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WO2019204625A1 - Compositions ignifuges sans halogène pour mousses de polyuréthane souples - Google Patents

Compositions ignifuges sans halogène pour mousses de polyuréthane souples Download PDF

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Publication number
WO2019204625A1
WO2019204625A1 PCT/US2019/028151 US2019028151W WO2019204625A1 WO 2019204625 A1 WO2019204625 A1 WO 2019204625A1 US 2019028151 W US2019028151 W US 2019028151W WO 2019204625 A1 WO2019204625 A1 WO 2019204625A1
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WO
WIPO (PCT)
Prior art keywords
composition
halogen
polyether polyol
group
phosphonate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2019/028151
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English (en)
Inventor
Lawino Kagumba
Charles MANZI-NSHUTI
Ken Wei
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FRX Polymers Inc
Original Assignee
FRX Polymers Inc
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Filing date
Publication date
Application filed by FRX Polymers Inc filed Critical FRX Polymers Inc
Publication of WO2019204625A1 publication Critical patent/WO2019204625A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4084—Esters with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1833—Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/08—Processes
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    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2081—Heterocyclic amines; Salts thereof containing at least two non-condensed heterocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/242—Catalysts containing metal compounds of tin organometallic compounds containing tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
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    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/388—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841—Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
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    • C08G2110/0058—≥50 and <150kg/m3
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/0066—≥ 150kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
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    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K7/14—Glass

Definitions

  • the present invention relates generally to the field of flame -retardant compositions, and in particular to halogen-free flame-retardant compositions for flexible polyurethane foams.
  • Flexible polyurethane foams can be used for a wide variety of applications, such as vehicle, construction, furniture, mattresses, insulation, protection, support, and the like, wherein the polyurethane is often required to have a number of specific properties, such as flame retardancy properties.
  • flexible polyurethane foams In order to meet flame retardancy requirements, flexible polyurethane foams generally need to couple with flame retardant materials.
  • the state-of-the-art approach to rendering flexible polyurethane foams flame retardant is to use additives such as halogen-based compounds or compounds containing aluminum and/or phosphorus.
  • Use of the additives with certain polymers can have a deleterious effect on the processing characteristics and/or the mechanical performance of articles produced from them.
  • some of these compounds are toxic, and can leach into the environment over time making their use less desirable.
  • certain halogenated additives are being phased-out of use because of environmental concerns.
  • halogen-free composition comprising: Part A, at least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof; and Part B, at least one isocyanate reactive polyether polyol, wherein one polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%, a phosphonate oligomer, and at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof.
  • MDI 4,4'-methyl diphenyl diisocyanate
  • Part B at least one isocyanate reactive polyether polyol, wherein one polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%, a phosphonate oligomer, and at least one additional component selected from the group consisting of blowing agent, surfactant,
  • the composition can have a density ranging from about 80 kg/m 3 to about -140 kg/m 3 .
  • the co-flame retardant can not comprise graphite.
  • the composition can be a polyurethane foam or a flexible polyurethane foam.
  • the co-flame retardant can be selected from the group consisting in , ammonium polyphosphate, melamine, melamine polyphosphate, melamine cyanurate, aluminum trihydrate, carbon nanotubes, silica or any combinations thereof.
  • the composition can lose a maximum of about 50% of its tensile strength after heat aging at least about 150 °C for about 7 days.
  • the composition can achieve FMVSS302 rating.
  • the composition can achieve a V-0 rating at about 0.5 inch according to Underwriter’s Laboratories Standard UL94 Flammability test before and after heat aging.
  • Some other embodiments pertain to a method for producing a flexible polyurethane foam comprising mixing and reacting Part A and Part B to form a foam, wherein Part A comprises at least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof, and Part B comprises at least one isocyanate reactive polyether polyol, wherein one polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%, a phosphonate oligomer, and at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof.
  • MDI 4,4'-methyl diphenyl diisocyanate
  • Part B comprises at least one isocyanate reactive polyether polyol, wherein one polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%, a
  • Some other embodiments pertain to a halogen-free flexible polyurethane foam for use in thermal applications including engine compartment of vehicle, underbody thermal part, or a combination thereof.
  • Embodiment 1 A halogen-free composition comprising:
  • blowing agent at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof,
  • Part A or Part B further comprises a phosphonate oligomer.
  • Embodiment 2 A halogen-free composition comprising:
  • At least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof ;
  • At least one isocyanate reactive polyether polyol wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%;
  • blowing agent selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof.
  • Embodiment 3 The halogen-free composition of embodiment 1 or 2, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%
  • Embodiment 4 The halogen -free composition of embodiment 1 or 2, wherein the composition has a density ranging from about 80 kg/m 3 to about 140 kg/m 3 .
  • Embodiment 5 The halogen-free composition of claim 1 or 2, wherein the composition has a density ranging from about 20 kg/m 3 to about 80 kg/m 3 .
  • Embodiment 6 The composition of embodiment 1 or 2, wherein the co-flame retardant does not comprise graphite.
  • Embodiment 7 The composition of embodiment 1 or 2, wherein the composition is a polyurethane foam.
  • Embodiment 8 The composition of embodiment 7, wherein the polyurethane foam is a flexible polyurethane foam.
  • Embodiment 9 The composition of embodiment 1 or 2, wherein the co-flame retardant is selected from the group consisting in ammonium polyphosphate, melamine polyphosphate, melamine, melamine cyanurate, aluminum trihydrate, carbon nanotubes, silica, or any combinations thereof.
  • Embodiment 10 The composition of embodiment 7, wherein the composition loses a maximum of about 50% of its tensile strength after heat aging at least about 150 °C for about 7 days.
  • Embodiment 11 The composition of embodiment 7, wherein the composition achieves FMVSS302 rating.
  • Embodiment 12 The composition of embodiment 7, where the composition achieves a V-0 rating at about 0.5 inch according to Underwriter’s Laboratories Standard UL94 Flammability test before and after heat aging.
  • Embodiment 13 A method for producing a flexible polyurethane foam comprising the composition any of embodiments 1 to 12, wherein Part A and Part B are mixed and reacted to form a foam.
  • Embodiment 14 A halogen-free flexible polyurethane foam according to any of embodiments 1 to 12 for use in thermal applications including engine compartment of vehicle, underbody thermal part, or a combination thereof.
  • Embodiment 15 A halogen -free composition comprising:
  • At least one isocyanate selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof ;
  • At least one isocyanate reactive polyether polyol wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%;
  • blowing agent at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof,
  • Part A or Part B further comprises a phosphonate oligomer.
  • Embodiment 16 The halogen -free composition of embodiment 15, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%.
  • FIG. 1A shows an image of polyurethane foam composition, polyurethane with 5% expandable graphite
  • FIG. 1B shows an image of polyurethane foam composition, polyurethane with 2.5% expandable graphite and 2.5% NOFIA OL1001
  • FIG. 1C shows an image of polyurethane foam composition polyurethane with 2.5% expandable graphite and 5% NOFIA OL1001;
  • FIG. 2 shows a graph from the thermogravimetric analysis of pristine polyurethane foam (curve A) and polyurethane with 5.6% NOFIA OL1001 (curve B).
  • FIG. 3A shows a graph depicting Temperature at 50% mass loss.
  • FIG. 3B shows a graph depicting Residue at 400 °C.
  • substantially no means that the subsequently described event may occur at most about less than 10 % of the time or the subsequently described component may be at most about less than 10 % of the total composition, in some embodiments, and in others, at most about less than 5 %, and in still others at most about less than 1 %.
  • alkyl or“alkyl group” refers to a branched or unbranched hydrocarbon or group of 1 to 20 carbon atoms, such as but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t- butyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like.
  • Cycloalkyl or“cycloalkyl groups” are branched or unbranched hydrocarbons in which all or some of the carbons are arranged in a ring such as but not limited to cyclopentyl, cyclohexyl, methylcyclohexyl and the like.
  • the term“lower alkyl” includes an alkyl group of 1 to 10 carbon atoms.
  • the term“aryl” or“aryl group” refers to monovalent aromatic hydrocarbon radicals or groups consisting of one or more fused rings in which at least one ring is aromatic in nature. Aryls may include but are not limited to phenyl, napthyl, biphenyl ring systems and the like.
  • the aryl group may be unsubstituted or substituted with a variety of substituents including but not limited to alkyl, alkenyl, halide, benzylic, alkyl or aromatic ether, nitro, cyano and the like and combinations thereof.
  • Substituent refers to a molecular group that replaces a hydrogen in a compound and may include but are not limited to trifluoromethyl, nitro, cyano, Ci_ 2 o alkyl, aromatic or aryl, halide (F, Cl, Br, I), Ci_2o alkyl ether, Ci_ 2 o alkyl ester, benzyl halide, benzyl ether, aromatic or aryl ether, hydroxy, alkoxy, amino, alkylamino (-NHR’), dialkylamino (-NR’R”) or other groups which do not interfere with the formation of the intended product.
  • an“arylol” or an“arylol group” is an aryl group with a hydroxyl, OH substituent on the aryl ring.
  • Non-limiting examples of an arylol are phenol, naphthol, and the like.
  • a wide variety of arlyols may be used in the embodiments of the invention and are commercially available.
  • alkanol or“alkanol group” refers to a compound including an alkyl of 1 to 20 carbon atoms or more having at least one hydroxyl group substituent.
  • alkanols include but are not limited to methanol, ethanol, 1- and 2-propanol, 1,1- dimethylethanol, hexanol, octanol and the like.
  • Alkanol groups may be optionally substituted with substituents as described above.
  • alkenol or“alkenol group” refers to a compound including an alkene 2 to 20 carbon atoms or more having at least one hydroxyl group substituent.
  • the hydroxyl may be arranged in either isomeric configuration (cis or trans).
  • Alkenols may be further substituted with one or more substituents as described above and may be used in place of alkenols in some embodiments of the invention. Alkenols are known to those skilled in the art and many are readily available commercially.
  • the term“about” means plus or minus 10% of the numerical value of the number with which it is being used. Therefore, about 50% means in the range of 45%-55%.
  • LOI limiting oxygen index
  • ASTM D2863 provides quantitative information about a material's ability to bum or "ease of bum". If a polymeric material has an LOI of at least 27, it will, generally, bum only under very high applied heat.
  • Fire resistance may also be tested both by measuring the 0 2 index in accordance with ASTM D 2863-70 and also by measuring the after-burning time in accordance with the UL test (Subject 94).
  • the tested materials are given classifications of UL-94 VO, UL-94 VI and UL-94 V2 based on the results obtained with the ten test bars of a given thickness. Briefly, the criteria for each of these UL-94 V-classifications are as follows:
  • UL-94 V2 the total flaming combustion for each specimen after removal of the ignition flame should not exceed 30 seconds and the total flaming combustion for 5 specimens should not exceed 250 seconds. Test specimens may release flaming particles, which ignite absorbent cotton wool.
  • Fire resistance may also be tested by measuring after-burning time.
  • These test methods provide a laboratory test procedure for measuring and comparing the surface flammability of materials when exposed to a prescribed level of radiant heat energy to measure the surface flammability of materials when exposed to fire. The test is conducted using small specimens that are representative, to the extent possible, of the material or assembly being evaluated. The rate at which flames travel along surfaces depends upon the physical and thermal properties of the material, product or assembly under test, the specimen mounting method and orientation, the type and level of fire or heat exposure, the availability of air, and properties of the surrounding enclosure. If different test conditions are substituted or the end- use conditions are changed, it may not always be possible by or from this test to predict changes in the fire-test-response characteristics measured. Therefore, the results are valid only for the fire test exposure conditions described in this procedure.
  • M n number average
  • M w weight average molecular weight
  • the molecular weight of a polymer is based on the calibration of the chromatograph columns using known molecular weights of polystyrene standards. It is known that the molecular weight distribution of a polymer is important to properties such as thermo-oxidative stability (due to different amount of end groups), toughness, melt flow, and fire resistance, for example, low molecular weight polymers drip more when burned. [0050] Description general phosphonate structures
  • Embodiments of the invention are not limited by the type of phosphonate component included and may include, for example, polyphosphonates, branched polyphosphonates, or hyberbranched polyphosphonates, random or block copolyphosphonates, co-oligo(phosphonate ester)s, or co- oligo(phosphonate carbonate)s, phosphonate oligomers, branched phosphonate oligomers, or hyperbranched phosphonates, and in certain embodiments, the phosphonate component may have the structures described and claimed in U.S. Patent Nos. US7,645,850, US7, 816,486, US8,389,664, US8,563,638, US8,648,l63, US8,779,04l, US8,530,044, each of which is hereby incorporated by reference in its entirety.
  • Such phosphonate components may include repeating units derived from diaryl
  • such phosphonate components include structural units illustrated by Formula I:
  • Ar is an aromatic group and -O-Ar-O- may be derived from an aromatic dihydroxy compound or aromatic diol
  • R is a Ci_ 2 o alkyl, C2-20 alkene, C 2-20 alkyne, C 5-20 cycloalkyl, or C 6-20 aryl
  • nl is an integer from 2 to about 200, 2 to about 100, 2 to about 75, 2 to about 50, 2 to about 20, 2 to about 10, or 2 to about 5, or any integer between these ranges.
  • aromatic diol is meant to encompass any aromatic or predominately aromatic compound with at least two associated hydroxyl substitutions of the formula (II):
  • n2, p2, and q2 are each independently 0, 1, 2, 3, or 4; R a is independently at each occurrence unsubstituted or substituted C MO hydrocarbyl; and X a is a single bond,— O— ,— S— ,— S(O)— ,— S(0) 2— ,— C(O)— , or a C 1-18 hydrocarbylene, which can be cyclic or acyclic, aromatic or nonaromatic, and can further comprise one or more heteroatoms selected from oxygen, nitrogen, sulfur, silicon, or phosphorus.
  • hydrocarbyl refers to a residue that contains only carbon and hydrogen unless it is specifically identified as“substituted hydrocarbyl”.
  • the hydrocarbyl residue can be aliphatic or aromatic, straight-chain, cyclic, bicyclic, branched, saturated, or unsaturated. It can also contain combinations of aliphatic, aromatic, straight chain, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties.
  • substituted means including at least one substituent such as a hydroxyl, amino, thiol, carboxyl, carboxylate, amide, nitrile, sulfide, disulfide, nitro, Cn 8 alkyl, Cn 8 alkoxyl, C 6 _i 8 aryl, C 6 _i 8 aryloxyl, C 7 _i 8 alkylaryl, or C 7 _i 8 alkylaryloxyl.
  • halogens i.e., F, Cl, Br, I
  • dihydroxy compounds include the following: bisphenol compounds such as 4,4'-dihydroxybiphenyl, l,4-dihydroxynaphthalene, l,5-dihydroxynaphthalene, 1,6- dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, bis(4- hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-3,5-dichlorophenyl)methane, bis(4-hydroxy- 3 ,5 -dibromophenyl)methane, bis(4-hydroxy-3 -methylphenyl)methane, bis(4-hydroxy-3 - chlorophenyl)methane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy
  • hydroquinone 2-ethyl hydroquinone, 2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone, 2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethyl hydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, chlorohydroquinone, acetoxyhydroquinone, and nitrohydroquinone.
  • the Ar may be derived from bisphenol A and R may be a methyl group providing polyphosphonates, phosphonate copolymers, random and block co-oligo(phosphonate carbonate)s and co-oligo(phosphonate ester)s, and oligomeric phosphonates that may have structures such as, but not limited to, structures of Formulae III:
  • a single aromatic diol may be used, and in other embodiments, various combinations of such aromatic diols may be incorporated into the polymer.
  • the phosphorous content of phosphonate component may be controlled by the molecular weight (MW) of the aromatic diol used in the oligomeric phosphonates, polyphosphonates, or copolyphosphonates.
  • MW molecular weight
  • a lower molecular weight aromatic diol may produce an oligomeric phosphonate, polyphosphonate, or copolyphosphonate with a higher phosphorus content.
  • An aromatic diol such as resorcinol, hydroquinone, or a combination thereof or similar low molecular weight aromatic diols may be used to make oligomeric phosphonates or polyphosphonates with high phosphorous content.
  • the phosphorus content, expressed in terms of the weight percentage, of the phosphonate oligomers, phosphonates, or copolyphosphonates may be in the range from about 2 wt. % to about 18 wt. %, about 4 wt. % to about 16 wt. %, about 6 wt. % to about 14 wt. %, about 8 wt. % to about 12 wt. %, or a value between any of these ranges.
  • phosphonate oligomers, polyphosphonates, or copolyphosphonates prepared from bisphenol A or hydroquinone may have phosphorus contents of 10.5 wt. % and 18 wt. %, respectively.
  • the phosphonate component may be a polyphosphonate containing long chains of the structural unit of Formula I.
  • the polyphosphonates may have a weight average molecular weight (Mw) according polystyrene standards of about 10,000 g/mole to about 100,000 g/mole as determined by GPC, and in other embodiments, the polyphosphonates may have an Mw of from about 12,000 to about 80,000 g/mole as determined by GPC.
  • the number average molecular weight (Mn) in such embodiments may be from about 5,000 g/mole to about 50,000 g/mole, or from about 8,000 g/mole to about 15,000 g/mole, and in certain embodiments the Mn may be greater than about 9,000 g/mole.
  • the molecular weight distribution (i.e., Mw/Mn) of such polyphosphonates may be from about 2 to about 10 in some embodiments and from about 2 to about 5 in other embodiments.
  • the phosphonate component may be a polyphosphonate containing branched structures of the structural unit of Formula I.
  • a branching agent i.e. tri or tetrahydroxy aromatic compound
  • the branched polyphosphonates may have a molecular weight distribution (i.e., Mw/Mn) of from about 2 to about 10 in some embodiments and from about 2.3 to about 3.2 in other embodiments.
  • the phosphonate component may be copolymers containing carbonate linkages [i.e., copoly(phosphonate carbonate)] or ester linkages [i.e., copoly(phosphonate esters)].
  • copoly (phosphonate carbonate)s may include repeating units derived from at least 20 mole percent high purity diaryl alkylphosphonate or optionally substituted diaryl
  • the alkylphosphonate, one or more diaryl carbonate, and one or more aromatic dihydroxy compounds wherein the mole percent of the high purity diaryl alkylphosphonate is based on the total amount of transesterification components, i.e., total diaryl alkylphosphonate and total diaryl carbonate.
  • the monomers of the copoly(phosphonate carbonate)s of various embodiments may be incorporated into polymer chain randomly. Therefore, the polymer chain may include alternating phosphonate and carbonate monomers linked by one or more aromatic dihydroxide and/or various segments in which several phosphonate or several carbonate monomers form phosphonate or carbonate segments. Additionally, the length of various phosphonate or carbonate segments may vary within individual copoly (phosphonate carbonate)s.
  • the phosphonate and carbonate content of the copoly(phosphonate carbonate)s may vary among embodiments, and embodiments are not limited by the phosphonate and/or carbonate content or range of phosphonate and/or carbonate content.
  • the phosphonate and/or carbonate content may vary among embodiments, and embodiments are not limited by the phosphonate and/or carbonate content or range of phosphonate and/or carbonate content.
  • the phosphonate and carbonate content of the copoly(phosphonate carbonate)s may vary among embodiments, and embodiments are not limited by the phosphonate and/or carbonate content or range of phosphonate and/or carbonate content.
  • the phosphonate and/or carbonate content may vary among embodiments, and embodiments are not limited by the phosphonate and/or carbonate content or range of phosphonate and/or carbonate content.
  • copoly(phosphonate carbonate)s may have a phosphorus content of from about 1% to about 20% by weight of the total copoly(phosphonate carbonate), and in other embodiments, the phosphorous content of the copoly(phosphonate carbonate)s of the invention may be from about 2% to about 10% by weight of the total polymer.
  • the copoly(phosphonate carbonate)s or copoly(phosphonate ester)s may have structures such as, but not limited to, those structures of Formulae IV and V, respectively:
  • Ar 1 and Ar 2 are each, independently, an aromatic group and -O-Ar'-O- and -0-Ar 2 -0- may be derived from a dihydroxy compound as described by structure (II).
  • R is a Ci_ 2 o alkyl, C2-20 alkene, C 2-20 alkyne, C 5-20 cycloalkyl, or C 6-20 aryl.
  • R 1 may be a Ci_ 20 alkylene or cycloalkylene, such as methylene, ethylene, propylene, butylene, pentylene, and the like, and in particular embodiments, R 1 can be derived from aliphatic diols such as, but not limited to, 1,4- cyclohexyldimethanol, 1, 4-butane diol, 1, 3-propane diol, ethylene diol, ethylene glycol, and the like and combinations thereof.
  • R 2 is, independently, a Ci_ 20 alkylene, C 2-20 alkylenylene, C 2-20 alkylynylene, C 5-20 cycloalkylene, or C 6-20 arylene.
  • R 2 can be derived from adipic acid, dimethyl terephthabc acid, terephthalic acid, isophthabc acid, naphthalene dicarboxylic acid and the like or derivatives thereof or combinations thereof.
  • R 2 may be an aromatic group such as naphthalene, phenylene, biphenylene, propane-2, 2-diyldibenzylene, and in some embodiments, R 2 can be derived from, for example, dimethyl terephthalate, dimethyl isophthalate, dimethyl naphthalate, and the like and combinations thereof.
  • R 2 may be, for example, naphthalene, phenyl, both of which may be substituted at any position on the rings.
  • Such copoly(phosphonate carbonates) or copoly(phosphonate esters) may be block copoly(phosphonate carbonates) or copoly(phosphonate esters) in which each m4, n4, and p5 is greater than about 1, and the copolymers contain distinct repeating phosphonate and carbonate blocks or phosphonate and ester blocks.
  • the copoly(phosphonate carbonates) or copoly(phosphonate esters) can be random copolymers in which each m4, n4, and p5 are each, independently, an integer from 1 to about 200, 1 to about 100, 1 to about 75, 1 to about 50, 1 to about 20, 1 to about 10, or 1 to about 5, or any integer between these ranges.
  • the Ar 1 and Ar 2 may be derived from bisphenol A and R may be a methyl group providing random and block co(phosphonate carbonate)s and co(phosphonate ester)s that may have structures such as, but not limited to, structures of Formulae VI and VII:
  • the copoly(phosphonate carbonate)s of various embodiments exhibit both a high molecular weight and a narrow molecular weight distribution (i.e., low polydispersity).
  • the copoly(phosphonate carbonate)s may have a weight average molecular weight (Mw) of about 10,000 g/mole to about 100,000 g/mole as determined by GPC, and in other embodiments, the copoly(phosphonate carbonate)s may have a Mw of from about 12,000 to about 80,000 g/mole as determined by GPC.
  • the number average molecular weight (Mn) in such embodiments may be from about 5,000 g/mole to about 50,000 g/mole, or from about 8,000 g/mole to about 15,000 g/mole, and in certain embodiments the Mn may be greater than about 9,000 g/mole.
  • the narrow molecular weight distribution (i.e., Mw/Mn) of such copoly(phosphonate carbonate)s may be from about 2 to about 7 in some embodiments and from about 2 to about 5 in other embodiments.
  • the molecular weight (weight average molecular weight as determined by gel permeation chromatography based on polystyrene calibration) range of the oligophosphonates, random or block co-oligo(phosphonate ester)s and co-oligo(phosphonate carbonate)s may be from about 500 g/mole to about 18,000 g/mole or any value within this range. In other embodiments, the molecular weight range may be from about 1,500 g/mole to about 15,000 g/mole, about 3,000 g/mole to about 10,000 g/mole, or any value within these ranges.
  • the molecular weight range may be from about 700 g/mole to about 9,000 g/mole, about 1,000 g/mole to about 8,000 g/mole, about 3,000 g/mole to about 4,000 g/mole, or any value within these ranges.
  • the oligomeric phosphonates can have about 60% to about 100% of the total of oligomeric phosphonates have two or more reactive end-groups. In other embodiments, about 75% to about 99% of the total of oligomeric phosphonates have two or more reactive end-groups.
  • the reactive end-groups may be, for example, epoxy, vinyl, vinyl ester, isopropenyl, isocyanate, or combinations thereof, and in certain embodiments, about 80% to about 100% of the total oligomeric phosphonates may have two or more hydroxyl end groups.
  • the oligomeric phosphonates or portions thereof may include oligophosphonate, random co-oligo(phosphonate ester), block co-oligo(phosphonate ester), random co-oligo(phosphonate carbonate), block co-oligo(phosphonate carbonate), or combinations thereof.
  • the oligomeric phosphonates may include linear oligomeric phosphonates, branched oligomeric phosphonates, or a combination thereof, and in other embodiments, such oligomeric phosphonates may further include hyperbranched
  • a halogen-free composition comprising: Part A: at least one isocyanate; Part B: (1) at least one isocyanate reactive polyether polyol, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%; and (2) at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof, wherein at least one of Part A or Part B further comprises a phosphonate oligomer.
  • Part A at least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof
  • Part B (1) at least one isocyanate reactive polyether polyol, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%
  • at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof, wherein at least one of Part A or Part B further comprises a phosphonate oligomer.
  • a halogen-free composition comprising: Part A, at least one isocyanate selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof; and Part B, at least one isocyanate reactive polyether polyol, a phosphonate oligomer, and at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof.
  • MDI 4,4'-methyl diphenyl diisocyanate
  • Part B at least one isocyanate reactive polyether polyol, a phosphonate oligomer, and at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof.
  • a halogen-free composition comprising: Part A, at least one isocyanate selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof and a phosphonate oligomer, and Part B, at least one isocyanate reactive polyether polyol and at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof.
  • MDI 4,4'-methyl diphenyl diisocyanate
  • polymeric MDI polymeric MDI
  • phosphonate oligomer Part B, at least one isocyanate reactive polyether polyol and at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof.
  • the polyether polyol can contain a content of ethylene oxide unit of about 20% to about 100%, or about 20% to about 90%, or about 20% to about 80%, or about 20% to about 70%, or about 20% to about 60%, or about 20% to about 50%, or about 20% to about 40%, or about 20% to about 30%.
  • the polyether polyol can contain a content of ethylene oxide units of at least about 20%, or at least about 30%, or at least about 40%, or at least about 50%, or at least about 60%, or at least about 70%, or at least about 80%, or at least about 90%.
  • the composition can have a density ranging from about 40 kg/m 3 to about 200 kg/m , or from about 40 kg/m to about 180 kg/m , or from about 40 kg/m to about 160 kg/m , or from about 40 kg/m 3 to about 140 kg/m 3 .
  • the composition can have a density ranging from about 50 kg/m 3 to about 180 kg/m 3 , or from about 60 kg/m 3 to about 160 kg/m 3 , or from about 70 kg/m 3 to about 140 kg/m 3 .
  • the composition can have a density ranging from about 80 kg/m 3 to about 140 kg/m 3 .
  • the co-flame retardant cannot comprise graphite.
  • the composition can be a polyurethane foam or a flexible polyurethane foam. In some embodiments, the composition is substantially free of graphite. In some embodiments, the composition is free of graphite.
  • the co-flame retardant can be selected from the group consisting in ammonium polyphosphate, melamine , melamine polyphosphate, melamine cyanurate, aluminum trihydrate, silica, carbon nanotubes, or any combinations thereof.
  • the composition can lose a maximum of about 5% of its tensile strength after heat aging at least about 150 °C for about 7 days, or a maximum of about 10% of its tensile strength after heat aging at least about 150 °C for about 7 days, or a maximum of about 15% of its tensile strength after heat aging at least about 150 °C for about 7 days, or a maximum of about 20% of its tensile strength after heat aging at least about 150 °C for about 7 days, or a maximum of about 25% of its tensile strength after heat aging at least about 150 °C for about 7 days, or a maximum of about 30% of its tensile strength after heat aging at least about 150 °C for about 7 days, or a maximum of about 35% of its tensile strength after heat aging at least about 150 °C for about 7 days or a maximum of about 40% of its tensile strength after heat aging at least about 150 °C for about 7 days, or
  • the composition can achieve FMVSS302 rating.
  • the composition can achieve a V-0 rating at about 0.5 inch according to Underwriter’s Laboratories Standard UL94 Flammability test before and after heat aging.
  • Some other embodiments pertain to a method for producing a flexible polyurethane foam comprising mixing and reacting Part A and Part B to form a foam, wherein Part A: at least one isocyanate; Part B: (1) at least one isocyanate reactive polyether polyol, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%; and (2) at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof, wherein at least one of Part A or Part B further comprises a phosphonate oligomer.
  • Some other embodiments pertain to a method for producing a flexible polyurethane foam comprising mixing and reacting Part A and Part B to form a foam, wherein Part A: at least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof, and Part B: (1) at least one isocyanate reactive polyether polyol, wherein one of the polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%; and (2) at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof, wherein at least one of Part A or Part B further comprises a phosphonate oligomer.
  • Part A at least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof
  • Some other embodiments pertain to a method for producing a flexible polyurethane foam comprising mixing and reacting Part A and Part B to form a foam, wherein Part A comprises at least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof, and Part B comprises at least one isocyanate reactive polyether polyol, wherein one polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%, a phosphonate oligomer, and at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co-flame retardant, or any combinations thereof.
  • MDI 4,4'-methyl diphenyl diisocyanate
  • Part B comprises at least one isocyanate reactive polyether polyol, wherein one polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%, a
  • Some other embodiments pertain to a method for producing a flexible polyurethane foam comprising mixing and reacting Part A and Part B to form a foam, wherein Part A comprises a phosphonate oligomer, and at least one isocyanates selected from the group consisting of 4,4'-methyl diphenyl diisocyanate (MDI), polymeric MDI, or a combination thereof, and Part B comprises at least one isocyanate reactive polyether polyol, wherein one polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%, and at least one additional component selected from the group consisting of blowing agent, surfactant, chain extender, catalyst, crosslinking agent, filler, cell opener, co flame retardant, or any combinations thereof.
  • MDI 4,4'-methyl diphenyl diisocyanate
  • Part B comprises at least one isocyanate reactive polyether polyol, wherein one polyether polyol contains a content of ethylene oxide units of at least about 20% to about 100%, and at least
  • Some other embodiments pertain to a halogen-free flexible polyurethane foam for use in thermal applications including engine compartment of vehicle, underbody thermal part, or a combination thereof.
  • polymer composition refers to a composition that comprises at least one of the present invention and at least one other polymer, oligomer, or monomer mixture.
  • the other polymer, oligomer, or monomer mixture may include those that comprise, or are partially comprised of, or are comprised of monomers intended to produce the following polymer families including but not limited to a polycarbonate, polyacrylate, polyacrylonitrile, polyester, polyether, polyamide, polystyrene, polyurethane, polyurea, polyurethane urea, polyepoxy, poly(acrylonitrile butadiene styrene), polyimide, polyarylate, poly(arylene ether), polyethylene, polypropylene, polyphenylene sulfide, poly(vinyl ester), polyvinyl chloride, bismaleimide polymer, polyanhydride, liquid crystalline polymer, cellulose polymer, benzoxazine resin, another polyphosphonate, or a
  • Any epoxy resin can be used for the purpose(s) of the invention provided that the resin contains at least one glycidyl group, alicyclic epoxy group, or a similar epoxy group (i.e., oxirane or ethoxyline group).
  • the resin contains at least one glycidyl group, alicyclic epoxy group, or a similar epoxy group (i.e., oxirane or ethoxyline group).
  • a similar epoxy group i.e., oxirane or ethoxyline group.
  • an epoxy resin having two or more epoxy groups is preferred.
  • Such a component can be represented by novolac-type epoxy resin, cresol-novolac epoxy resin, triphenolalkane-type epoxy resin, aralkyl-type epoxy resin, aralkyl-type epoxy resin having a biphenyl skeleton, biphenyl-type epoxy resin, dicyclopentadiene-type epoxy resin, heterocyclic -type epoxy resin, epoxy resin containing a naphthalene ring, a bisphenol-A type epoxy resin, a methylene dianiline type epoxy resin, a bisphenol-F type epoxy compound, stilbene-type epoxy resin, trimethylol-propane type epoxy resin, terpene-modified epoxy resin, linear aliphatic epoxy resin obtained by oxidizing olefin bonds with peracetic acid or a similar peracid, alicyclic epoxy resin, or sulfur-containing epoxy resin.
  • the substrate may also be composed of two or more epoxy resins of the aforementioned types.
  • Preferable epoxy resins are those derived from bisphenol A or methylene dianiline.
  • Preferable for use are aralkyl -type epoxy resins with a biphenyl structure, a bisphenol A structure or a methylene dianiline structure.
  • the epoxy resin is typically commercially available, though this is not a requirement for applicability.
  • the epoxy may also contain as a component a benzoxazine compound, oligomer or resin.
  • the polymer compositions of the present invention may comprise other components, such as but not limited to other flame retardants, chopped or continuous glass, metal, carbon based, or ceramic fibers; fillers, surfactants, mold release agents, organic binders, polymeric binders, crosslinking agents, coupling agents, anti-dripping agents, colorants, inks, dyes, antioxidants or other stabilizers, or any combination thereof.
  • other components such as but not limited to other flame retardants, chopped or continuous glass, metal, carbon based, or ceramic fibers; fillers, surfactants, mold release agents, organic binders, polymeric binders, crosslinking agents, coupling agents, anti-dripping agents, colorants, inks, dyes, antioxidants or other stabilizers, or any combination thereof.
  • Some embodiments can be used as coatings on plastics, metals, ceramic, or wood products or they can be used to fabricate articles, such as free-standing films and extruded sheets, fibers, foams, molded articles, adhesives, filaments, and fiber reinforced composites. These articles may be well-suited for applications requiring fire resistance.
  • Some embodiments and polymer compositions including them exhibit outstanding flame resistance and good melt processability. Such improvements make these materials useful in applications in the automotive and electronic sectors that require outstanding fire retardancy, high temperature performance, and melt processability.
  • Expandable graphite (ExG) (Nyagraph 35) was obtained from Nyacol Nano Technologies. Halloysite nanotubes (Dragonite APA) was obtained from Applied Mineral Inc. Ammonium polyphosphate (APP) was obtained from Clariant and Melamine polyphosphate (Melapur 200) was obtained from BASF. Melamine, 99%, was purchased from Sigma Aldrich. Aerosil R8200, a hydrophobic silica, was obtained from Evonik.
  • (C) Isocyanate Suprasec 9634, modified monomeric 4,4' methyl diphenyl diisocyanate (MDI) was obtained from Huntsman and MDI based prepolymer Voralux HE 150 from Dow.
  • MDI modified monomeric 4,4' methyl diphenyl diisocyanate
  • Tegostab B4113 was obtained from Evonik.
  • UL-54 were obtained from Momentive. Dabco 33LV was obtained from Evonik. K-KAT XC-B221 was obtained from King Industries Specialties Chemicals. Di-n-butyltin dilaurate was purchased from Sigma Aldrich.
  • NOFIA OL1001 was incorporated into the polyol side of the formulation using two methods. (1) Pre-dissolving NOFIA OL1001 powder in a polyether polyol typically with >30% ethylene oxide content such as the polyether polyol Poly-G 55-56; 2000 MW.
  • Foam Preparation To initiate the foaming reaction, the required amount of isocyanate was metered into the polyol side containing all the ingredients described above. Finally, the mixture was poured into a mold where the complete foaming reaction occurred. The foam was allowed to fully react at room temperature for 1 day.
  • Thermal stability of the polyurethane foam formulations was evaluated by Thermogravimetric analysis (TGA) in air. The samples were heated at a ramp rate of 10 °C/min from 25 °C to 800 °C.
  • compositions disclosed below show the versatility of compositions that can be prepared using phosphonate oligomers as flame retardant compounds.
  • Example 1 [0107] Several polyurethane formulations containing 5% oligomeric phosphonate (NOFIA OL1001) were prepared to investigate the effect of the catalyst system on the reaction/ incorporation of NOFIA OL1001 into the polyurethane foam systems.
  • Table 1-1 provides the recipe for foam formulations prepared using a single catalyst and
  • Table 1-2 provides the recipes for foam formulations prepared using a blend of dibutyltin dilaurate plus a second catalyst.
  • amine catalysts Naax-Al and Dabco 33LV were observed to be more effective as compared to their Tin counterparts: Cream time was short (within 0-1 min after charging the isocyanate); the Tin catalysts (Fomrez catalyst series) were slow to react (foam rise kicks off within 2-5 minutes); and no foam rise was observed when the Bismuth catalyst was used.
  • Example 2 discloses the impact of blending NOFIA OL1001 with co-FR additives on the foaming process and the density values of polyurethane foam formulations.
  • Table 2-1 provides formulation recipes with loading levels of NOFIA OF 1001 ranging between 0-10%. The loading of the co-FR, Dragonite APA Halloysite nanotubes (HNT), or Melamine polyphosphate (MP) was 1%.
  • Comparable example C2-1 is the baseline formulation with no NOFIA OF1001 or other co-FR additives.
  • the viscosity of the formulation mixtures prior to charging the isocyanate to initiate the foaming process remained low, making the process appealing. Comparable final density values were observed for the resulting foam formulations (within experimental error, between 110 - 135 kg/m 3 ).
  • the NOFIA OLlOOl is first dissolved in PolyG-55-56, which is then added to the polyether polyol (Jeffol G31-28; 6000 MW).
  • the presence of NOFIA OL1001 in the recipes also improves the dispersion of other co-FR additives that can be used along NOFIA OLlOOl .
  • Table 2-2 the recipes of formulations containing expandable graphite (ExG) or a combination of ExG and NOFIA OLlOO l are provided.
  • ExG is insoluble in the polyols and quickly settles down during the sample preparation process if agitation is not maintained.
  • NOFIA OLlOOl helps to disperse ExG in the final foam formulation: dark spots indicate areas where aggregates or
  • Example 3 discloses the impact of polyols and NOFIA OL1001 on the thermal stability of the foam formulation.
  • the ratio of the polyol (Voranol CP6001; 6000 MW) to the polyol (PolyG-55-56; 2000 MW) was varied.
  • Table 3 comparative example 3-C1 and example 3-1 the ratio is set at 75 to 25 and, in comparative example 3-C2 and example 3-2, the ratio is set at 70 to 30 (Voranol CP6001 to PolyG-55- 56).
  • Poly-G 55-56 is used as the solubilizing polyol for NOFIA OF1001.
  • the resulting foam density of these formulations was 140 kg/m 3 .
  • Table 3-2 shows formulations used to prepare foam samples with 5% and 10% NOFIA OL1001 in the final foam.
  • the comparative example 3C-2 shows foam samples containing no NOFIA OL1001.
  • Example 4 discloses the synergistic effects of a combination of melamine and NOFIA OL1001 and silica on the fire behavior properties of the foams in UL94 test.
  • the total loading levels of the fire retardants in the final foam was set at 30 - 35%.
  • the comparative example 4-C1 containing melamine only, at 35% loading in the final foam, achieved a V-2 rating.
  • a V-0 is achieved.
  • the incorporation of silica was observed to improve upon the fire performance of the foam, especially dripping, is mitigated.
  • Silica is particularly effective when used in combination with melamine and NOFIA OL1001.
  • Table 5 discloses the fire properties of the foam formulations prepared using a premix of NOFIA
  • Isocyanate/NOFIA OLlOOl/PolyG-55-56 charged last to initiate the foaming process.
  • an extra surfactant, Pluronic L62LF is also used.
  • Both foam prepared using the modified process achieved V-0 in the UF-94 test and the density values achieved ranged between 110 and 125 kg/m 3 .
  • Table 6 shows examples of compositions used to make foams that achieve VO at density at 70-80 kg/m 3 .
  • Comparative example (6-C1) shows the formulation with melamine only, without the NOFIA OL1001 does not self extinguish (no rating NR).
  • the addition of 9.3% NOFIA OF1001 in example 6-A shows the foam self-extinguishes, but fails due to some burning drips.
  • Example 6-B shows the foam containing the addition of 3 php silica to melamine and NOFIA OF1001 achieves V0 rating.
  • Table 7 shows an example of a composition used to make 0.5 inch foams that are able to achieve V0 at density of 190 kg/m 3 (0.5 inch thickness) with combination of melamine, NOFIA OL1001 and silica.
  • Table 8 shows examples of compositions used to make flexible polyurethane foams of 40 kg/m 3 density containing NOFIA OL1001.
  • the NOFIA OF 1001 was used in powder form and dispersed into the Specflex NF766 polyol.
  • the combination of two silicon surfactants (Dow Coming 1280 additive and Tegostab B4113) was tested to determine the best foam cell structure when NOFIA OF 1001 incorporated into the low density foam.
  • Visual observation of a cross-section of the foams showed the samples prepared with the highest loading of the Dow Coming 1280 additive (Example 8-D) had the best consistency in cell structure.
  • Analysis of the foams determined 90-94% of NOFIA OF 1001 had reacted into the foam.
  • Foams with 6php NOFIA OF1001 and 6php melamine pass the flame test FMVSS302.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne d'une manière générale le domaine des compositions ignifuges, et en particulier des compositions ignifuges sans halogène, des procédés pour les préparer, leur utilisation pour des mousses de polyuréthane souples. En particulier, les compositions sont préparées à partir de deux parties, la partie A comprenant au moins un isocyanate et la partie B comprenant au moins un polyéther polyol réactif avec l'isocyanate; et au moins un composant supplémentaire, au moins l'une parmi la partie A ou la partie B comprenant en outre un oligomère phosphonate.
PCT/US2019/028151 2018-04-18 2019-04-18 Compositions ignifuges sans halogène pour mousses de polyuréthane souples Ceased WO2019204625A1 (fr)

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WO2021094501A1 (fr) * 2019-11-15 2021-05-20 Polyu Gmbh Composition de prépolymère ignifuge, composition de polymère ignifuge, et leurs procédés de fabrication et leurs utilisations
WO2021247630A1 (fr) 2020-06-05 2021-12-09 Dow Global Technologies Llc Mousse de polyuréthane souple à alvéoles ouverts présentant une performance améliorée d'auto-extinguibilité aux essais de résistance au feu
US20220119427A1 (en) * 2019-01-31 2022-04-21 Dow Global Technologies Llc Beta-hydroxyphosphonate functionalized polyols
CN116288783A (zh) * 2023-02-14 2023-06-23 江苏奥神新材料股份有限公司 一种高阻燃聚酰亚胺纤维及其制备方法
CN119060530A (zh) * 2024-11-05 2024-12-03 淮北师范大学 一种复合型陶瓷化材料的制备工艺

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WO2007019148A2 (fr) * 2005-08-04 2007-02-15 Syngenta Participations Ag Compositions moussantes a base d'urethanne destinees a la lutte contre les ravageurs
US20130046036A1 (en) * 2011-08-19 2013-02-21 Frx Polymers, Inc. Thermoplastic polyurethanes with exceptional fire resistance
US20140117271A1 (en) * 2011-06-29 2014-05-01 Dow Global Technologies Llc Thermally stable flame resistant flexible polyurethane foam
US20150099816A1 (en) * 2013-10-03 2015-04-09 Sabic Innovative Plastics Ip B.V. Flexible polyurethane foam and associated method and article
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WO2007019148A2 (fr) * 2005-08-04 2007-02-15 Syngenta Participations Ag Compositions moussantes a base d'urethanne destinees a la lutte contre les ravageurs
US20140117271A1 (en) * 2011-06-29 2014-05-01 Dow Global Technologies Llc Thermally stable flame resistant flexible polyurethane foam
US20130046036A1 (en) * 2011-08-19 2013-02-21 Frx Polymers, Inc. Thermoplastic polyurethanes with exceptional fire resistance
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US20220119427A1 (en) * 2019-01-31 2022-04-21 Dow Global Technologies Llc Beta-hydroxyphosphonate functionalized polyols
US12110306B2 (en) * 2019-01-31 2024-10-08 Dow Global Technologies Llc Beta-hydroxyphosphonate functionalized polyols
WO2021094501A1 (fr) * 2019-11-15 2021-05-20 Polyu Gmbh Composition de prépolymère ignifuge, composition de polymère ignifuge, et leurs procédés de fabrication et leurs utilisations
WO2021247630A1 (fr) 2020-06-05 2021-12-09 Dow Global Technologies Llc Mousse de polyuréthane souple à alvéoles ouverts présentant une performance améliorée d'auto-extinguibilité aux essais de résistance au feu
CN116288783A (zh) * 2023-02-14 2023-06-23 江苏奥神新材料股份有限公司 一种高阻燃聚酰亚胺纤维及其制备方法
CN119060530A (zh) * 2024-11-05 2024-12-03 淮北师范大学 一种复合型陶瓷化材料的制备工艺

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