl group. In some embodiments, R^a and R^b are independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl.

[00221] Each of R^a and R^b can independently be based on the epoxide monomer starting material (as described in more detail below) used to form the polymeric diol. For example, R^a and R^b can combine to form a cyclohexyl ring, n is zero or a positive integer (e.g., about 1 to about 300, such as about 1 to about 100, such as about 10 to about 70, such as about 15 to about 50, such as about 15 to about 25, alternatively about 25 to about 50). Each of p and m is independently a positive integer (e.g , about 1 to about 300, such as about 1 to about 100, such as about 10 to about 70, such as about 15 to about 50, such as about 15 to about 25, alternatively about 25 to about 50). m may be zero Each instance of “X-R^c” is independently a monomeric unit of alkyl, vinylene, ether, carbonyl-containing alkyl, or alkanoate (such as lactone or other ester). R^c is independently alkylene, vinylene, ether, carbonyl-containing hydrocarbon, or alkanoate,

[00222] In some embodiments, R^c is alkylene, vinylene, ether, carbonyl-containing hydrocarbon, or alkanoate. In some embodiments, R^c is selected from

, or combinations thereof, where

[00223] In some embodiments, the copolymer polyol units are represented by Formula (IVB), Formula (VB), Formula (VIJB), Formula (VIIB), Formula (VIIIB), or Formula (XXB):

poiyalkyiene carbonate poiyaikylene ether carbonate (PAC) (Formula {iVB» (PAEC) (Formula (VB))

polyaikyiene carbonate (PAC) (Formula (VIB))

polyalkyiene ether carbonate (PAEC) (Formula (VliB))

wherein: each instance of R^a and R^b i s independently hydrogen, ether, hydrocarbyl, or substituted hydrocarbyl, wherein R^a and R^b may combine to form a five-membered, six-membered, or sevenmembered ring; each of n, o, p, q, r, s, t, u, and v is independently a positive integer of about 1 to about 300, such as about 1 to about 100, such as about 1 to about 50, such as about 1 to about 25, such as about 1 to about 10, such as about 1 to about 5; wherein a wavy line indicates a point of bonding to another unit of the polyurethane, wherein the copolymer unit is a block copolymer or a random copolymer unit.

[00224] In some embodiments of Formula (IVB), Formula (VB), Formula (VIE), Formula (VIIB), Formula (VIIIB), or Formula (XXB), R^a and R^b can be independently an alkyl, substituted alkyl, aryl, or substituted aryl group, such as a C₁ to C₅₀ (such as C₂ to C₃₀, such as C₃ to C₂₀) alkyl, C₁ to C₅₀ (such as C₂ to C₃₀, such as C₃ to C₂₀) substituted alkyl, C₅ to C₅₀ (such as C₆ to C₃₀, such as C& to C₂₀) and, or C₅ to C₅₀ (such as C_;> to C₃₀, such as C₆ to C₂₀) substituted aryl group. In some embodiments, R^a and R^b are independently selected from hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl.

[00225] In some embodiments of Formula (IVB), Formula (VB), Formula (VIB), Formula (VIIB), Formula (VIIIB), or Formula (XXB), each of R^a and R^b can independently be based on the epoxide monomer starting material used to form the polymeric diol. For example, R^a and R^b can combine to form a cyclohexyl ring,

[00226] In some embodiments, a polyurethane of the present application having copolymer polymers (and with or without optional other polyol) can have a hardness that is from about 20 Shore A to about 90 Shore A, such as from about 30 Shore A to about 80 Shore A, such as from about 30 Shore A to about 70 Shore A, such as from about 30 Shore A to about 60 Shore A, as determined by the ASTM method (see experimental section).

[00227] In some embodiments, a polyurethane of the present application having copolymer polymers (and with or without optional other polyol) can have a hard segment content of about 10% to about 60%, such as about 20% to about 50%, such as about 25% to about 40%, such as about 25% to about 30%.

[00228] In some embodiments, a polyurethane of the present application having copolymer polymers (and with or without optional other polyol) can have a soft segment content of about 40% to about 90%, such as about 50% to about 80%, such as about 60% to about 75%>, such as about 70% to about 75%.

[00229] In some embodiments, a polyurethane of the present disclosure has a heat stability of about 150°C to about 220°C, as determined by ASTM El 131.

[00230] A polyurethane may have elasticity while in the melt phase. “Tan delta” is the ratio of viscous modulus (E") to elastic modulus (E') and is a useful quantifier of the presence and extent of elasticity in the melt. In some embodiments, the tan delta of the composition is a range of about 0.01 to about 2 or about 0.05 to about 1.5 or about 0.1 to about 1.

[00231] In at least one embodiment, a polyurethane of the present disclosure can have a viscous modulus (G”) at -40°C of from about 10 MPa to about 100 MPa, determined according to the method described below.

[00232] In at least, one embodiment, a polyurethane of the present disclosure can have a viscous modulus (G") at 100°C of from about 0.1 MPa to about 1 MPa, determined according to the method described below.

[00233] In at least one embodiment, a polyurethane of the present disclosure can have an elastic modulus (G) at -40°C of from about 100 MPa to about 1000 MPa, determined according to the method described below.

[00234] In at least one embodiment, a polyurethane of the present disclosure can have an elastic modulus (G') at 100°C of from about 0.5 MPa to about 2 MPa, determined according to the method described below. Molded and Extruded Products

[00235] A polyurethane of the present disclosure can provide low Shore A values while maintaining good tensile strength due to strain induced crystallization. In addition, polyurethanes of the present disclosure can provide oxidation resistance A polyurethane of the present disclosure is advantageous for high temperature applications dur to polymer samples resistance toward oxidation. A polyurethane may be used to prepare molded products in a molding process, such as injection molding, gas-assisted injection molding, extrusion blow' molding, injection blow molding, injection stretch blow molding, compression molding, rotational molding, foam molding, thermoforming, sheet extrusion, and profile extrusion. Molding processes are well known to those of ordinary skill in the art.

[00236] A polyurethane may be shaped into desirable end use articles by any suitable means known in the art. Thermoforming, vacuum forming, blow molding, rotational molding, slush molding, transfer molding, wet lay-up or contact molding, cast molding, cold forming, matched- die molding, injection molding, spray techniques, profile co-extrusion, or combinations thereof are typically used methods.

[00237] Compression molding can be performed by pressing a polyurethane between two plates (e.g., PTFE or Teflon® plates) into a shape (e.g., a sheet) which is cooled, cut into a desired shape, and compressed at an elevated temperature, such as about 100°C or greater, such as about 200°C or greater, such as about 300°C or greater, such as about 400°C or greater. A compression mold may be a Wabash press, (e.g., model 12-1212-2 TMB), with a mold cavity (e.g., dimensions 4.5"x4.5"x0.06" in a 4-cavity Teflon-coated mold). Material in the mold is initially preheated (e.g., for several minutes) at an initial pressure (e.g., 2-ton pressure on a 4" ram), after which the pressure is increased (e.g.. to 10-tons), and heating is continued for several more minutes. The mold platens are then cooled with water, and the mold pressure is released after cooling (e.g , at about 70°C).

[00238] Thermoforming is a process of forming at least one pliable plastic sheet into a desired shape. An embodiment of a thermoforming sequence is described, however, this should not be construed as limiting the thermoforming methods useful with the polymers and blends of the present disclosure. First, an extrudate film of the polymer (or blend) (and any other layers or materials) is placed on a shuttle rack to hold it during heating. The shuttle rack indexes into the oven which pre-heats the film before forming Once the film is heated, the shuttle rack indexes back to the forming tool. The film is then vacuumed onto the forming tool to hold it in place and the forming tool is closed. The forming tool can be either "male" or "female" type tools. The tool stays closed to cool the film and the tool is then opened. The shaped laminate is then removed from the tool Thermoforming is accomplished by vacuum, positive air pressure, plug-assisted vacuum forming, or combinations and variations of these, once the sheet of material reaches thennofonning temperatures, typically of 140° to 185°C or higher. A pre-stretched bubble step is used, especially on large parts, to improve material distribution. In one embodiment, an articulating rack lifts the heated laminate towards a male forming tool, assisted by the application of a vacuum from orifices in the male forming tool. Once the laminate is firmly formed about the male forming tool, the thermoformed shaped laminate is then cooled, typically by blowers. Plug- assisted forming is generally used for small, deep drawn parts. Plug material, design, and timing may be critical to optimization of the process. Plugs made from insulating foam avoid premature quenching of the plastic. The plug shape is usually similar to the mold cavity, but smaller and without part detail. A round plug bottom will usually promote even material distribution and uniform side-wall thickness For a semi -crystalline polymer, fast plug speeds generally provide the best material distribution in the part. The shaped laminate is then cooled in the mold. Sufficient cooling to maintain a mold temperature of about 30°C to about 65°C may be desirable. The part is below about 90°C to about 100°C before ejection in one embodiment. The shaped laminate is then trimmed of excess laminate material.

[00239] Blow molding is another suitable forming means, which includes injection blow molding, multi-layer blow' molding, extrusion blow⁷ molding, and stretch blow⁷ molding, and is especially suitable for substantially closed or hollow objects, such as, for example, gas tanks and other fluid containers. Blow molding is described in more detail in, for example. Concise Encyclopedia of Polymer Science and Engineering (Jacqueline I Kroschwitz, ed., John Wiley & Sons 1990).

[00240] In yet another embodiment of the formation and shaping process, profile co-extrusion can be used. The profile co-extrusion process parameters are as above for the blow molding process, except the die temperatures (dual zone top and bottom) are from about 150°C to about 235°C, the feed blocks are from about 90°C to about 250°C, and the water cooling tank temperatures are from about 10°C to about 40°C.

[00241] One embodiment of an injection molding process is described as follows. The shaped laminate is placed into the injection molding tool. The mold is closed and the substrate material is injected into the mold. The substrate material has a melt temperature of about 150°C to about 300^cC in one embodiment, and from about 200°C to about 250^c’C in another embodiment, and is injected into the mold at an injection speed of about 2 to about 10 seconds. After injection, the material is packed or held at a predetermined time and pressure to make the part dimensionally and aesthetically correct. Typical time periods are from about 5 to about 25 seconds and pressures from about 1,000 kPa to about 15,000 kPa. The mold is cooled between about 10°C and about 70°C to cool the substrate. The temperature will depend on the desired gloss and appearance. Typical cooling time is from about 10 to about 30 seconds, depending in part on the thickness. Finally, the mold is opened and the shaped composite article ejected.

[00242] Likewise, molded articles may be fabricated by injecting molten polymer into a mold that shapes and solidifies the molten polymer into desirable geometry' and thickness of molded articles. A sheet may be made either by extruding a substantially flat profile from a die, onto a chill roil, or alternatively by calendering. Sheet will generally be considered to have a thickness of from about 10 mils to about 100 mils (about 254 rn to about 2540 m), although sheet may be substantially thicker.

[00243] Tubing or pipe may be obtained by profile extrusion for uses in medical, potable water, land drainage applications or the like. Tubing or pipe may be unvulcanized or vulcanized. Vulcanization can be performed using, for example, a peroxide or silane during extrusion of the tubing/pipe. The profile extrusion process involves the extrusion of molten polymer (or blend) through a die. The extruded tubing or pipe is then solidified by chill water or cooling air into a continuous extruded article. The tubing may be of from about 0.31 cm to about 2.54 cm in outside diameter, and have a wall thickness of from about 254 m to about 0.5 cm. The pipe will generally be in the range of from about 2.54 cm to about 254 cm in outside diameter, and have a wall thickness of from about 0.5 cm to about 15 cm.

[00244] Sheet(s) made from a polyurethane (or blend thereof) of the present disclosure may be used to form containers. Such containers may be formed by thermoforming, solid phase pressure forming, stamping and other shaping techniques. Sheets may also be formed to cover floors or walls or other surfaces.

[00245] In an embodiment of the thermoforming process, the oven temperature is from about 160°C to about 195°C, the time in the oven of about 10 to about 20 seconds, and the die temperature, typically a male die, of about 10°C to about 71 °C. The final thickness of the cooled (room temperature), shaped laminate is about 10 Dm to about 6,000 Dm in one embodiment, from about 200 Dm to about 6,000 Dm in another embodiment, and from about 250 Dm to about 3,000 □ m in yet another embodiment, and from about 500 Dm to about 1550 Dm in yet another embodiment, a desirable range being any combination of any upper thickness limit with any lower thickness limit.

[00246] In an embodiment of the injection molding process, wherein a substrate material is injection molded into a tool including the shaped laminate, the melt temperature of the substrate material is from about 190°C to about 255°C in one embodiment, and from about 210°C to about 250°C in another embodiment, the fill time from about 2 to about 10 seconds in one embodiment, from about 2 to about 8 seconds in another embodiment, and a tool temperature of from about 25°C to about 65°C in one embodiment, and from about 27°C to about 60°C in another embodiment. In a desirable embodiment, the substrate material is at a temperature that is hot enough to melt any tie-layer material or backing layer to achieve adhesion between the layers.

[00247] In yet another embodiment, a polyurethane (or blend thereof) of the present disclosure may be secured to a substrate material using a blow molding operation. Blow molding is particularly useful in such applications for making closed articles, such as fuel tanks and other fluid containers, playground equipment, outdoor furniture and small enclosed structures

[00248] It will be understood by those skilled in the art that the steps outlined above may be varied, depending upon the desired result. For example, the extruded sheet of a polymer (or blend thereof) may be directly thermofomied or blow molded without cooling, thus skipping a cooling step. Other parameters may be varied as well in order to achieve a finished composite article having desirable features.

[00249] The enhanced properties of the polyurethane (or blends thereof) of the present disclosure are useful in a wide variety of applications, including transparent articles such as cook and storage ware, and in other articles such as furniture, automotive components, toys, sportswear, medical devices, sterilizable medical devices and sterilization containers, nonwoven fibers and fabrics and articles therefrom such as drapes, gowns, filters, hygiene products, diapers, and films, oriented films, sheets, tubes, pipes and other items where softness, high impact strength, and impact strength below freezing is important.

[00250] Additional examples of desirable articles of manufacture made from polyethylene copolymers (or blends thereof) of the present disclosure may include one or more of: films, sheets, fibers, woven and nonwoven fabrics, automotive components, furniture, sporting equipment, food storage containers, transparent and semi-transparent articles, toys, tubing and pipes, sheets, packaging, bags, sacks, coatings, caps, closures, crates, pallets, cups, non-food containers, pails, insulation, and/or medical devices. Further examples include automotive components, wire and cable jacketing, pipes, agricultural films, geomembranes, toys, sporting equipment, medical devices, casting and blowing of packaging films, extrusion of tubing, pipes and profiles, outdoor furniture (e.g garden furniture), playground equipment, boat and water craft components, and other such articles. In particular, the polyethylene copolymers (or blends thereof) are suitable for automotive components such as bumpers, grills, trim parts, dashboards, instrument panels, exterior door and hood components, spoiler, wind screen, hub caps, mirror housing, body panel, protective side molding, and other interior and external components associated with automobiles, trucks, boats, and other vehicles

[00251] Other useful articles and goods may include: crates, containers, packaging, labware, such as roller bottles for culture growth and media bottles, office floor mats, instrumentation sample holders and sample windows: liquid storage containers such as bags, pouches, and bottles for storage and IV infusion of blood or solutions, packaging material including those for medical devices or drugs including unit-dose or other blister or bubble pack as well as for wrapping or containing food preserved by irradiation. Other useful items include medical tubing and valves for any medical device including infusion kits, catheters, and respiratory therapy, as well as packaging materials for medical devices or food which is irradiated including trays, as vvefi as stored liquid, such as water, milk, or juice containers including unit servings and bulk storage containers as well as transfer means such as tubing and pipes.

[00252] Retail films are commonly used for packaging and/or bundling articles for consumer use, such as, for example, in supermarket goods. Such films are ty pically formed in a single bubble blown extrusion process to a thickness of, for example, about 10 to about 80, pm.

EXPERIMENTAL

Dynamic Mechanical Analysis (DMA)

[00253] The glass transition temperature (Tg) is measured using dynamic mechanical analysis A dynamic mechanical analysis test provides information about the small-strain mechanical response of a sample as a function of temperature over a temperature range that includes the glass transition region and the visco-elastic region prior to melting. Specimens are tested using a commercially available rheometer (TA Instruments ARES-G2) equipped with 8 mm serrated parallel plates. The specimen is cooled to -80°C then heated to 200°C at a heating rate of 2°C/min while subjecting to an oscillatory deformation at 0.1% strain and a frequency of 1 Hz. The output of these rheological experiments is the storage modulus (G') and loss modulus (G"). The storage modulus measures the elastic response or the ability of the material to store energy, and the loss modulus measures the viscous response or the ability of the material to dissipate energy. The ratio of G'7G', called Tan-delta, gives a measure of the damping ability of the material; peaks in Tandelta are associated with relaxation modes for the material. Tg is defined to be the G peak temperature associated with the p-relaxation mode, which typically occurs from about -80°C to about 20°C for polyolefins. In a heterophase blend, separate p-relaxation modes for each blend component can cause more than one Tg to be detected for the blend; assignment of the Tg for each component may be based on the Tg observed when the individual components are similarly analyzed by DMA (although slight temperature shifts are possible).

[00254] The above challenges were addressed by producing block copolymers of CO₂, derived polycarbonate polyol with various conventional polyols such as polyether, polycaprolactone, and polycarbonate polyols having minimum polydispersity and good processability for producing TPU with excellent properties. Copolymers were made via CO₂ polycarbonate polyol and conventional polyether/polycaprolactone/polycarbonate/polyester polyols with relatively low MWs, narrow and monomodal MW distributions (MWDs), high thermal stability, and hydroxyl end group functionality. These novel ABA triblock diols are highly interesting polyurethane starting materials bring benefits in terms of properties. The process of preparing triblock polyols eliminates need for producing physical blends of conventional polyols with new⁷ CO₂-derived polycarbonate polyols,

[00255] Tensile test (Method A): Young's Modulus, tensile strength at yield, Ultimate tensile strength (“UTS”), modulus at 100% extension (“Ml 00”), and ultimate elongation (“UE”) and tensile strain at yield were measured according to ASTM D638. The samples were tested using crosshead speed of 2 in/niin at 23°C on a compression molded plastic plaque.

[00256] Shore A/D test: Shore A Hardness was measured using a Zwick automated durometer according to ASTM D2240 (15 sec. delay). Shore D Hardness was measured using a Zwick automated durometer according to ASTM D2240. Scheme 3

[00257] The triblock polyols produced can be used for producing a formulation of soft TPU having Shore A hardness less than 90, such as less than 80, such as less than 70 comprising no added plasticizers, The TPUs of the present disclosure can be produced via one-step process without the need for producing physical blends of polyether and polycarbonate polyols. The inventors have found that soft TPU with Shore A hardness less than 90 can be produced by using the triblock polyols of the present disclosure, organic diisocyanate and glycol chain extender in a one-step reaction. Specifically, the one-step process includes synthesizing TPU by polymerization of i) triblock linear polyol, ii) organic diisocyanate and iii) glycol chain extender mainly comprising butanediol, where in the linear polyol has the following chemical composition and molecular weight.

[00258] The composition of the triblock can be independently selected from polyether, polycaprolactone, polylactone, poly alkylene carbonate, or polyester, with molecular mass ranging of about 500 g/mol to about 80,000 g/mol.

[00259] Another advantage of the present triblock polyol is the ability to reduce hard segment ratio for producing soft TPUs without the challenges of sticking to mold, and tackiness. It was also found that the TPU produced here can be molded to TPU particles in practicable processing cycles. Although the TPU compositions of the present disclosure are very soft in nature, they offer the advantage of having little tendency to stick to molds. Accordingly, they are highly advantageous for utilization in injection molding application. Moreover, the TPU articles molded have good low-temperature properties and good mechanical properties, and do not harden substantially at low temperature, such as lower than -10°C. We demonstrate here that such TPUs can be produced with HS contents less than about 30%, such as less than about 20%, such as less than about 15%.

[00260] General procedure for the synthesis of polyalkylene carbonate (PAC) and polyalkylene ether carbonate (PAEC) polyols (Ingredients D and E). To a 600 mL Parr reactor was charged one or more than one epoxide monomers, a phosphonium borane catalyst such as Catalyst A or Catalyst B (catalyst applications filed here: PCT/US2023/064022 and PCT/US2023/064023), and a dialcohol. The reactor was then charged with 400 to 500 psi carbon dioxide and heated to 30 to 150°C for 1 to 24 hours. The reaction is then depressurized to afford the PAC or PAEC polyol. [00261] General procedure for the synthesis of block copolymer polyols of PAC or PAEC (Ingredients F). To a 600 mL Parr reactor was charged one or more than one epoxide monomers, a phosphonium borane Catalyst A (catalyst applications filed here: PCT/US2023/064022 and PCT/US2023/064023), and a polyol (Ingredient C, I), or E). The reactor was then charged with •400 to 500 psi carbon dioxide and heated to 30 to 150°C for 1 to 48 hours. The reaction is then depressurized to afford the desired block copolymers.

[00262] Example: Synthesis of triblock PCHC-PCL-PCHC polyol (AH4903). To a 600 mL Pair reactor was charged cyclohexene oxide (81 mL), Catalyst A (177 nig, catalyst applications filed here: PCT/US2023/064022 and PCT/US2023/064023), and a poly caprolactone polyol (80 g, Mn = 2,000 g/mol; Aldrich). The reactor was then charged with 400 to 500 psi carbon dioxide and heated to 100°C for 16 hours. The reaction is then depressurized to afford the desired triblock copolymer which was then dried under reduced pressured at 90°C. ^lH NMR analysis on the dried polymers indicated a PCL/PCHC weight ratio of 67/33. ^lH NMR Chain-end analysis indicated a Mn of 3 , 124 g/mol .

[00263] Example: Synthesis of triblock PCHC-PTMO-PCHC polyol (AG8864). To a 600 mL Parr reactor was charged cyclohexene oxide (83.8 mL), Catalyst B (172.8 mg, catalyst applications filed here: PCT/US2023/064022 and PCT/US2023/064023), and a polytetramethyleneoxide (PTMO) polyol (120 g, Mn =^; 2,900 g/mol; Aldrich). The reactor was then charged with 400 to 500 psi carbon dioxide and heated to 100°C for 16 hours. The reaction is then depressurized to afford the desired triblock copolymer which was then dried under reduced pressured at 90°C. ’H NMR analysis on the dried polymers indicated a PTMO/PCHC weight ratio of 68/32. ¹H NMR Chain-end analysis indicated a Mn of 4,221 g/mol.

[00264] General procedure for the synthesis of polyurethanes. Method A (melt reactive extrusion): The TPU blends were prepared using an Intelli-Torque C. W. Brabender, assembled with a 3-piece mixer head, Plasti -Corder torque rheometer, and Cam blades. Data was collected using Winmix programming. The brabender was heated to 150°C and the initial stirring rate was set to 20 rpm. The chain-extender and polyols (Ingredients B, C, D, E, F) were mixed in a brabender at 150°C (60 rmp) for 3 minutes. Then, stannous octanoate (0 08 wt% of the total mass) was added, and the blend continued stirring for 3 minutes at 60 rpm. The stir rate was increased to 100 rpm after 4,4'-Methylenebis(phenyl isocyanate) (MDI) was added and left to mix for 6 minutes. Irganox 1010 (0.24 wt% of the total mass) and Tinuvin 622 (0.24 wt% of the total mass) were added to the mixer, and the blend was left to stir for an additional 2 minutes. The instrument was stopped and the mixer head was disassembled to remove the product.

Table 1 : The formulations (phr) of polyurethanes synthesized from reactive extrusion (Method A). The PCL polyol (Ingredient C) has a Mn of 2,000 g/mol (purchased from Aldrich). The PCHC polyol (Ingredient D) has a Mn of 2,258 g/mol (synthesized following the general procedure). The triblock PCL-PCHC-PCL polyol (Ingredient F) has a Mn of 3, 124 g/mol and a PCL/PCHC weight ratio of 67/33 (synthesized following the general procedure).

Table 2: Properties of PCL/PCHC-based TPUs.

Table 3: The formulations (phr) of polyurethanes synthesized from reactive extrusion (Method A). The PTMO polyol (Ingredient C) has aMn of 2,900 g/mol (purchased from Aldrich). The PCHC polyol (Ingredient D) has a Mn of 3,284 g/mol (synthesized following the general procedure). The triblock PCL-PTMO-PCL polyol (Ingredient F) has a Mn of 4,221 g/mol and a PTMO/PCHC weight ratio of 68/32 (synthesized following the general procedure).

[00265] Overall, copolymer polyurethanes of the present disclosure show improved properties. When a polyurethane formulation (see FIG 1, TABLE 1) comprises both a conventional polyol (Ingredient C, such as PCL or PTMO) and a CO₂-dereived polyol (Ingredient D or E such as PCHC polyol), the shore A values become lower (<70 A), consistent with softer polyurethane materials that are desirable. Meanwhile the tensile data suggest that such soft materials remain good mechanical properties as indicated by the tensile strength and elongation at break (FIG 2, TABLE 2). In particular, the soft materials appear to have a PCHC/(PCL+PCHC) ratio ranging from 20% to 60%, preferably from 30% to 50%, more preferably from 33% to 45% (FIG 3).

[00266] We observed the occurrence of strain-induced-crystallization in AHI 590- 17 (FIG 4). We also observed bi-continuous structures in AHI 590-17 and AHI 590-18 (FIG 5).

[00267] Additionally, copolymer polyurethanes of the present disclosure can provide improved properties when the formulation comprises two C Ch-dereived polyols (c.g,, from Ingredient D or E, such as PCHC polyol and PBC polyol, or PBC polyol and PEGC polyol).

[00268] Additionally, copolymer polyurethanes of the present disclosure can provide improved properties when the formulation comprises a CO₂-dereived block copolymer polyol (Ingredient F such as a PCHC-PCL-PCHC polyol). The triblock copolymer employed in AHI 590-14 results in a very soft polyurethane (shore A = 51) whose tensile strength (19.5 MPa) exceeds that of AH1590-17 (10.3 MPa), a polyurethane that has the same PCHC/(PCL+PCHC) ratio of 33%.

[00269] The phrases, unless otherwise specified, "consists essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the present disclosure, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[00270] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every-' point or individual value between its end points even though not explicitly recited. Thus, every' point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

[00271] All documents described herein are incorporated by reference herein, including any priority documents and or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. .Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term “comprising” is considered synonymous with the term “including”. Likewise, whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

[00272] While the present disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the present disclosure.

Claims

What is claimed is:

wherein: each of Q¹ and Q² of Formula (II) is independently hydrogen,

each instance of X is independently oxygen or sulfur; each instance of R^a and R^b is independently hydrogen, substituted or unsubstituted ether, or substituted or unsubstituted hydrocarbyl, wherein R³ and R^b may combine to form a substituted or unsubstituted five-membered, six-membered, or seven-membered ring; n is zero or a positive integer of about 1 to about 300; m is zero or a positive integer of about 1 to about 300; p is a positive integer of about 1 to about 300; q is zero or 1; each instance of R^c is independently substituted or un substituted alkylene, substituted or unsubstituted vinylene, substituted or unsubstituted ether, substituted or unsubstituted carbonylcontaining hydrocarbon, or substituted or unsubstituted alkanoate; and each instance of E is independently an oxygen, sulfur, or methylene (CH?), wherein the copolymer of formula (I), (II), (III), and (IX) is independently a block copolymer or random copolymer.

The copolymer of claim 1, wherein q is 0, E is independently an oxygen or sulfur; and each instance of R^c is independently selected from the group consisting

combinations thereof.

3. The copolymer of claim 1 , wherein q is 1 ; E is a methylene (CH₂); and each instance of R^c is independently selected from the group consisting of

and combinations thereof.

4 The copolymer of claim 1, wherein the copolymer is triblock copolymer.

5 The copolymer of claim 1 , wherein the copolymer has an Mn of about 500 g/mol to about 50,000 g/mol, as determined by gel permeation chromatography.

6. The copolymer of claim 1, wherein the copolymer has an Mw/Mn value of about 1.01 to about. 3.

7. The copolymer of claim 1, wherein the copolymer has a thermal stability of about 150°C to about 220°C as determined by AS' TM El 131 .

8. The copolymer of claim 1, wherein R^a and R” combine to form a cyclohexyl ring

9. The copolymer of claim 1 , wherein the copolymer is the copolymer is a random copolymer represented by Formula (IX), wherein p and m are independently a positive integer of about 5 to about 300, n is zero, Q¹ is hydrogen, and Q² is -OH.

10. The copolymer of claim 9, wherein the copolymer of Formula (IX) is represented by Formula (V):

(Formula (V)) wherein each instance of R^a and R° of Formula (V) combine to form a five-membered, sixmembered, or seven-membered ring, and each of o and p of Formula (V) is independently a positive integer of about 5 to about 300.

11. The copolymer of claim 9, wherein the copolymer of Formula (IX) is represented by Formula (VH):

(Formula (VII)) wherein each instance of R^a and R^b of Formula (VII) combine to form a five-membered, sixmembered, or seven-membered ring, and each of s, t, u, and v of Formula (VII) is independently a positive integer of about 5 to about 50.

12. The copolymer of claim 1 , wherein the copolymer is the copolymer is a random copolymer represented by Formula (III), wherein p and m are independently a positive integer of about 5 to about 300, n is zero, Q¹ is hydrogen, and Q² is -OH.

13. The copolymer of claim 12, wherein the copolymer of Formula (III) is represented by

Formula (VI):

(Formula (VI)) wherein each instance of R^a and R^b of Formula (VI) combine to form a five-membered, sixmembered, or seven-membered ring, and each of q and r of Formula (VI) is independently a positive integer of about 10 to about 100.

1-4. The copolymer of claim 1, wherein the copolymer is the copolymer is a block copolymer represented by Formula (III), wherein n, p, and m are independently a positive integer of about 5 to about 50, q is 0, each X and E is oxygen, R^c is alkanoate, Q¹ is hydrogen, and Q² is -OH.

15. The copolymer of claim 1-4, wherein the copolymer of Formula (III) is represented by Formula (VIII): (Formula (VIII))

wherein each instance of R^a and R^b of Formula (VIII) combine to form a five-membered, sixmembered, or seven-membered ring, and each instance of n and p of Formula (VIII) is independently a positive integer of about 10 to about 100.

16. The copolymer of claim 1, wherein the copolymer of Formula (III) is represented byFormula (XX):

wherein each instance of R^a and R^b of Formula (XX) combine to form a five-membered, sixmembered, or seven-membered ring, and each instance of n and p of Formula (XX) is independently a positive integer of about 10 to about 100.

17. A method of forming the copolymer of claim 1, the method comprising introducing a catalyst with an epoxide monomer, a polymeric diol, and one or more compounds selected from the group consisting of CO₂, COS, CS₂, and combinations thereof.

18. The method of claim 17, wherein the epoxide monomer is cyclohexene oxide.

19. The method of claim 18, wherein the polymeric diol is selected from the group consisting of a polyester diol, a polyether diol, a polycarbonate diol, a polycaprolactone diol, and a combination thereof’ and wherein the polymeric diol has a number average molecular weight (Mn) of about 1,000 g/mol to about 8,000 g/mol.

20. The method of claim 17, wherein the catalyst is represented by Formula (la):

wherein:

B* is a group 13 element;

P is a tertiary phosphine moiety wherein P is not directly bonded to more than two nitrogen atoms; each of R¹, R², R³, and R⁴ is independently a hydrocarbyl, a non-halogenated substituted hydrocarbyl group, or a heteroatom-containing group; each of R¹, R², R³, and R⁴ optionally comprises a tri-substituted borane or tri-substituted phosphine moiety;

R¹ and R², R³ and R⁴, R⁵ and Y, R³ and Y, R¹ and R³, and R¹ and R² and R³ are optionally fused to form cyclic or multi cyclic rings, and

Y is a non-halogenated linking group having about 1 to about 50 non-hydrogen atoms.

21 . The method of claim 17, wherein the catalyst is represented by Formula (lb):

wherein:

Pn is a Group 15 pnictogen element;

Pn⁺ constitutes a cationic tertian,/ pnictogenium moiety,

(the number of pnictogenium raoieties, Pn+) ^x Z = T ^x Q;

B* is a group 13 element;

Z is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, where if Z is greater than 1, then the catalyst units are present individually or are bound together in linear, branched or cyclic groups;

T is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, indicating the anionic charge of X;

Q is 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, indicating the number of X present, each of R¹, R², R³ and R⁴ is independently a hydrocarbyl group, a non -halogenated substituted hydrocarbyl, or a heteroatom-containing group, and can optionally comprise a trisubstituted borane or cationic tertiary pnictogenium moiety;

Y is independently a linking group having about 1 to about 50 non-hydrogen atoms, and

X is independently a mono-anionic group, a multi -anionic group, or a combination thereof.

22. The method of claim 17, wherein the catalyst is represented by

23. A method of forming a polyurethane, the method comprising introducing a catalyst with the copolymer of claim 1, a diisocyanate and a chain extender.

24. The method of claim 23, wherein the chain extender is butanediol.

25. The method of claim 23, wherein the method is a one-step method comprising charging en bloc the copolymer polyol, the polyisocyanate, and the chain extender

26. The method of claim 23, wherein the polyurethane has a hardness that is about 10 Shore A to about 90 Shore ,4, as determined by ASTM D2240.

27. The method of claim 23, wherein the polyurethane has a hard segment content of about 25% to about 40%.

28. The method of claim 23, wherein the polyurethane has a tan delta of about 1 MPa to 100 MPa.

29. A polyurethane consisting of: a plurality of polyisocyanate units; two or more end groups; a plurality of copolymer polyol units, optionally a plurality of homopolymer polyol units; and optionally a plurality of chain extender units, wherein the plurality of copolymer polyol units are represented by Formula (IB), Formula (IIB), Formula (IIIB), or Formula (IXB):

wherein: each instance of X is independently oxygen or sulfur, each instance of R^a and R'' is independently hydrogen, substituted or unsubstituted ether, or substituted or unsubstituted hydrocarbyk wherein R^a and R^b may combine to form a substituted or unsubstituted five-membered, six-membered, or seven-membered ring; n is zero or a positive integer of about 1 to about 300; m is zero or a positive integer of about I to about 300; p is a positive integer of about I to about 300; q is zero or 1 ; each instance of R^c is independently substituted or unsubstituted alkylene, substituted or unsubstituted vinylene, substituted or unsubstituted ether, substituted or unsubstituted carbonylcontaining hydrocarbon, or substituted or unsubstituted alkanoate; each instance of E is independently an oxygen, sulfur, or methylene (CH?.), wherein a wavy line indicates a point of bonding to another unit or end group of the polyurethane, wherein the copolymer polyol unit is a block (b) copolymeric unit or a random (r) copolymeric polyol unit.

30. The polyurethane of claim 29, wherein the two or more end groups are hydrogen atoms.

31 . The polyurethane of any of claims 29 or 30, wherein the polyisocyanate units are methylene diphenyl diisocyanate units.

32. The polyurethane of any of claims 29 to 3 I, wherein the plurality of copolymeric polyol units is a combination of two or more different copolymeric polyol units represented by the Formula (IB), the Formula (IIB), the Formula (IIIB), or the Formula (IXB).

33. The polyurethane of any of claims 29 to 32, wherein the plurality of copolymeric polyol units includes the copolymeric polyol represented by Formula (IIB) and is represented by Formula (IVB):

(Formula (IVB)) wherein each instance of R^a and R^b of Formula (IVB) combine to form a five-membered, sixmembered, or seven-membered ring and n of Formula (IVB) is a positive integer of about 10 to about 300

34. The polyurethane of any of claims 29 to 33, wherein the plurality of copolymeric polyol units includes the copolymeric polyol represented by Formula (IXB) and is a random copolymeric polyol unit represented by Formula (VB):

(Formula (VB)) wherein each instance of R^a and R^b of Formula (VB) combine to form a five-membered, sixmembered, or seven-membered ring, and each of o and p of Formula (VB) is independently a positive integer of about 10 to about 300.

35. The polyurethane of any of claims 29 to 34, wherein the plurality of copolymeric polyol units includes the copolymeric polyol represented by Formula (IXB) and is a random copolymeric polyol unit represented by Formula (VIIB):

(Formula (VIIB)) wherein each instance of R^a and R^b of Formula (VIIB) combine to form a five-membered, sixmembered, or seven-membered ring, and each of s, t, u, and v of Formula (VIIB) is independently a positive integer of about 10 to about 50.

36. The polyurethane of any of claims 29 to 35, wherein the plurality of copolymeric polyol units includes the copolymeric polyol represented by Formula (IIIB) and is a random copolymeric polyol unit represented by Formula (VIB):

(Formula (VIB) wherein each instance of R^a and R^b of Formula (VIB) combine to form a five-membered, sixmembered, or seven-membered ring, and each of q and r of Formula (VIB) is independently a positive integer of about 10 to about 300.

37. The polyurethane of any of claims 29 to 36, wherein the plurality of copolymeric polyol units includes the copolymeric- polyol represented by Formula (IIIB) and is a block copolymeric polyol unit represented by Formula (VIIIB):

(Formula (VilIB))

wherein each instance of R^a and R¹' of Formula (VIIIB) combine to form a five-membered, sixmembered, or seven-membered ring, and each instance of n and p of Formula (VIIIB) is independently a positive integer of about 10 to about 300.

38. The polyurethane of any of claims 29 to 37, wherein the plurality of copolymeric polyol units includes the copolymeric polyol represented by Formula (IIIB) and is a block copolymeric polyol unit represented by Formula (XXB): (Formula (XXB))

wherein each instance of R^a and R^b of Formula (XXB) combine to form a five-membered, sixmembered, or seven-membered ring, and each instance of n and p of Formula (XXB) is independently a positive integer of about 10 to about 300.

39. The polyurethane of claim 29, wherein: the polyurethane has the chain extender units, the polyurethane has the homopolymer polyol units, and the homopolymer polyol units are selected from the group consisting of a polytetramethylene oxide (PTMO) unit, a polycaprolactone (PCL) unit, a polyethylene (PE) unit, a polybutadiene (PBD) unit, or combinations thereof; and the polyisocyanate units are methylene diphenyl diisocyanate units.

40. A composition comprising the polyurethane of any of claims 29 to 39 and one or more non- CO₂-derived polyols.

41. A polyurethane composition comprising at least a CO₂-derived polyol, and at least a non- CO₂-derived polyol.

42. A polyurethane composition comprising at least one CO₂-derived polyol of polycyclohexene oxide (PCHC), polycyclopentene oxide (PCPC) or polybutylene oxide (PBC), and at least a n on-CO₂-derived polyol of polytetramethylene oxide (PTMO), poly caprolactone (PCL), or combinations thereof.