Inhibition of solids formation in co2 polyurethane production

Abstract

Described herein are compositions and methods for producing polyurethane foams. An exemplary method includes contacting at least one organic isocyanate with at least one polyol in the presence of a blowing agent and a catalyst composition.

Description

Technical Field

[0001] Described herein are compositions and methods for producing polyurethane foams. An exemplary method includes contacting at least one organic isocyanate with at least one polyol in the presence of a blowing agent and a catalyst composition. Background Art

[0002] Tertiary amines are commonly used as catalysts in the preparation of polyurethane materials, which are widely used in durable consumer goods (such as automobiles, household appliances, furniture, toys, and other products) as well as in commercial and residential insulation. Minimizing chemical emissions in these applications is crucial to eliminating potential exposure of workers and end users to hazards associated with foreign contaminants or byproducts generated by these contaminants, which may be present in some of the raw materials used to make polyurethane-based products. Several components are used in the preparation of polyurethane foam, such as polyols, isocyanates, surfactants, blowing agents, crosslinking agents, cell openers, pigments, fillers, flame retardants, metal catalysts, and tertiary amine catalysts. In some cases, certain tertiary, secondary, and primary amines are combined with auxiliary blowing agents, such as CO2, to achieve lower foam densities. However, the combination of amines and CO2 preferentially and undesirably leads to the formation of solid intermediate carbamates. Premature formation of any solids in polyurethane foam manufacturing equipment, especially when specialized auxiliary blowing agents are used, often results in accelerated pressure buildup within the equipment, leading to premature downtime and financial losses.

[0003] There is a need for low emission amine catalyst compositions that minimize the formation of solid intermediate urethanes during the production of polyurethane foams. Summary of the Invention

[0004] Overview

[0005] One embodiment described herein is a method of making a polyurethane foam, the method comprising:

[0006] The foam formulation was prepared as follows:

[0007] At least one organic isocyanate is contacted with at least one polyol in the presence of a blowing agent and a catalyst composition, wherein the catalyst composition comprises:

[0008] at least one tertiary amine comprising an isocyanate-reactive group; and

[0009] Monohydric alcohol, wherein the monohydric alcohol comprises at least one alcohol selected from the group consisting of: C 1-7 Straight chain alkyl -OH, C 3-6 Branched alkyl -OH and C 3-6 Cycloalkyl-OH.

[0010] In one aspect, the at least one tertiary amine comprising an isocyanate-reactive group comprises at least one moiety selected from: In another aspect, the blowing agent comprises at least one selected from carbon dioxide (CO 2 ), water, acetone, methyl formate, hydrofluorocarbon (HFC), hydrofluoroolefin (HFO) and hydrocarbon. In another aspect, the blowing agent comprises carbon dioxide (CO 2) and water. In another aspect, the at least one organic isocyanate is toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric isocyanate or a combination thereof. In another aspect, the at least one polyol is a polyether polyol, polyester polyol, copolymer polyol or natural oil polyol. In another aspect, the at least one polyol is new or recycled. In another aspect, the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of a crosslinking agent. In another aspect, the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of an organosilicon surfactant. In another aspect, the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of an additional amine.

[0011] In another aspect, the additional amine comprises at least one selected from the group consisting of triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole, N-methylmorpholine, N-ethylmorpholine, triethylamine, N,N′-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 2,4,6-tris(dimethylaminomethyl)phenol, N-methyldicyclohexylamine, pentamethyldipropylenetriamine, N-methyl-N '-(2-Dimethylamino)-ethyl-piperazine, tributylamine, pentamethyl-diethylenetriamine, hexamethyl-triethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexyl-amine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl) ether, tris(3-dimethylaminopropyl)amine, 1,8-diazabicyclo[5.4.0]undecane, and acid-blocked derivatives of 1,8-diazabicyclo[5.4.0]undecane.

[0012] In another aspect, the contacting of at least one organic isocyanate with at least one polyol is carried out in the presence of a metal catalyst. In another aspect, the metal catalyst is a metal carboxylate. In another aspect, the metal carboxylate comprises a metal and a carboxylate anion. In another aspect, the metal is at least one selected from tin (Sn), bismuth (Bi), lead (Pb), iron (Fe), zinc (Zn) and potassium (K). In another aspect, the carboxylate is a carboxylate anion of at least one carboxylic acid selected from the group consisting of acetic acid, propionic acid, butyric acid, pentanoic acid, pivalic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid and octadecanoic acid. In another aspect, the metal catalyst is an organotin catalyst. In another aspect, the organotin catalyst is at least one selected from the group consisting of dibutyltin diacetate, dimethyltin dilauryl mercaptan, dibutyltin dilauryl mercaptan, dimethyltin diisooctyl maleate, dibutyltin diisooctyl maleate, dimethyltin bis(2-ethylhexyl mercaptoacetate), dibutyltin bis(2-ethylhexyl mercaptoacetate), dimethyltin neodecanoate, dibutyltin neodecanoate, dimethyltin isononanoate, dibutyltin isononanoate, stannous octoate, stannous neodecanoate, stannous isononanoate, and stannous carboxylates. In another aspect, the metal catalyst is present in an amount of about 0 parts per hundred parts of polyol (pphp) to about 20 pphp. In another aspect, the polyurethane foam has an isocyanate index of between 80 and 120. In another aspect, the polyurethane foam has a density of between 0.8 pounds per cubic foot (pcf) and 3.5 pcf. In another aspect, the monohydric alcohol is present in the catalyst composition at 5 mass percent (wt%) to 15 wt%. In another aspect, the monohydric alcohol is present in less than 0.5 wt% of the foam formulation. In another aspect, the monohydric alcohol, tertiary amine, is present in less than 1.0 wt% of the foam formulation. In another aspect, the monohydric alcohol comprises at least one alcohol selected from methanol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, cyclopentanol and cyclohexanol.

[0013] In another aspect, the at least one tertiary amine is a tertiary amine of the formula:

[0014]

[0015] in:

[0016] R 1 is hydrogen or -C 1-4 alkyl;

[0017] R 2 It is hydrogen, -C1-6 alkyl,

[0018] R 3 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; and

[0019] R 4 and R 5 are independently hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2.

[0020] In another aspect, the at least one tertiary amine is selected from:

[0021]

[0022] In another aspect, the at least one tertiary amine is a tertiary amine of the formula:

[0023]

[0024] in:

[0025] yes

[0026] R 6 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH, -C 1-6 Alkyl-NH2, -C 1-6 Alkyl-N(CH3)2;

[0027] R 7 It is hydrogen, -C 2-6 Alkyl-OH, -C 2-6 Alkyl-NH2, -C 2-6 Alkyl-N(CH3)2 or

[0028] R 8 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2;

[0029] R 9 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; and

[0030] R10 and R 11 are independently hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2.

[0031] In another aspect, the at least one tertiary amine is selected from:

[0032]

[0033] In another aspect, the at least one tertiary amine is selected from:

[0034]

[0035] In another aspect, the catalyst composition comprises at least two tertiary amines. In another aspect, the catalyst composition further comprises a tertiary amine that does not contain an isocyanate-reactive group. In another aspect, the tertiary amine that does not contain an isocyanate-reactive group is one or more selected from the following:

[0036]

[0037] Another embodiment described herein is a method of making a polyurethane foam, the method comprising:

[0038] The foam formulation was prepared as follows:

[0039] At least one organic isocyanate is contacted with at least one polyol in the presence of a blowing agent and a catalyst composition, wherein the catalyst composition comprises:

[0040] at least one tertiary amine comprising an isocyanate-reactive group; and

[0041] Monohydric alcohol, wherein the monohydric alcohol comprises a compound selected from C 1-7 Straight chain alkyl -OH, C 3-6 Branched alkyl -OH and C 3-6 at least one alcohol of a cycloalkyl-OH group;

[0042] in:

[0043] The monohydric alcohol is present in the catalyst composition at 5 wt % to 15 wt %; and

[0044] The polyurethane foam has an isocyanate index between 80 and 120.

[0045] In one aspect, the at least one tertiary amine comprising an isocyanate-reactive group comprises at least one moiety selected from: In another aspect, the blowing agent comprises at least one selected from carbon dioxide (CO 2 ), water, acetone, methyl formate, hydrofluorocarbon (HFC), hydrofluoroolefin (HFO) and hydrocarbon. In another aspect, the at least one organic isocyanate is toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) or a combination thereof. In another aspect, the at least one polyol is a polyether polyol, a polyester polyol, a copolymer polyol or a natural oil polyol. In another aspect, the at least one polyol is new or recycled. In another aspect, the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of a crosslinking agent. In another aspect, the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of an organosilicon surfactant. In another aspect, the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of an additional amine.

[0046] In another aspect, the additional amine comprises at least one selected from the group consisting of triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole, N-methylmorpholine, N-ethylmorpholine, triethylamine, N,N′-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 2,4,6-tris(dimethylaminomethyl)phenol, N-methyldicyclohexylamine, pentamethyldipropylenetriamine, N-methyl-N '-(2-Dimethylamino)-ethyl-piperazine, tributylamine, pentamethyl-diethylenetriamine, hexamethyl-triethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexyl-amine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl) ether, tris(3-dimethylaminopropyl)amine, 1,8-diazabicyclo[5.4.0]undecane, and acid-blocked derivatives of 1,8-diazabicyclo[5.4.0]undecane.

[0047] In another aspect, the contacting of at least one organic isocyanate with at least one polyol is carried out in the presence of a metal catalyst. In another aspect, the metal catalyst is a metal carboxylate. In another aspect, the metal carboxylate comprises a metal and a carboxylate anion. In another aspect, the metal is at least one selected from tin (Sn), bismuth (Bi), lead (Pb), iron (Fe), zinc (Zn) and potassium (K). In another aspect, the carboxylate is a carboxylate anion of at least one carboxylic acid selected from the group consisting of acetic acid, propionic acid, butyric acid, pentanoic acid, pivalic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid and octadecanoic acid. In another aspect, the metal catalyst is an organotin catalyst. In another aspect, the organotin catalyst is at least one selected from the group consisting of dibutyltin diacetate, dimethyltin dilauryl mercaptan, dibutyltin dilauryl mercaptan, dimethyltin diisooctylmaleate, dibutyltin diisooctylmaleate, dimethyltin bis(2-ethylhexylmercaptoacetate), dibutyltin bis(2-ethylhexylmercaptoacetate), dimethyltin neodecanoate, dibutyltin neodecanoate, dimethyltin isononanoate, dibutyltin isononanoate, stannous octoate, stannous neodecanoate, stannous isononanoate, and stannous carboxylates. In another aspect, the metal catalyst is present in an amount of from about 0 parts per 100 parts of polyol (pphp) to about 20 pphp.

[0048] In another aspect, the at least one tertiary amine is a tertiary amine of the formula:

[0049]

[0050] in:

[0051] R 1 is hydrogen or -C 1-4 alkyl;

[0052] R 2 It is hydrogen, -C 1-4 alkyl,

[0053] R 3 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; and

[0054] R 4 and R 5 are independently hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2.

[0055] In another aspect, the at least one tertiary amine is selected from:

[0056]

[0057]

[0058] In another aspect, the at least one tertiary amine is a tertiary amine of the formula:

[0059]

[0060] in:

[0061] yes

[0062] R 6 It is hydrogen, -C 1-4 Alkyl, -C 1-4 Alkyl-OH, -C 1-4 Alkyl-NH2, -C 1-4 Alkyl-N(CH3)2;

[0063] R 7 It is hydrogen, -C 2-6 Alkyl-OH, -C 2-6 Alkyl-NH2, -C 2-6 Alkyl-N(CH3)2 or

[0064]

[0065] R 8 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2;

[0066] R 9 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; and

[0067] R 10 and R 11 are independently hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2.

[0068] In another aspect, the at least one tertiary amine is selected from:

[0069] BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Figure 1 A comparative Fourier transform infrared spectroscopy (FTIR) spectrum is shown, which illustrates possible FTIR at 1600-1736 cm -1 Carbonyl absorption band of carbamate in the range of 1600-1700 cm (spectrum AD). -1 The wavenumber range is indicated by the dashed line. The carbamate peak is at ∼1674 cm -1 The peaks of the NE300 peaks are shown in Figures 4 and 5. Spectrum A (blue) shows the NE300 control without CO treatment and without a carbamate peak. Spectrum B (green) shows the NE300 with 10% isopropyl alcohol treated with CO and without a carbamate peak. Spectrum C (purple) shows the NE300 with 5% isopropyl alcohol treated with CO and with a small but noticeable carbamate peak. Spectrum D (red) shows the NE300 without isopropyl alcohol treated with CO and with a significant carbamate peak.

[0071] Details

[0072] Methods for making polyurethane foam are described herein. The method for making polyurethane foam may include preparing a foam formulation by contacting at least one organic isocyanate with at least one polyol in the presence of a blowing agent and a catalyst composition. The catalyst composition may include at least one tertiary amine containing an isocyanate-reactive group and a monool. The monool may include a tertiary amine selected from C 1-7 Straight chain alkyl -OH, C 3-6 Branched alkyl -OH and C 3-6 At least one alcohol containing a cycloalkyl-OH group. In various cases, the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of an additional amine. Various aspects of suitable organic isocyanates, polyols, blowing agents, tertiary amines, additional amines, metal catalysts, and other formulation components are described below.

[0073] definition

[0074] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those of ordinary skill in the art are generally understood. For example, any nomenclature used in connection with chemistry as described herein, synthetic organic chemistry and polymer chemistry and their technology are well known in the art and commonly used. In the event of conflict, the present disclosure (including definitions) shall prevail. Exemplary methods and materials are described below, although methods and materials similar or equivalent to those described herein can be used in the practice or test of embodiments as described herein and aspects.

[0075] As used herein, terms such as "including," "comprising," and "having" mean "comprising." The present disclosure also contemplates other embodiments that "include," "consist of," and "consist essentially of" the embodiments or elements presented herein, whether explicitly stated or not.

[0076] As used herein, unless otherwise indicated herein or clearly contradicted by context, the terms "a," "an," "the," and similar terms used in the context of this disclosure (especially in the claims) should be construed to cover both the singular and the plural. Furthermore, unless otherwise indicated herein or clearly contradicted by context, "a," "an," or "the" means "one or more."

[0077] As used herein, the term "or" can be conjunctive or disjunctive.

[0078] As used herein, the term "substantially" means to a great or significant extent, but not completely.

[0079] As used herein, the term "about" or "approximately" applied to one or more related numerical values ​​refers to a numerical value that is similar to a specified reference value or within an acceptable error range of a specific value as determined by one of ordinary skill in the art, which will depend in part on how to measure or determine the numerical value, such as the limitations of the measurement system. In one aspect, the term "about" refers to any numerical value within a variation of up to ±10% of the numerical value modified by the term "about", including both integers and decimal parts. Alternatively, according to practice in the art, "about" can refer to within 3 or more standard deviations. Alternatively, as with respect to a biological system or method, the term "about" can refer to within an order of magnitude of a numerical value, in some embodiments within 5 times, and in some embodiments within 2 times. As used herein, the symbol "~" refers to "about" or "approximately".

[0080] All ranges disclosed herein include both endpoints as discrete values ​​and all integers and decimals specified within the range. For example, a range of 0.1-2.0 includes 0.1, 0.2, 0.3, 0.4 ... 2.0. If an endpoint is modified by the term "about," the specified range is extended by a variation of up to ±10% of any value (including the endpoint) within the range or within 3 or more standard deviations.

[0081] As used herein, the terms "control" or "reference" are used interchangeably herein. A "reference" or "control" level can be a predetermined value or range used as a baseline or benchmark against which measurements are evaluated. "Control" also refers to a controlled experiment.

[0082] As used herein, the terms "room temperature," "RT," or "ambient temperature" refer to the typical temperature in an indoor laboratory environment. In one aspect, the laboratory environment is climate controlled to maintain the temperature at a substantially uniform temperature or within a specific temperature range. In one aspect, "room temperature" refers to a temperature of approximately 20-30°C, including all integers and endpoints within the specified range. In another aspect, "room temperature" refers to a temperature of approximately 20-27°C; approximately 22-25°C; approximately 22-27°C; approximately 25-27°C; approximately 22°C ± 10%; approximately 25°C ± 10%; approximately 27°C ± 10%; ~20°C, ~22°C, ~25°C, or ~27°C at standard atmospheric pressure.

[0083] Definitions of specific functional groups and chemical terms are described in more detail below.For purposes of this disclosure, the chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th ed., inside cover, and specific functional groups are generally defined as described therein. Additionally, general principles of organic chemistry as well as specific functional moieties and reactivities are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March, March's Advanced Organic Chemistry, 5th ed., John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3rd ed., Cambridge University Press, Cambridge, 1987; the entire contents of each of which are incorporated herein by reference.

[0084] As used herein, the term "alkoxy" refers to the group -O-alkyl. Representative examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, 2-propoxy, butoxy, and tert-butoxy.

[0085] As used herein, the term "alkyl" refers to a straight or branched saturated hydrocarbon chain. 1-6 "Alkyl" refers to a straight or branched chain hydrocarbon containing 1 to 6 carbon atoms. The term "C 1-4“Alkyl” refers to a straight or branched chain hydrocarbon containing from 1 to 4 carbon atoms. Representative examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0086] As used herein, the term "alkenyl" refers to a straight or branched hydrocarbon chain containing at least one carbon-carbon double bond.

[0087] The term "alkoxyalkyl," as used herein, means an alkoxy group, as defined herein, appended to the parent molecular moiety through an alkyl group, as defined herein.

[0088] The term "alkoxyfluoroalkyl," as used herein, means an alkoxy group, as defined herein, appended to the parent molecular moiety through a fluoroalkyl group, as defined herein.

[0089] As used herein, the term "alkylene" refers to a divalent group derived from a straight or branched chain hydrocarbon of 1 to 10 carbon atoms, for example, 2 to 5 carbon atoms. Representative examples of alkylene include, but are not limited to, -CH2-, -CD2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, and -CH2CH2CH2CH2CH2-.

[0090] The term "alkylamino" as used herein, means at least one alkyl group, as defined herein, appended to the parent molecular moiety through an amino group, as defined herein.

[0091] As used herein, the term "amide" refers to -C(O)NR- or -NRC(O)-, where R can be hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, alkenyl, or heteroalkyl.

[0092] The term "aminoalkyl" as used herein, means at least one amino group, as defined herein, appended to the parent molecular moiety through an alkylene group, as defined herein.

[0093] As used herein, the term "amino" refers to -NR x R y , where R x and R y It can be hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, alkenyl or heteroalkyl. In the case of aminoalkyl or any other moiety in which an amino group attaches two other moieties together, the amino group can be -NR x -, where R x It can be hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, alkenyl or heteroalkyl.

[0094] As used herein, the term "aryl" refers to a phenyl group or a phenyl group attached to a parent molecular moiety and fused to a cycloalkyl group (e.g., an aryl group can be indan-4-yl), fused to a 6-membered arene group (i.e., an aryl group is naphthyl), or fused to a non-aromatic heterocycle (e.g., an aryl group can be benzo[d][1,3]dioxol-5-yl). The term "phenyl" is used when referring to a substituent, and the term 6-membered arene is used when referring to a fused ring. A 6-membered arene is a monocyclic ring (e.g., benzene or benzo). An aryl group can be monocyclic (phenyl) or bicyclic (e.g., a 9- to 12-membered fused bicyclic ring system).

[0095] The term "cyanoalkyl," as used herein, means at least one -CN group attached to the parent molecular moiety through an alkylene group, as defined herein.

[0096] The term "cyanofluoroalkyl" as used herein, refers to at least one -CN group attached to the parent molecular moiety through a fluoroalkyl group, as defined herein.

[0097] The term "cycloalkoxy" as used herein, means a cycloalkyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom.

[0098] As used herein, the term "cycloalkyl" or "cycloalkane" refers to a saturated ring system containing all carbon atoms as ring members and zero double bonds. The term "cycloalkyl" is used herein to refer to a cycloalkane when present as a substituent. A cycloalkyl group can be a monocyclic cycloalkyl group (e.g., cyclopropyl), a fused bicyclic cycloalkyl group (e.g., decalinyl), or a bridged cycloalkyl group in which two non-adjacent atoms of the ring are connected by an alkylene bridge of 1, 2, 3, or 4 carbon atoms (e.g., bicyclo[2.2.1]heptyl).

[0099] Representative examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, and bicyclo[1.1.1]pentanyl.

[0100] As used herein, the term "cycloalkenyl" or "cycloalkene" refers to a non-aromatic monocyclic or polycyclic ring system containing all carbon atoms as ring members and at least one carbon-carbon double bond and preferably having 5-10 carbon atoms per ring. The term "cycloalkenyl" is used herein to refer to a cycloalkene when present as a substituent. A cycloalkenyl group can be a monocyclic cycloalkenyl group (e.g., cyclopentenyl), a fused bicyclic cycloalkenyl group (e.g., octahydronaphthyl), or a bridged cycloalkenyl group in which two non-adjacent atoms of the ring are linked by an alkylene bridge of 1, 2, 3, or 4 carbon atoms (e.g., bicyclo[2.2.1]heptenyl).

[0101] Exemplary monocyclic cycloalkenyl rings include cyclopentenyl, cyclohexenyl, or cycloheptenyl.Exemplary monocyclic cycloalkenyl rings include cyclopentenyl, cyclohexenyl, or cycloheptenyl.

[0102] The term "carbocyclyl" refers to a "cycloalkyl" or "cycloalkenyl". The term "carbocycle" refers to a "cycloalkane" or "cycloalkene". The term "carbocyclyl" refers to a "carbocycle" when present as a substituent.

[0103] The terms "cycloalkylene" and "heterocyclylene" refer to divalent groups derived from a base ring, i.e., a cycloalkane, a heterocycle. For illustration, examples of cycloalkylene and heterocyclylene include, respectively and Cycloalkylene and heterocyclylene include geminal divalent groups such as 1,1-C 3-6 Cycloalkylene (i.e., Another example is 1,1-cyclopropylene (ie, ).

[0104] As used herein, the term "fluoroalkyl" refers to an alkyl group, as defined herein, in which one, two, three, four, five, six, seven, or eight hydrogen atoms are replaced by fluorine. Representative examples of fluoroalkyl groups include, but are not limited to, 2-fluoroethyl, 2,2,2-trifluoroethyl, trifluoromethyl, difluoromethyl, pentafluoroethyl, and trifluoropropyl, such as 3,3,3-trifluoropropyl.

[0105] As used herein, the term "fluoroalkylene" refers to an alkylene group as defined herein in which one, two, three, four, five, six, seven, or eight hydrogen atoms are replaced by fluorine. Representative examples of fluoroalkyl groups include, but are not limited to, -CF2-, -CH2CF2-, 1,2-difluoroethylene, 1,1,2,2-tetrafluoroethylene, 1,3,3,3-tetrafluoropropylene, 1,1,2,3,3-pentafluoropropylene, and perfluoropropylene groups such as 1,1,2,2,3,3-hexafluoropropylene.

[0106] As used herein, the term "halogen" or "halo" refers to Cl, Br, I, or F.

[0107] As used herein, the term "haloalkyl" refers to an alkyl group as defined herein wherein one, two, three, four, five, six, seven or eight hydrogen atoms are replaced by halogen.

[0108] The term "haloalkoxy," as used herein, means at least one haloalkyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom.

[0109] As used herein, the term "halocycloalkyl" refers to a cycloalkyl group, as defined herein, wherein one or more hydrogen atoms are replaced by a halogen.

[0110] As used herein, the term "heteroalkyl" refers to an alkyl group as defined herein wherein one or more of the carbon atoms is replaced by a heteroatom selected from S, O, P, and N. Representative examples of heteroalkyl groups include, but are not limited to, alkyl ethers, secondary and tertiary alkylamines, amides, and alkyl sulfides.

[0111] As used herein, the term "heteroaryl" refers to an aromatic monocyclic ring containing a heteroatom (monocyclic heteroaryl) or a bicyclic ring system containing at least one monocyclic heteroaromatic ring (bicyclic heteroaryl). The term "heteroaryl" is used herein to refer to heteroaromatic hydrocarbons when present as substituents. Monocyclic heteroaryl is a five-membered or six-membered ring containing at least one heteroatom independently selected from N, O, and S (e.g., 1, 2, 3, or 4 heteroatoms independently selected from O, S, and N). The ring of the five-membered aromatic monocyclic ring has two double bonds, and the ring of the six-membered aromatic monocyclic ring has three double bonds. Bicyclic heteroaryl is an 8- to 12-membered ring system and includes fused bicyclic heteroaromatic ring systems (i.e., 10π electron systems), such as a monocyclic heteroaryl ring fused to a 6-membered arene (e.g., quinolin-4-yl, indol-1-yl), a monocyclic heteroaryl ring fused to a monocyclic heteroarene (e.g., naphthyridinyl), and a phenyl fused to a monocyclic heteroarene (e.g., quinolin-5-yl, indol-4-yl). Bicyclic heteroaryl / heteroarene groups include 9-membered fused bicyclic heteroaromatic ring systems having four double bonds and at least one heteroatom which donates a lone electron pair to the fully aromatic 10π electron system, such as ring systems having nitrogen atoms at the ring junctions (e.g., imidazopyridine) or benzopyridine. Oxazolyl. Bicyclic heteroaryl also includes fused bicyclic ring systems consisting of one heteroaromatic ring and one non-aromatic ring, such as a monocyclic heteroaryl ring fused to a monocyclic carbocyclic ring (e.g., 6,7-dihydro-5H-cyclopenta[b]pyridinyl), or a monocyclic heteroaryl ring fused to a monocyclic heterocyclic ring (e.g., 2,3-dihydrofuro[3,2-b]pyridinyl). Bicyclic heteroaryl is attached to the parent molecular moiety at an aromatic ring atom. Other representative examples of heteroaryl include, but are not limited to, indolyl (e.g., indol-1-yl, indol-2-yl, indol-4-yl), pyridyl (including pyridin-2-yl, pyridin-3-yl, pyridin-4-yl), pyrimidinyl, pyrazinyl, pyridazinyl, pyrazolyl (e.g., pyrazol-4-yl), pyrrolyl, benzopyrazolyl, 1,2,3-triazolyl (e.g., triazol-4-yl), 1,3,4-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4- oxadiazole, 1,2,4- oxadiazolyl, imidazolyl, thiazolyl (e.g., thiazol-4-yl), isothiazolyl, thienyl, benzimidazolyl (e.g., benzimidazolyl-5-yl), benzothiazolyl, benzo Azolyl, benzo oxadiazolyl, benzothienyl, benzofuranyl, isobenzofuranyl, furanyl, Azolyl, iso oxazolyl, purinyl, isoindolyl, quinoxalinyl, indazolyl (e.g., indazol-4-yl, indazol-5-yl), quinazolinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, isoquinolinyl, quinolinyl, imidazo[1,2-a]pyridinyl (e.g., imidazo[1,2-a]pyridin-6-yl), naphthyridinyl, pyridoimidazolyl, thiazolo[5,4-b]pyridin-2-yl, and thiazolo[5,4-d]pyrimidin-2-yl.

[0112] As used herein, the term "heterocycle" or "heterocyclic" refers to a monocyclic heterocycle, a bicyclic heterocycle, or a tricyclic heterocycle. The term "heterocyclyl" is used herein to refer to a heterocycle when present as a substituent. A monocyclic heterocycle is a three-, four-, five-, six-, seven-, or eight-membered ring containing at least one heteroatom independently selected from O, N, and S. A three- or four-membered ring contains zero or one double bond and one heteroatom selected from O, N, and S. A five-membered ring contains zero or one double bond and one, two, or three heteroatoms selected from O, N, and S. A six-membered ring contains zero, one, or two double bonds and one, two, or three heteroatoms selected from O, N, and S. A seven- and eight-membered ring contains zero, one, two, or three double bonds and one, two, or three heteroatoms selected from O, N, and S. Representative examples of monocyclic heterocyclyls include, but are not limited to, azetidinyl, azepanyl, aziridinyl, diazepanyl, 1,3-dioxanyl, 1,3-dioxolanyl, 1,3-dithiolanyl, 1,3-dithianyl, imidazolinyl, imidazolidinyl, isothiazolinyl, isothiazolidin ... Oxazoline, iso Oxazolidinyl, morpholinyl, 2-oxo-3-piperidinyl, 2-oxoazepan-3-yl, oxadiazolinyl, diazolidinyl, Oxazoline, oxazolidinyl, oxetanyl, oxepanyl, oxocanyl, piperazinyl, piperidinyl, pyranyl, pyrazolinyl, pyrazolidinyl, pyrrolinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydropyridinyl, tetrahydrothiophenyl, thiadiazolinyl, thiadiazolidinyl, 1,2-thiomorpholinyl, 1,3-thiomorpholinyl, thiazolinyl, thiazolidinyl, thiomorpholinyl, 1,1-dioxothiomorpholinyl (thiomorpholine sulfone), thiopyranyl, and trithianyl. Bicyclic heterocycles are monocyclic heterocycles fused to a 6-membered arene, or a monocyclic heterocycle fused to a monocyclic cycloalkane, or a monocyclic heterocycle fused to a monocyclic cycloalkene, or a monocyclic heterocycle fused to a monocyclic heterocycle, or a monocyclic heterocycle fused to a monocyclic heteroaromatic hydrocarbon, or a spiroheterocyclic group, or a bridged monocyclic heterocyclic ring system in which two non-adjacent atoms of the ring are connected by an alkylene bridge of 1, 2, 3, or 4 carbon atoms or an alkenylene bridge of 2, 3, or 4 carbon atoms. The bicyclic heterocyclyl is attached to the parent molecular moiety (e.g., indoline-1-yl) at a non-aromatic ring atom. Representative examples of bicyclic heterocyclyl include, but are not limited to, chroman-4-yl, 2,3-dihydrobenzofuran-2-yl, 2,3-dihydrobenzothiophen-2-yl, 1,2,3,4-tetrahydroisoquinolin-2-yl, 2-azaspiro[3.3]heptan-2-yl, 2-oxa-6-azaspiro[3.3]heptan-6-yl, azabicyclo[2.2.1]heptyl (including 2-azabicyclo[2.2.1]hept-2-yl), azabicyclo[3.1.0]hexanyl (including 3-azabicyclo[3.1.1]hexanyl), 2-oxa-6-azaspiro[3.3]heptan-6-yl, 2-oxa-6-azaspiro[3.3]heptan-6-yl, 2-oxa-6-azaspiro[3.3]heptan-2 ... ]heptan-3-yl), 2,3-dihydro-1H-indol-1-yl, isoindol-2-yl, octahydrocyclopenta[c]pyrrolyl, octahydropyrrolopyridinyl, tetrahydroisoquinolinyl, 7-oxabicyclo[2.2.1]heptanyl, hexahydro-2H-cyclopenta[b]furanyl, 2-oxaspiro[3.3]heptanyl, 3-oxaspiro[5.5]undecyl, 6-oxaspiro[2.5]octan-1-yl, and 3-oxabicyclo[3.1.0]hexan-6-yl. Examples of tricyclic heterocycles are bicyclic heterocycles fused to a 6-membered arene, or bicyclic heterocycles fused to a monocyclic cycloalkane, or bicyclic heterocycles fused to a monocyclic cycloalkene, or bicyclic heterocycles fused to a monocyclic heterocycle, or bicyclic heterocycles wherein two non-adjacent atoms of the bicyclic ring are linked by an alkylene bridge of 1, 2, 3, or 4 carbon atoms or an alkenylene bridge of 2, 3, or 4 carbon atoms. Examples of tricyclic heterocycles include, but are not limited to, octahydro-2,5-epoxypentalene, hexahydro-2H-2,5-methanocyclopenta[b]furan, hexahydro-1H-1,4-methanocyclopenta[c]furan, aza-adamantane (1-azatricyclo[3.3.1.13,7]decane), and oxa-adamantane (2-oxatricyclo[3.3.1.13,7]decane). The monocyclic, bicyclic, and tricyclic heterocyclyls are attached to the parent molecular moiety at a non-aromatic ring atom.

[0113] As used herein, the term "hydroxyl" or "hydroxy" refers to an -OH group.

[0114] The term "hydroxyalkyl," as used herein, means at least one -OH group is appended to the parent molecular moiety through an alkylene group, as defined herein.

[0115] The term "hydroxyfluoroalkyl," as used herein, means at least one -OH group is appended to the parent molecular moiety through a fluoroalkyl group, as defined herein.

[0116] For example, terms such as "alkyl," "cycloalkyl," and "alkylene" may be preceded by an identifier indicating the number of atoms present in the group in that particular instance (e.g., "C 1-4 Alkyl", "C 3-6 Cycloalkyl", "C 1-4 These designations are used as commonly understood by those skilled in the art. For example, the expression "C" followed by a subscript number indicates the number of carbon atoms present in the group described below. Thus, "C3 alkyl" is an alkyl group having three carbon atoms (i.e., n-propyl, isopropyl). Where ranges are given, as in "C 1-4 ”, the members of the subsequent group may have any number of carbon atoms falling within the stated range. For example, “C 1-4 An "alkyl" group is an alkyl group having from 1 to 4 carbon atoms, however arranged (ie, linear or branched).

[0117] The term "substituted" refers to a group that can be further substituted with one or more non-hydrogen substituents. Substituents include, but are not limited to, halogen, =O (oxo), =S (thio), cyano, nitro, fluoroalkyl, alkoxyfluoroalkyl, fluoroalkoxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkoxy, heteroalkyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocycle, cycloalkylalkyl, heteroarylalkyl, arylalkyl, hydroxy, hydroxyalkyl, alkoxy, alkoxyalkyl, alkylene, aryloxy, phenoxy, benzyloxy, amino, alkylamino, acylamino, aminoalkyl, arylamino, sulfonylamino, sulfinylamino, sulfonyl, alkylsulfonyl, arylsulfonyl, aminosulfonyl, sulfinyl, -COOH, ketone, amide, carbamate, and acyl.

[0118] The term "pphp" means "parts per hundred parts polyol" and is used to describe the amounts of other foam components (eg, amine catalyst) as a ratio based on the polyol.

[0119] The compositions and methods described herein provide a method for making an amine composition wherein a monohydric alcohol is included in the amine catalyst composition to mitigate solid carbamate formation. This method is a cost-effective solution for preventing / reducing the formation of solid intermediate carbamates during the polyurethane foam production process.

[0120] One aspect as described herein relates to a method for producing polyurethane foam using an amine catalyst composition of the present invention, the amine catalyst composition comprising an amine catalyst and a monohydric alcohol. The composition comprises an amine catalyst and a monohydric alcohol, wherein the concentration of the monohydric alcohol in the composition is between 1-50% by weight (wt%), 3-25% by weight (wt%), or 3-20% by weight (wt%). The amine catalyst composition can be obtained by thoroughly blending 1-20% by weight (wt%) of the monohydric alcohol with a tertiary, secondary, or primary amine catalyst for at least several minutes (e.g., from about 5 minutes to about 60 minutes). Various aspects of exemplary amine catalysts and monohydric alcohols are described below.

[0121] Amine catalyst

[0122] Suitable amine catalysts may comprise tertiary amines, secondary amines, primary amines, or combinations thereof. Exemplary amine catalysts may comprise tertiary amines containing at least one isocyanate reactive group. Typically, the amine catalyst, such as a tertiary amine containing at least one isocyanate reactive group, is present in less than 1% by weight of the total foam formulation. The isocyanate reactive group typically comprises an amino / amine moiety (e.g., a primary or secondary amine moiety), a hydroxyl, an amide, or a urea moiety. In various cases, at least one isocyanate reactive group may comprise at least one selected from structural part.

[0123] The at least one tertiary amine may be a tertiary amine of the formula:

[0124]

[0125] in:

[0126] R 1 is hydrogen or -C 1-4 alkyl;

[0127] R 2 It is hydrogen, -C 1-6 alkyl,

[0128] R 3 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; and

[0129] R 4 and R5 are independently hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2.

[0130] For example, the at least one tertiary amine may be selected from:

[0131]

[0132]

[0133] In some cases, the at least one tertiary amine can be a tertiary amine of the formula:

[0134]

[0135] in:

[0136] yes

[0137] R 6 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH, -C 1-6 Alkyl-NH2, -C 1-6 Alkyl-N(CH3)2;

[0138] R 7 It is hydrogen, -C 2-6 Alkyl-OH, -C 2-6 Alkyl-NH2, -C 2-6 Alkyl-N(CH3)2 or

[0139]

[0140] R 8 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2;

[0141] R 9 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; and

[0142] R 10 and R 11 are independently hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2.

[0143] For example, the at least one tertiary amine may be selected from:

[0144]

[0145]

[0146] In some cases, the at least one tertiary amine can be selected from:

[0147]

[0148] In some cases, the catalyst composition may include at least two tertiary amines. For example, the catalyst composition may further include a tertiary amine that does not contain an isocyanate-reactive group. In some cases, the tertiary amine that does not contain an isocyanate-reactive group may be one or more selected from the following:

[0149]

[0150]

[0151] Suitable tertiary amines containing at least one isocyanate reactive group include gelling and foaming amine catalysts. Exemplary gelling amine catalysts include at least one selected from the group consisting of N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, N,N-dimethylaminoethyl-N′-methylethanolamine ( T, Evonik Corporation of Allentown, Pa.), N,N,N′-trimethylaminopropylethanolamine ( 17, Evonik Corporation), N,N-dimethylethanolamine ( DMEA), N,N-dimethyl-N′,N′-2-hydroxy(propyl)-1,3-propanediamine, dimethylaminopropylamine (DMAPA), (N,N-dimethylaminoethoxy)ethanol, methyl-hydroxy-ethyl-piperazine, bis(N,N-dimethyl-3-aminopropyl)amine ( 15) N,N-dimethylaminopropyl urea ( NE1060, NE1070), N,N′-bis(3-dimethylaminopropyl)urea( NE1070, NE1080), bis(dimethylamino)-2-propanol, N-(3-aminopropyl)imidazole, N-(2-hydroxypropyl)imidazole and N-(2-hydroxyethyl)imidazole.

[0152] Exemplary amine blowing catalysts include at least one selected from the group consisting of 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, N,N-dimethylaminoethyl-N′-methyl-N′-ethanol ( -T), dimethylaminoethoxyethanol and N,N,N′-trimethyl-N′-3-aminopropyl-bis(aminoethyl) ether ( NE300).

[0153] Suitable amine catalyst compositions may further comprise a gelling catalyst that is highly volatile and non-reactive with isocyanate groups, such as a volatile gelling catalyst. Suitable volatile gelling catalysts may include, for example, at least one selected from the group consisting of diazabicyclooctane (triethylenediamine) (as 33-LV catalyst commercially available), tris(hydroformylationyl)amine ( 9) Dimethylaminocyclohexylamine ( 8) and bis(dimethylaminopropyl)-N-methylamine ( 77), N,N-dimethylcyclohexylamine (Polycat-8, Evonik Corporation of Allentown, Pa.), N-methyldicyclohexylamine (Polycat-12, Evonik Corporation of Allentown, Pa.). Suitable volatile blowing catalysts include, for example, at least one selected from the group consisting of: bis-dimethylaminoethyl ether (available from Evonik Corporation as BL-11 catalyst commercially available); and pentamethyldiethylenetriamine ( 5, Evonik Corporation), hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine and related compositions, higher permethylated polyamines, 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol and related structures, alkoxylated polyamines, imidazole-boron compositions, or aminopropyl-bis(amino-ethyl)ether compositions.

[0154] Typically, the loading of non-volatile amines used to make the foams described herein will be in the range of about 0.1 to about 20 pphp, more typically about 0.1 to about 10 pphp, and most typically about 0.1 to about 5 pphp. However, any effective amount may be used. The amount of volatile amine in the foam formulation may be about 0.05 to about 20 pphp.

[0155] Monohydric alcohol

[0156] Exemplary monohydric alcohols contain less than 10 carbon atoms. In each case, the monohydric alcohol comprises at least one alcohol selected from the group consisting of:1-7 Straight chain alkyl -OH, C 3-6 Branched alkyl -OH and C 3-6 Cycloalkyl-OH. In each case, the monohydric alcohol comprises at least one alcohol selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, cyclopentanol, and cyclohexanol. Typically, the monohydric alcohol is present in no more than 0.5% by weight of the total foam formulation.

[0157] Preparation of foam formulations

[0158] Any of the various types of foams known in the art can be made using typical polyurethane formulations using the methods described herein. For example, flexible polyurethane foams having the excellent physical properties described herein typically contain the components shown in Table 1 below in the amounts shown. The components shown in Table 1 are discussed in detail below.

[0159]

[0160] The amount of organic isocyanate used in the polyurethane formulations as described herein is not limited, but it will generally be within those ranges known to those skilled in the art. Exemplary ranges are listed in Table 1 above, with reference to the "NCO index" (isocyanate index). As known in the art, the NCO index is defined as the number of isocyanate equivalents divided by the total number of active hydrogen equivalents, multiplied by 100. The NCO index is represented by the following formula. NCO index = [NCO / (OH + NH)] × 100. The isocyanate index can be from about 80 to about 500, depending on the type of foam formulation. For example, flexible foams typically have an isocyanate index of 80 to 120, while rigid foams, such as those commonly used for appliances, laminations, and spray foam applications, can have an index in the range of 100 to 500, depending on the application. Higher indices are typically used with trimerization catalysts to produce polyisocyanurate (PIR) foams. PIR foams are typically used in foam laminates that require effective thermal insulation. Regarding foam density, exemplary polyurethane foams generally have a density between 0.8 pounds per cubic foot (pcf) and 3.5 pcf.

[0161] Another embodiment relates to a method for making polyurethane, comprising contacting at least one organic isocyanate with at least one polyol in the presence of a catalytically effective amount of the amine catalyst composition. The polyurethane is produced by reacting the organic isocyanate with hydroxyl groups in the polyol (typically a mixture of polyols). The at least one polyol can be a polyether polyol, a polyester polyol, a copolymer polyol, or a natural oil polyol. The at least one polyol can be virgin or recycled. Various aspects of exemplary organic isocyanates and polyols are discussed below.

[0162] Organic isocyanates

[0163] Suitable organic isocyanate compounds include, but are not limited to, at least one selected from the group consisting of hexamethylene diisocyanate (HDI), phenylene diisocyanate (PDI), toluene diisocyanate (TDI), and 4,4′-methylenediphenyl diisocyanate (MDI). In one aspect described herein, 2,4-TDI, 2,6-TDI, or any mixture thereof may be used to produce polyurethane foam. Suitable organic isocyanates include monomeric isocyanates, such as MDI, and polymeric isocyanates, such as polymeric 4,4′-methylenediphenyl diisocyanate (PMDI). Other suitable isocyanate compounds are diisocyanate mixtures commercially known as “crude MDI.” One example is commercially available from Dow Chemical Company under the trade name PAPI. TM It is sold as 4,4′-diphenylmethane diisocyanate and contains approximately 60% 4,4′-diphenylmethane diisocyanate (MDI) as well as other isomers and similar higher polyisocyanates.

[0164] polyols

[0165] The polyols of the foam formulations described herein may comprise at least a primary or "base" polyol. Base polyols suitable for use as described herein include, by way of non-limiting example, at least one selected from polyether polyols. Exemplary polyether polyols may have a molecular weight (MW) of 2000 g / mol to 4000 g / mol and a polyol functionality of 2.5 to 3.3. As used herein, "polyol functionality" refers to the number of -OH- groups per molecule. Polyether polyols include poly(alkylene oxide) polymers, such as poly(ethylene oxide) and poly(propylene oxide) polymers and copolymers having terminal hydroxyl groups derived from polyols (including diols and triols). Examples of diols and triols for reaction with ethylene oxide or propylene oxide include at least one selected from the group consisting of ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylolpropane, and similar low molecular weight polyols. Other examples of base polyols known in the art include polyhydroxy-terminated acetal resins, hydroxy-terminated amines, and hydroxy-terminated polyamines. Examples of these and other suitable isocyanate-reactive materials can be found in U.S. Pat. No. 4,394,491, which is incorporated herein by reference. Suitable polyols also include those containing tertiary amine groups that can catalyze the gelation and foaming reactions of the polyurethane, such as those described in WO 2003 / 016373 A1, WO 2001 / 58976 A1, WO 2004 / 060956 A1, WO 2003 / 016372 A1, and WO 2003 / 055930 A1, the disclosures of which are incorporated herein by reference. Other useful polyols may include polyalkylene carbonate-based polyols and polyphosphate-based polyols. The amount of polyether polyol may be from about 20 to about 100 parts per 100 parts of polyol (pphp).

[0166] In one aspect, a single high molecular weight polyether polyol can be used as the base polyol. Alternatively, a mixture of high molecular weight polyether polyols can be used, such as a mixture of difunctional and trifunctional materials and / or materials of different molecular weights or different chemical compositions. Such difunctional and trifunctional materials include, but are not limited to, at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, glyceryl polyether triol, trimethylolpropane-based polyether triol, and other similar compounds or mixtures, provided that they are ester-free. In some embodiments as described herein, at least about 50% by weight (wt%) of the ester-free polyol component is composed of one or more polyether polyols.

[0167] In addition or in place of above-mentioned basic polyol, the material that is often called " copolymer polyol " can be comprised in the polyol component of using as described herein. In polyurethane foam, copolymer polyol can be used to improve the deformation resistance of foam, for example, to improve the load-bearing properties of foam. According to the load requirement of polyurethane foam, copolymer polyol can constitute 0 to about 80 weight % of total polyol content. The example of copolymer polyol includes but not limited to graft polyol and polyurea-modified polyol, both of which are known in the art and can be bought.

[0168] Graft polyols are prepared by copolymerizing vinyl monomers, typically styrene and acrylonitrile, in a starting polyol. The starting polyol is typically a glycerol-initiated triol and is typically end-capped with ethylene oxide (approximately 80-85% primary hydroxyl groups). Some of the copolymer is grafted onto some of the starting polyol. The graft polyol also contains homopolymers of styrene and acrylonitrile and the unchanged starting polyol. The graft polyol typically has a styrene / acrylonitrile solids content of about 5% by weight (wt%) to about 45% by weight (wt%), but any type of graft polyol known in the art can be used.

[0169] Polyurea-modified polyols are formed by the reaction of diamines and diisocyanates in the presence of a starting polyol, the product comprising a polyurea dispersion. A variation of polyurea-modified polyols also suitable for use are polyisocyanate polyaddition (PIPA) polyols formed by the in situ reaction of isocyanates and alkanolamines in the polyol.

[0170] Useful polyester polyols include those produced when a dicarboxylic acid reacts with an excess diol, such as adipic acid or phthalic acid or phthalic anhydride with ethylene glycol or butanediol, or when a lactone reacts with an excess diol, such as caprolactone with propylene glycol. Mannich polyols are also commonly used in spray formulations. Mannich polyols are made by condensing phenols with aldehydes and amines to produce a polyol containing multiple hydroxyl groups (2-8) and tertiary amine centers. Polyester polyols can be present in a range of about 0 pphp to about 100 pphp. Flexible foams typically use copolymer polyols as part of the total polyol content in the foam composition, along with a base polyol having a weight average molecular weight of about 3000-6000 and a hydroxyl number of about 28-60.

[0171] Natural oil polyols

[0172] In order to minimize the consumption of fossil fuels and other unsustainable resources, all or a portion of the polyols that can be used to prepare polyurethane foams come from cheap and renewable resources. Natural oils contain triglycerides of saturated and unsaturated fatty acids. One natural oil polyol is castor oil—a natural triglyceride of ricinoleic acid that is commonly used to make polyurethane foams, although it has certain limitations, such as a low hydroxyl content. Other natural oils can be chemically modified to introduce sufficient hydroxyl content to make them useful in the production of polyurethane polymers. When attempting to modify natural oils or fats into usable polyols, there are two chemically reactive sites that can be considered: (1) unsaturated sites (double bonds); and (2) ester functionality. Unsaturated sites present in oils or fats can be hydroxylated by epoxidation / ring opening or hydroformylation / hydrogenation. Alternatively, transesterification can be used to introduce -OH groups into natural oils and fats. Chemical methods for preparing natural polyols using the epoxidation route involve a reaction mixture requiring an epoxidized natural oil, a ring-opening acid catalyst, and a ring-opening agent. Epoxidized natural oils include epoxidized plant-based oils (epoxidized vegetable oils) and epoxidized animal fats. The epoxidized natural oils may be fully or partially epoxidized and include at least one selected from the group consisting of soybean oil, corn oil, sunflower oil, olive oil, canola oil, sesame oil, palm oil, rapeseed oil, tung oil, cottonseed oil, safflower oil, peanut oil, linseed oil, and combinations thereof. Animal fats include fish oil, beef tallow, and lard. These natural oils are C 12 to C 24The peroxy acids are triglycerides of fatty acids of various chain lengths, which may be saturated or unsaturated. These acids may be: (1) saturated: lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and lignoceric acid; (2) monounsaturated: palmitoleic acid, oleic acid, (3) polyunsaturated: linoleic acid, linolenic acid, arachidonic acid. When peroxy acids are reacted under appropriate reaction conditions, partially or fully epoxidized natural oils may be prepared. Examples of peroxy acids used in the epoxidation of oils are described in WO 2006 / 116456 A1; which is incorporated herein by reference. The epoxidized oils may be ring-opened with alcohols, water and other compounds having one or more nucleophilic groups. Depending on the reaction conditions, oligomerization of the epoxidized oil may also occur. The ring opening produces natural oil polyols that can be used to make polyurethane products. In the hydroformylation / hydrogenation process, the oil is hydroformylated in the presence of a suitable catalyst (usually cobalt or rhodium) in a reactor filled with a hydrogen / carbon monoxide mixture to form an aldehyde, which is hydrogenated in the presence of a cobalt or nickel catalyst to form a polyol. Alternatively, the polyol from natural oils and fats can be produced by using an alkali metal or alkaline earth metal base or salt as a transesterification catalyst with a suitable polyhydroxy-containing material transesterification. Any natural oil or alternatively any partially hydrogenated oil can be used in the transesterification process. The example of oil includes, but is not limited to, at least one selected from the following: soybean oil, corn oil, cottonseed oil, peanut oil, castor oil, sunflower oil, mustard oil, rapeseed oil, safflower oil, fish oil, seal oil, palm oil, tung oil, olive oil or any blend. Any polyfunctional hydroxy compound can also be used, such as lactose, maltose, raffinose, sucrose, sorbitol, xylitol, erythritol, mannitol or any combination. The amount of natural oil polyol may range from about 0 to about 40 pphp of the foam formulation.

[0173] foaming agent

[0174] Polyurethane foam production can be assisted by incorporating a blowing agent to create voids in the polyurethane matrix during the polymerization process. Any blowing agent known in the art can be used. Suitable blowing agents include low-boiling point compounds that vaporize during the exothermic polymerization reaction. Such blowing agents are generally inert and therefore do not decompose or react during the polymerization reaction. Examples of inert blowing agents include, but are not limited to, at least one selected from the following: water, carbon dioxide, chlorofluorocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, fluoroolefins, chlorofluoroolefins, hydrofluoroolefins, hydrochlorofluoroolefins, acetone, and low-boiling point hydrocarbons, such as cyclopentane, isopentane, n-pentane, and mixtures thereof. Other suitable blowing agents include compounds that react with isocyanate compounds to produce gas, such as water.

[0175] In various cases, the blowing agent comprises at least one member selected from the group consisting of carbon dioxide (CO2), water, acetone, methyl formate, hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), and hydrocarbons.

[0176] The amount of blowing agent is typically from about 0 pphp to about 80 pphp. The amount of water may be from about 0 pphp to about 60 pphp. In various cases, the amount of water may be from about 1.0 pphp to about 10 pphp, and in some cases from about 2.0 pphp to about 5 pphp.

[0177] Optional components

[0178] Various other components or ingredients may be included in the foam formulations described herein. Examples of optional components include, but are not limited to, at least one selected from the group consisting of cell stabilizers, crosslinkers, chain extenders, pigments, dyes, fillers, flame retardants, flame-melt lamination additives, auxiliary urethane gelling catalysts, auxiliary urethane blowing catalysts, metal catalysts, additional amines, and combinations thereof. Cell stabilizers may be used in amounts of about 0.1 to about 20 pphp, typically about 0.1 to about 10 pphp, and in some cases about 0.1 to about 5.0 pphp. Flame retardants may be used in amounts of about 0 to about 20 pphp, about 0 to about 10 pphp, and about 0 to about 5 pphp.

[0179] The cell stabilizer may include, for example, an organosilicon surfactant or an anionic surfactant. Examples of suitable organosilicon surfactants include, but are not limited to, at least one selected from the group consisting of polyalkylsiloxanes, polyoxyalkylene polyol-modified dimethylpolysiloxanes, alkylene glycol-modified dimethylpolysiloxanes, or combinations thereof. Suitable anionic surfactants include, but are not limited to, salts of fatty acids, salts of sulfates, salts of phosphates, salts of sulfonic acids, and any combinations thereof.

[0180] Crosslinking agents include, but are not limited to, at least one selected from the group consisting of low molecular weight compounds containing at least two moieties selected from the group consisting of hydroxyl groups, primary amino groups, secondary amino groups, and other active hydrogen-containing groups reactive with isocyanate groups. Crosslinking agents include, for example, at least one selected from the group consisting of polyols (particularly triols, such as glycerol and trimethylolpropane), polyamines, and combinations thereof. Non-limiting examples of polyamine crosslinking agents include diethyltoluenediamine, chlorodiaminobenzene, diethanolamine, diisopropanolamine, triethanolamine, tripropanolamine, hexamethylenediamine, and combinations thereof. Typical diamine crosslinking agents contain 12 carbon atoms or fewer, more typically 7 or fewer. The amount of crosslinking agent is typically from about 0.1 pphp to about 20 pphp.

[0181] Examples of chain extenders include, but are not limited to, compounds having hydroxyl or amino functional groups, such as glycols, amines, diols, and water. Specific non-limiting examples of chain extenders include at least one selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, ethoxylated hydroquinone, 1,4-cyclohexanediol, N-methylethanolamine, N-methylisopropanolamine, 4-aminocyclohexanol, 1,2-diaminoethane, 2,4-toluenediamine, or any mixture thereof.

[0182] Pigments can be used to color code polyurethane foam during the manufacturing process, for example to identify product grade, or to mask yellowing. Pigments can include any suitable organic or inorganic pigments known in the polyurethane art. For example, organic pigments or colorants include, but are not limited to, those selected from azo / diazo dyes, phthalocyanines, diazonium At least one of oxazine and carbon black. Examples of inorganic pigments include, but are not limited to, titanium dioxide, iron oxide, or chromium oxide. The amount of any pigment is generally from about 0 pphp to about 15 pphp.

[0183] Fillers can be used to increase the density and load-bearing properties of the polyurethane foam. Suitable fillers include, but are not limited to, barium sulfate or calcium carbonate. The amount of any filler is generally from about 0 pphp to about 30 pphp.

[0184] Flame retardants can be used to reduce the flammability of polyurethane foam. For example, suitable flame retardants include, but are not limited to, chlorinated phosphates, chlorinated paraffins, or melamine powder.

[0185] In some cases, the contact of at least one organic isocyanate with at least one polyol can be carried out in the presence of a metal catalyst. The metal catalyst can be a metal carboxylate, wherein the metal carboxylate comprises a metal and a carboxylate anion. The metal can be at least one selected from tin (Sn), bismuth (Bi), lead (Pb), iron (Fe), zinc (Zn) and potassium (K). The carboxylate can be a carboxylate anion selected from at least one carboxylic acid: acetic acid, propionic acid, butyric acid, pentanoic acid, pivalic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid and octadecanoic acid. In some cases, the metal catalyst can be an organotin catalyst. The organotin catalyst may be at least one selected from dibutyltin diacetate, dimethyltin dilauryl mercaptan, dibutyltin dilauryl mercaptan, dimethyltin diisooctyl maleate, dibutyltin diisooctyl maleate, dimethyltin bis(2-ethylhexyl mercaptoacetate), dibutyltin bis(2-ethylhexyl mercaptoacetate), dimethyltin neodecanoate, dibutyltin neodecanoate, dimethyltin isononanoate, dibutyltin isononanoate, stannous octoate, stannous neodecanoate, stannous isononanoate, and stannous carboxylates. The metal catalyst may be present in an amount of about 0 parts per 100 parts of polyol (pphp) to about 20 pphp. In some cases, the metal catalyst may be present in an amount of about 0 pphp to about 10 pphp.

[0186] In some cases, the contacting of the at least one organic isocyanate with the at least one polyol can be carried out in the presence of an additional amine. The additional amine can include at least one selected from the group consisting of triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole, N-methylmorpholine (which can be used as NMM), N-ethylmorpholine (available as NEM), triethylamine (available as TETN), N,N′-dimethylpiperazine (can be used as 41), 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine (can be used as DABCO 30 purchased), 2,4,6-tris(dimethylaminomethyl)phenol, N-methyldicyclohexylamine (can be used as 12 available), pentamethyldipropylenetriamine (available as 77), N-methyl-N′-(2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyl-diethylenetriamine (available as 5 available), hexamethyl-triethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexyl-amine (available as 8 purchased), triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl) ether (can be used as BL19), tris(3-dimethylaminopropyl)amine (can be used as 9 commercially available), 1,8-diazabicyclo[5.4.0]undecane, and acid-blocked derivatives of 1,8-diazabicyclo[5.4.0]undecane.

[0187] Examples of TDI and MDI based polyurethane foam formulations used to evaluate various amine catalyst compositions of the present invention are given below. In the case of flexible molded foams, the mats were removed from the heated mold and allowed to cool to room temperature to monitor dimensional stability (shrinkage) or mechanically crushed to evaluate their physical and mechanical properties.

[0188] It will be apparent to those skilled in the relevant art that suitable modifications and adaptations may be made to the compositions, formulations, methods, processes and applications described herein without departing from the scope of any embodiment or aspect thereof. The compositions and methods provided are exemplary and are not intended to limit the scope of any specified embodiment. The various embodiments, aspects and options disclosed herein may be combined in any variation or iteration. The scope of the compositions, formulations, methods and processes described herein includes all actual or potential combinations of the embodiments, aspects, options, examples and preferences described herein.

[0189] The exemplary compositions and formulations described herein may omit any component, replace any component disclosed herein, or include any component disclosed elsewhere herein. The mass of any component of any composition or formulation disclosed herein to the mass of any other component in the formulation or to the ratio of the total mass of other components in the formulation is hereby disclosed, just as if they were explicitly disclosed; this can be expressed as a percentage of the total mass of all components of the formulation or as a ratio of components. If the meaning of any term in any patent or publication incorporated by reference conflicts with the meaning of the term used in this disclosure, the meaning of the term or phrase in this disclosure shall prevail. In addition, the foregoing discussion discloses and describes only exemplary embodiments. All patents and publications cited herein are incorporated herein by reference for their specific teachings.

[0190] The various embodiments and aspects of the invention described herein are summarized by the following clauses:

[0191] Clause 1. A method of making a polyurethane foam, the method comprising:

[0192] The foam formulation was prepared as follows:

[0193] At least one organic isocyanate is contacted with at least one polyol in the presence of a blowing agent and a catalyst composition, wherein the catalyst composition comprises:

[0194] at least one tertiary amine comprising an isocyanate-reactive group; and

[0195] Monohydric alcohol, wherein the monohydric alcohol comprises a compound selected from C 1-7 Straight chain alkyl -OH, C 3-6 Branched alkyl -OH and C 3-6 At least one alcohol having a cycloalkyl-OH group.

[0196] Clause 2. The method of clause 1, wherein the at least one tertiary amine comprising an isocyanate-reactive group comprises at least one selected from structural part.

[0197] Clause 3. The method of clause 1 or 2, wherein the blowing agent comprises at least one member selected from the group consisting of carbon dioxide (CO2), water, acetone, methyl formate, hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), and hydrocarbons.

[0198] Clause 4. The method of any of Clauses 1-3, wherein the blowing agent comprises carbon dioxide (CO2) and water.

[0199] Clause 5. The process of any of Clauses 1-4, wherein the at least one organic isocyanate is toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), a polymeric isocyanate, or a combination thereof.

[0200] Clause 6. The method of any of Clauses 1-5, wherein at least one polyol is a polyether polyol, a polyester polyol, a copolymer polyol, or a natural oil polyol.

[0201] Clause 7. The process of any of Clauses 1-6, wherein the at least one polyol is virgin or recycled.

[0202] Clause 8. The process of any of Clauses 1-7, wherein the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of a crosslinking agent.

[0203] Clause 9. The process of any of Clauses 1-8, wherein the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of an organosilicon surfactant.

[0204] Clause 10. The process of any of Clauses 1-9, wherein the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of an additional amine.

[0205] Clause 11. The method of clause 10, wherein the additional amine comprises at least one selected from the group consisting of triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole, N-methylmorpholine, N-ethylmorpholine, triethylamine, N,N′-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 2,4,6-tris(dimethylaminomethyl)phenol, N-methyldicyclohexylamine, pentamethyldipropylenetriamine, N -methyl-N′-(2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyl-diethylenetriamine, hexamethyl-triethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexyl-amine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl) ether, tris(3-dimethylaminopropyl)amine, 1,8-diazabicyclo[5.4.0]undecane, and acid-blocked derivatives of 1,8-diazabicyclo[5.4.0]undecane.

[0206] Clause 12. The process of any of Clauses 1-11, wherein the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of a metal catalyst.

[0207] Item 13. The method of Item 12, wherein the metal catalyst is a metal carboxylate.

[0208] Clause 14. The method of Clause 13, wherein the metal carboxylate comprises a metal and a carboxylate anion.

[0209] Item 15. The method of Item 14, wherein the metal is at least one selected from tin (Sn), bismuth (Bi), lead (Pb), iron (Fe), zinc (Zn), and potassium (K).

[0210] Clause 16. The method of clause 14, wherein the carboxylate is a carboxylate anion of at least one carboxylic acid selected from the group consisting of acetic acid, propionic acid, butyric acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexylcarboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid.

[0211] Item 17. The method of Item 12, wherein the metal catalyst is an organotin catalyst.

[0212] Item 18. The method of Item 17, wherein the organotin catalyst is at least one selected from the group consisting of dibutyltin diacetate, dimethyltin dilauryl mercaptan, dibutyltin dilauryl mercaptan, dimethyltin diisooctylmaleate, dibutyltin diisooctylmaleate, dimethyltin di(2-ethylhexylmercaptoacetate), dibutyltin di(2-ethylhexylmercaptoacetate), dimethyltin neodecanoate, dibutyltin neodecanoate, dimethyltin isononanoate, dibutyltin isononanoate, stannous octoate, stannous neodecanoate, stannous isononanoate, and stannous carboxylates.

[0213] Clause 19. The method of any of Clauses 12-18, wherein the metal catalyst is present at about 0 parts per hundred parts of polyol (pphp) to about 20 pphp.

[0214] Clause 20. The method of any of Clauses 1-19, wherein the polyurethane foam has an isocyanate index of between 80 and 120.

[0215] Clause 21. The method of any of Clauses 1-20, wherein the polyurethane foam has a density between 0.8 pounds per cubic foot (pcf) and 3.5 pcf.

[0216] Clause 22. The process of any of Clauses 1-21, wherein the monohydric alcohol is present in the catalyst composition at 5 mass percent (wt%) to 15 wt%.

[0217] Clause 23. The method of any of Clauses 1-22, wherein the monohydric alcohol is present at less than 0.5% by weight of the foam formulation.

[0218] Clause 24. The method of any of Clauses 1-23, wherein the monohydric alcohol, tertiary amine, is present at less than 1.0% by weight of the foam formulation.

[0219] Clause 25. The process of any of clauses 1 to 24, wherein the monohydric alcohol comprises at least one alcohol selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, cyclopentanol, and cyclohexanol.

[0220] Clause 26. The method of any one of clauses 1 to 25, wherein the at least one tertiary amine is a tertiary amine of the formula:

[0221]

[0222] in:

[0223] R 1 is hydrogen or -C 1-4 alkyl;

[0224] R 2 It is hydrogen, -C 1-6 alkyl,

[0225] R 3 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; and

[0226] R 4 and R 5 are independently hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2.

[0227] Clause 27. The method of any one of clauses 1 to 26, wherein the at least one tertiary amine is selected from:

[0228]

[0229] Clause 28. The method of any one of clauses 1 to 27, wherein the at least one tertiary amine is a tertiary amine of the formula:

[0230]

[0231] in:

[0232] yes

[0233] R 6 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH, -C 1-6 Alkyl-NH2, -C 1-6 Alkyl-N(CH3)2;

[0234] R 7 It is hydrogen, -C 2-6 Alkyl-OH, -C 2-6 Alkyl-NH2, -C 2-6 Alkyl-N(CH3)2 or

[0235] R 8 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2;

[0236] R 9 It is hydrogen, -C 1-6 Alkyl, -C 1-6Alkyl-OH or -C 1-6 Alkyl-NH2; and

[0237] R 10 and R 11 are independently hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2.

[0238] Clause 29. The method of any one of clauses 1 to 28, wherein the at least one tertiary amine is selected from:

[0239]

[0240] Clause 30. The method of any one of clauses 1 to 29, wherein the at least one tertiary amine is selected from:

[0241]

[0242] Clause 31. The process of any of Clauses 1-30, wherein the catalyst composition comprises at least two tertiary amines.

[0243] Clause 32. The process of any of Clauses 1-31, wherein the catalyst composition further comprises a tertiary amine lacking an isocyanate-reactive group.

[0244] Clause 33. The method of Clause 32, wherein the tertiary amine containing no isocyanate-reactive groups is one or more selected from the group consisting of:

[0245]

[0246] Clause 34. A method of making a polyurethane foam, the method comprising:

[0247] The foam formulation was prepared as follows:

[0248] At least one organic isocyanate is contacted with at least one polyol in the presence of a blowing agent and a catalyst composition, wherein the catalyst composition comprises:

[0249] at least one tertiary amine comprising an isocyanate-reactive group; and

[0250] Monohydric alcohol, wherein the monohydric alcohol comprises a compound selected from C 1-7 Straight chain alkyl -OH, C 3-6 Branched alkyl -OH and C 3-6 at least one alcohol of a cycloalkyl-OH group;

[0251] in:

[0252] The monohydric alcohol is present in the catalyst composition at 5 wt % to 15 wt %; and

[0253] The polyurethane foam has an isocyanate index between 80 and 120.

[0254] Clause 35. The method of Clause 34, wherein the at least one tertiary amine containing an isocyanate-reactive group comprises at least one selected from structural part.

[0255] Clause 36. The method of clause 34 or 35, wherein the blowing agent comprises at least one member selected from the group consisting of carbon dioxide (CO2), water, acetone, methyl formate, hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), and hydrocarbons.

[0256] Clause 37. The process of any of clauses 34-36, wherein the at least one organic isocyanate is toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), or a combination thereof.

[0257] Clause 38. The method of any of clauses 34-37, wherein at least one polyol is a polyether polyol, a polyester polyol, a copolymer polyol, or a natural oil polyol.

[0258] Clause 39. The process of any of clauses 34-38, wherein the at least one polyol is virgin or recycled.

[0259] Clause 40. The process of any of Clauses 34-39, wherein the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of a crosslinking agent.

[0260] Clause 41. The process of any of Clauses 34-40, wherein the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of an organosilicon surfactant.

[0261] Clause 42. The process of any of Clauses 34-41, wherein the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of an additional amine.

[0262] Clause 43. The method of clause 42, wherein the additional amine comprises at least one selected from the group consisting of triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole, N-methylmorpholine, N-ethylmorpholine, triethylamine, N,N′-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 2,4,6-tris(dimethylaminomethyl)phenol, N-methyldicyclohexylamine, pentamethyldipropylenetriamine, N -methyl-N′-(2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyl-diethylenetriamine, hexamethyl-triethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexyl-amine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl) ether, tris(3-dimethylaminopropyl)amine, 1,8-diazabicyclo[5.4.0]undecane, and acid-blocked derivatives of 1,8-diazabicyclo[5.4.0]undecane.

[0263] Clause 44. The process of any of Clauses 34-43, wherein the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of a metal catalyst.

[0264] Clause 45. The method of Clause 44, wherein the metal catalyst is a metal carboxylate.

[0265] Clause 46. The method of Clause 45, wherein the metal carboxylate comprises a metal and a carboxylate anion.

[0266] Clause 47. The method of Clause 46, wherein the metal is at least one selected from tin (Sn), bismuth (Bi), lead (Pb), iron (Fe), zinc (Zn), and potassium (K).

[0267] Clause 48. The method of Clause 46, wherein the carboxylate is a carboxylate anion of at least one carboxylic acid selected from the group consisting of acetic acid, propionic acid, butyric acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexylcarboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid.

[0268] Item 49. The method of Item 44, wherein the metal catalyst is an organotin catalyst.

[0269] Item 50. The method of Item 49, wherein the organotin catalyst is at least one selected from the group consisting of dibutyltin diacetate, dimethyltin dilaurylmercaptate, dibutyltin dilaurylmercaptate, dimethyltin diisooctylmaleate, dibutyltin diisooctylmaleate, dimethyltin di(2-ethylhexylmercaptoacetate), dibutyltin di(2-ethylhexylmercaptoacetate), dimethyltin neodecanoate, dibutyltin neodecanoate, dimethyltin isononanoate, dibutyltin isononanoate, stannous octoate, stannous neodecanoate, stannous isononanoate, and stannous carboxylates.

[0270] Clause 51. The method of any of clauses 34-50, wherein the metal catalyst is present at about 0 parts per hundred parts of polyol (pphp) to about 20 pphp.

[0271] Clause 52. The method of any of clauses 34-51, wherein the at least one tertiary amine is a tertiary amine of the formula:

[0272]

[0273] in:

[0274] R 1 is hydrogen or -C 1-4 alkyl;

[0275] R 2 It is hydrogen, -C 1-4 alkyl,

[0276] R 3 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; and

[0277] R 4 and R 5 are independently hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2.

[0278] Clause 53. The method of any of clauses 34-52, wherein the at least one tertiary amine is selected from:

[0279]

[0280] Clause 54. The method of any of clauses 34-53, wherein the at least one tertiary amine is a tertiary amine of the formula:

[0281]

[0282] in:

[0283] yes

[0284] R 6 It is hydrogen, -C 1-4 Alkyl, -C 1-4 Alkyl-OH, -C 1-4 Alkyl-NH2, -C 1-4 Alkyl-N(CH3)2;

[0285] R 7 It is hydrogen, -C 2-6 Alkyl-OH, -C 2-6 Alkyl-NH2, -C 2-6 Alkyl-N(CH3)2 or

[0286] R 8 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2;

[0287] R 9 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; and

[0288] R 10 and R 11 are independently hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2.

[0289] Clause 55. The method of any of clauses 34-54, wherein at least one tertiary amine is selected from:

[0290]

[0291] DETAILED DESCRIPTION

[0292] Example

[0293] Example 1

[0294] Manual Hybrid Assessment

[0295] The hand mixing experiment was performed using the following procedure. Using a mechanical mixer equipped with a 7.6 cm diameter high shear mixing blade rotating at 5000 RPM, the formulations were blended together for approximately 10 minutes. The premixed formulations were maintained at 23° C. using a low-temperature incubator. Mondur TD-80 (an 80 / 20 2,4 / 2,6 isomer blend of toluene diisocyanate) or modified MDI was added to the premix in the correct stoichiometric amount for the reporting index of each foam. The mixture was blended together and dispersed for approximately 5 seconds using a Premier Mill Corporation Series 2000, Model 89. The foaming mixture was transferred to an Imperial Bondware #GDR-170 paper bucket and allowed to rise freely while recording data.

[0296] Example 2

[0297] The model tertiary amine N,N,N′-trimethyl-N′-3-aminopropyl-bis(aminoethyl) ether ( NE300 (amine catalyst) is a popular polyurethane foaming catalyst used in many commercial applications. This catalyst is a commonly used polyurethane foaming catalyst in flexible molding and flexible block applications, where chemical emissions are a significant concern. However, this catalyst is also used in many other applications, such as rigid, semi-rigid, spray coatings, and any other application where water is used to foam polyurethane polymers.

[0298] Evaluation of solid carbamate formation under ambient conditions

[0299] Approximately 20 grams of the amine catalyst is mixed with approximately 12 grams of solid CO2 in an open glass container and briefly immersed in a 2°C (35°F) cold water bath. The glass container of amine catalyst is then transferred to a 28°C (82°F) warm water bath for approximately 20 minutes to dissolve the solid CO2. The glass container is then removed from the warm water bath and allowed to stand at 24°C (75°F) for 5 minutes. Visually observe the amine catalyst liquid for solid formation. Secure the container with a lid and place it in a controlled temperature environment at 10°C (50°F), such as an incubator, overnight. Periodically visually observe the amine catalyst for solid formation.

[0300] Various alcohols were added at various ratios to mitigate the formation of solid urethane intermediates. Table 2 shows the results.

[0301]

[0302] Example 3

[0303] The amine catalyst composition can be used as a blowing catalyst to produce polyurethane foams of various polyurethane foam densities.

[0304] The foam pad was prepared by adding the amine catalyst to approximately 320 grams of the premix (prepared as in Table 3) in a 951 mL (32 oz) paper cup. The formulation was mixed at approximately 6,000 RPM for approximately 20 seconds using an overhead stirrer equipped with a 5.1 cm (2 inch) diameter paddle.

[0305] Toluene diisocyanate (TDI) was then added and the formulation was thoroughly mixed using the same agitator at approximately 6,000 RPM for approximately another 6 seconds before being poured into a 5-gallon plastic bucket at room temperature. Rise time and foam height were monitored for 5 minutes. The foam was allowed to fully cure overnight and removed from the bucket the following day. The foam samples were stored under constant temperature and humidity conditions for 48 hours before being cut and tested.

[0306]

[0307] Table 4 shows the physical properties of flexible slabstock polyurethane foam samples in a low-density slabstock formulation with an amine catalyst having two different monohydric alcohols (isopropanol and 1-pentanol). The flexible slabstock samples were made using a single blowing agent of the amine catalyst to show the effect of each individual cosolvent on the foam physical properties. The gelling amine catalyst in each case was triethylenediamine (TEDA).

[0308]

[0309] Example 4

[0310] The foam pad was prepared by adding the amine catalyst to approximately 320 grams of the premix (prepared as in Table 4) in a 951 mL (32 oz) paper cup. The formulation was mixed at approximately 6000 RPM for approximately 20 seconds using an overhead stirrer equipped with a 5.1 cm (2 inch) diameter paddle.

[0311] Toluene diisocyanate (TDI) was then added and the formulation was thoroughly mixed using the same agitator at approximately 6000 RPM for approximately another 6 seconds before being poured into a 3.5 gallon plastic bucket at room temperature. Rise time and foam height were monitored for 5 minutes. The foam was allowed to fully cure overnight and removed from the bucket the following day. The foam samples were stored under constant temperature and humidity conditions for 48 hours before being cut and tested.

[0312]

[0313] Table 6 shows the physical properties of flexible slabstock polyurethane foam samples in a high density slabstock formulation with an amine catalyst composition having two different monohydric alcohols (isopropanol and 1-pentanol). The flexible slabstock samples were made using a single foaming reaction using the amine catalyst to show the effect of each individual cosolvent on the foam physical properties. The gelling amine catalyst in each case was triethylenediamine (TEDA).

[0314]

[0315] Example 5

[0316] As previously described in Example 2, approximately 20 grams of the amine catalyst, either alone or with the addition of 1-2 grams of isopropanol, is mixed with approximately 12 grams of solid CO2 in an open glass container and briefly immersed in a 2°C (35°F) cold water bath. The glass container of amine / alcohol catalyst is then transferred to a 28°C (82°F) warm water bath for approximately 20 minutes to dissolve the solid CO2. The glass container is then removed from the warm water bath and allowed to stand at 24°C (75°F) for 5 minutes. The amine / alcohol catalyst liquid is visually observed for solid formation. The container is secured with a lid and placed in a controlled temperature environment, such as an incubator, at 10°C (50°F) overnight. The amine / alcohol catalyst is visually observed for solid formation periodically.

[0317] Four samples were each analyzed for carbamate content by FTIR. A droplet of each sample was placed on a ThermoScientific FTIR window for analysis. The four samples included (1) NE300 without solid CO2 exposure (control, spectrum A), (2) NE300 with solid CO2 exposure (spectrum D), (3) NE300 with solid CO2 exposure and 5% isopropanol blend (spectrum C), and (4) NE300 with 10% CO2 exposure (spectrum B). For the samples corresponding to spectra C and D, the NE300 was analyzed by FTIR at 1674 cm -1 The presence of a peak near the wavenumber is evident from the urethane growth.

[0318] Example 6

[0319] Tables 7 and 8 show the physical properties of flexible slabstock polyurethane foam samples using amine catalyst compositions with three linear monohydric alcohols and cyclic and branched alcohols. They also show the physical properties of non-alcoholic amine catalyst compositions. Flexible slabstock samples were made using a single blowing agent of the amine catalyst to demonstrate the effect of each individual cosolvent on the foam's physical properties. Control gelling amine catalysts, triethylenediamine (TEDA) and DABCONE 1082, were used for comparison.

[0320]

[0321]

Claims

1. A method for producing polyurethane foam, the method comprising: The foam formulation was prepared as follows: At least one organic isocyanate is contacted with at least one polyol in the presence of a blowing agent and a catalyst composition, wherein the catalyst composition comprises: at least one tertiary amine comprising an isocyanate-reactive group; and Monohydric alcohol, wherein the monohydric alcohol comprises at least one selected from C 1-7 Straight chain alkyl -OH, C 3-6 Branched alkyl -OH and C 3-6 Alcohols containing cycloalkyl-OH.

2. The method according to claim 1, wherein the at least one tertiary amine comprising an isocyanate-reactive group comprises at least one moiety selected from the group consisting of:

3. The method according to claim 1, wherein the blowing agent comprises at least one substance selected from the group consisting of carbon dioxide (CO2), water, acetone, methyl formate, hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), and hydrocarbons.

4. The method of claim 3, wherein the blowing agent comprises carbon dioxide (CO2) and water.

5. The method of claim 1, wherein the at least one organic isocyanate is toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), a polymeric isocyanate, or a combination thereof.

6. The method of claim 1, wherein the at least one polyol is a polyether polyol, a polyester polyol, a copolymer polyol, or a natural oil polyol.

7. The process according to claim 6, wherein the at least one polyol is new or recycled.

8. The process of claim 1, wherein the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of a crosslinking agent.

9. The process of claim 1, wherein the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of an organosilicon surfactant.

10. The process according to claim 1, wherein the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of an additional amine.

11. The method according to claim 10, wherein the additional amine comprises at least one selected from the group consisting of triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole, N-methylmorpholine, N-ethylmorpholine, triethylamine, N,N′-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 2,4,6-tris(dimethylaminomethyl)phenol, N-methyldicyclohexylamine, pentamethyldipropylenetriazine, amine, N-methyl-N′-(2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyl-diethylenetriamine, hexamethyl-triethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexylamine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl) ether, tris(3-dimethylaminopropyl)amine, 1,8-diazabicyclo[5.4.0]undecane, and acid-blocked derivatives of 1,8-diazabicyclo[5.4.0]undecane.

12. The process of claim 1, wherein the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of a metal catalyst.

13. The method of claim 12, wherein the metal catalyst is a metal carboxylate.

14. The method of claim 13, wherein the metal carboxylate comprises a metal and a carboxylate anion. 15 . The method according to claim 14 , wherein the metal is at least one selected from tin (Sn), bismuth (Bi), lead (Pb), iron (Fe), zinc (Zn), and potassium (K).

16. The method of claim 14, wherein the carboxylate is a carboxylate anion of at least one carboxylic acid selected from the group consisting of acetic acid, propionic acid, butyric acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexylcarboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid.

17. The method of claim 12, wherein the metal catalyst is an organotin catalyst.

18. The method according to claim 17, wherein the organotin catalyst is at least one selected from the group consisting of dibutyltin diacetate, dimethyltin dilaurylmercaptate, dibutyltin dilaurylmercaptate, dimethyltin diisooctylmaleate, dibutyltin diisooctylmaleate, dimethyltin bis(2-ethylhexylmercaptoacetate), dibutyltin bis(2-ethylhexylmercaptoacetate), dimethyltin neodecanoate, dibutyltin neodecanoate, dimethyltin isononanoate, dibutyltin isononanoate, stannous octoate, stannous neodecanoate, stannous isononanoate, and stannous carboxylates.

19. The method of claim 12, wherein the metal catalyst is present in an amount of about 0 parts per hundred parts of polyol (pphp) to about 20 pphp.

20. The method of claim 1, wherein the polyurethane foam has an isocyanate index between 80 and 120.

21. The method of claim 1, wherein the polyurethane foam has a density between 0.8 pounds per cubic foot (pcf) and 3.5 pcf.

22. The method of claim 1, wherein the monohydric alcohol is present in the catalyst composition at 5 mass percent (wt%) to 15 wt%.

23. The method of claim 1, wherein the monohydric alcohol is present in less than 0.5% by weight of the foam formulation.

24. The method of claim 1 wherein the monohydric alcohol, tertiary amine, is present in less than 1.0% by weight of the foam formulation.

25. The method of claim 1, wherein the monohydric alcohol comprises at least one alcohol selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, cyclopentanol, and cyclohexanol.

26. The method of claim 1, wherein the at least one tertiary amine is a tertiary amine of the formula: in: R 1 is hydrogen or -C 1-4 alkyl; R 2 It is hydrogen, -C 1-6 alkyl, R 3 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; and R 4 and R 5 are independently hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2.

27. The method of claim 1, wherein the at least one tertiary amine is selected from:

28. The method of claim 1, wherein the at least one tertiary amine is a tertiary amine of the formula: in: yes R 6 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH, -C 1-6 Alkyl-NH2, -C 1-6 Alkyl-N(CH3)2; R 7 It is hydrogen, -C 2-6 Alkyl-OH, -C 2-6 Alkyl-NH2, -C 2-6 Alkyl-N(CH3)2 or R 8 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; R 9 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; and R 10 and R 11 are independently hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2.

29. The method of claim 1, wherein the at least one tertiary amine is selected from:

30. The method of claim 1, wherein the at least one tertiary amine is selected from:

31. The method of claim 1, wherein the catalyst composition comprises at least two tertiary amines.

32. The method of claim 1, wherein the catalyst composition further comprises a tertiary amine lacking an isocyanate-reactive group.

33. The method of claim 32, wherein the tertiary amine containing no isocyanate-reactive group is one or more selected from the group consisting of:

34. A method of making a polyurethane foam, the method comprising: The foam formulation was prepared as follows: At least one organic isocyanate is contacted with at least one polyol in the presence of a blowing agent and a catalyst composition, wherein the catalyst composition comprises: at least one tertiary amine comprising an isocyanate-reactive group; and Monohydric alcohol, wherein the monohydric alcohol comprises at least one alcohol selected from the group consisting of: C 1-7 Straight chain alkyl -OH, C 3-6 Branched alkyl -OH and C 3-6 Cycloalkyl-OH; in: The monohydric alcohol is present in the catalyst composition at 5 wt % to 15 wt %; and The polyurethane foam has an isocyanate index between 80 and 120.

35. The method of claim 34, wherein the at least one tertiary amine comprising an isocyanate-reactive group comprises at least one moiety selected from the group consisting of:

36. The method of claim 34, wherein the blowing agent comprises at least one selected from the group consisting of carbon dioxide (CO2), water, acetone, methyl formate, hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), and hydrocarbons.

37. The method of claim 34, wherein the at least one organic isocyanate is toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), or a combination thereof.

38. The method of claim 34, wherein at least one polyol is a polyether polyol, a polyester polyol, a copolymer polyol, or a natural oil polyol.

39. The method of claim 34, wherein the at least one polyol is virgin or recycled.

40. The method of claim 34, wherein contacting the at least one organic isocyanate with the at least one polyol is performed in the presence of a crosslinking agent.

41. The method of claim 34, wherein contacting the at least one organic isocyanate with the at least one polyol is carried out in the presence of an organosilicon surfactant.

42. The process of claim 34, wherein the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of an additional amine.

43. The method of claim 42, wherein the additional amine comprises at least one selected from the group consisting of triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole, N-methylmorpholine, N-ethylmorpholine, triethylamine, N,N′-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 2,4,6-tris(dimethylaminomethyl)phenol, N-methyldicyclohexylamine, pentamethyldipropylenetriamine , N-methyl-N′-(2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyl-diethylenetriamine, hexamethyl-triethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexyl-amine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl) ether, tris(3-dimethylaminopropyl)amine, 1,8-diazabicyclo[5.4.0]undecane, and acid-blocked derivatives of 1,8-diazabicyclo[5.4.0]undecane.

44. The process of claim 34, wherein the contacting of the at least one organic isocyanate with the at least one polyol is carried out in the presence of a metal catalyst.

45. The method of claim 44, wherein the metal catalyst is a metal carboxylate.

46. ​​The method of claim 45, wherein the metal carboxylate comprises a metal and a carboxylate anion.

47. The method of claim 46, wherein the metal is at least one selected from the group consisting of tin (Sn), bismuth (Bi), lead (Pb), iron (Fe), zinc (Zn), and potassium (K).

48. The method of claim 46, wherein the carboxylate is a carboxylate anion of at least one carboxylic acid selected from the group consisting of acetic acid, propionic acid, butyric acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexylcarboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid.

49. The method of claim 44, wherein the metal catalyst is an organotin catalyst.

50. The method of claim 49, wherein the organotin catalyst is at least one selected from the group consisting of dibutyltin diacetate, dimethyltin dilaurylmercaptate, dibutyltin dilaurylmercaptate, dimethyltin diisooctylmaleate, dibutyltin diisooctylmaleate, dimethyltin bis(2-ethylhexylmercaptoacetate), dibutyltin bis(2-ethylhexylmercaptoacetate), dimethyltin neodecanoate, dibutyltin neodecanoate, dimethyltin isononanoate, dibutyltin isononanoate, stannous octoate, stannous neodecanoate, stannous isononanoate, and stannous carboxylates.

51. The method of claim 44, wherein the metal catalyst is present in an amount of about 0 parts per hundred parts of polyol (pphp) to about 20 pphp.

52. The method of claim 32, wherein the at least one tertiary amine is a tertiary amine of the formula: in: R 1 is hydrogen or -C 1-4 alkyl; R 2 It is hydrogen, -C 1-4 alkyl, R 3 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; and R 4 and R 5 are independently hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2.

53. The method of claim 32, wherein the at least one tertiary amine is selected from:

54. The method of claim 32, wherein the at least one tertiary amine is a tertiary amine of the formula: in: yes R 6 It is hydrogen, -C 1-4 Alkyl, -C 1-4 Alkyl-OH, -C 1-4 Alkyl-NH2, -C 1-4 Alkyl-N(CH3)2; R 7 It is hydrogen, -C 2-6 Alkyl-OH, -C 2-6 Alkyl-NH2, -C 2-6 Alkyl-N(CH3)2 or R 8 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; R 9 It is hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2; and R 10 and R 11 are independently hydrogen, -C 1-6 Alkyl, -C 1-6 Alkyl-OH or -C 1-6 Alkyl-NH2.

55. The method of claim 32, wherein the at least one tertiary amine is selected from:

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