WO2025024345A1

WO2025024345A1 - Catalysts having an electron withdrawing group and their use in polyurethane formulations

Info

Publication number: WO2025024345A1
Application number: PCT/US2024/038935
Authority: WO
Inventors: Yun-Shan Liu; Haibo Zhao; Sylvia RIETHMEYER
Original assignee: Huntsman Petrochemical Llc
Priority date: 2023-07-26
Filing date: 2024-07-22
Publication date: 2025-01-30

Abstract

The present disclosure generally relates to catalysts having an electron withdrawing group for use in a polyurethane formulation. The polyurethane formulation includes the catalyst having an electron withdrawing group, a compound containing an isocyanate functional group, an active hydrogen-containing compound, a halogenated olefin and optionally one or more of an amine catalyst having at least one tertiary amine group, a non-amine catalyst and an additive.

Description

CATALYSTS HAVING AN ELECTRON WITHDRAWING GROUP

AND THEIR USE IN POLYURETHANE FORMULATIONS

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This Application claims priority to United States Provisional Application No. 63/529,084 filed July 26, 2023. The noted application is incorporated herein by reference.

FIELD

[0002] The present disclosure generally relates to catalysts for use in generating a thermosetting polyurethane and/or polyisocyanurate material. More specifically, the present disclosure relates to polyurethane catalysts containing an electron withdrawing group.

BACKGROUND

[0003] Thermosetting polyurethane foam compositions are widely known and used in a variety of applications, such as in the automotive and housing industries. For example, sprayable thermosetting polyurethane foam compositions typically include an isocyanate (“A-side”) and polyol resin blend (“B-side”) that are co-mixed and immediately sprayed onto a substrate which often times is a vertical wall or ceiling. In addition to a polyol or mixture of polyols, the B-side can also include surfactants, flame retardants, blowing agents, water, and catalysts which accelerate the foam reaction and are therefore integral to the performance of the sprayable polyurethane foam. This finetuned mixture allows the polyurethane mixture to contact the substrate, foam up, and cure in less than a minute.

[0004] In order to produce an industrially viable polyurethane foam, the polyol resin blend must impart sufficient strength to the foam and enable the foam to form sufficiently fast enough to maintain a desired cellular structure. For example, if the composition is not sufficiently quick enough or does not impart sufficient strength, the foam may collapse during formation or lack physical strength in its finished form rendering the foam inadequate.

[0005] Recently, new blowing agents have been introduced into the polyurethane and/or polyisocyanurate foam market that have little or no effect on ozone degradation or global warming in contrast to their predecessors (for e.g., chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs)). These new blowing agents, known as halogenated olefin blowing agents, hydrofluoroolefins (HFOs), or hydrocholorofluoroolefins (HCFOs), are being widely adopted in spray thermosetting foam applications. The performance of spray thermosetting foam is dependent on the reaction between the polyisocyanate and polyol resin blend which is exothermic and releases heat and carbon dioxide (CO2) causing the blowing agent to boil resulting in synchronous, rapid polymerization and cellular structure formation. Metal and amine catalysts can accelerate this reaction to acceptable rates which is a necessary part of any sprayed thermosetting foam formulation.

[0006] Traditional amine catalysts that have been used in spray thermosetting foam compositions may contain multiple methylamine groups which minimize steric hinderance around the amine group and enable faster catalysis of the polyurethane and/or polyisocyanurate foam-forming reactions while minimizing catalyst loading. Structures of several such amine catalysts include the compounds below:

[0007] However, the use of these amine catalysts in polyol resin blends containing HFOs can result in unwanted reactions between the amine catalysts, the HFO blowing agents, and the surfactants resulting in the degradation or failure of the polyol resin blend. For example, the unwanted reactions can cause, without limitation, the release of chloride and/or fluoride ions which can reduce the activity of the amine catalysts and possibly destroy the blowing agents. In addition, the fluoride ions that are eliminated from the HFO molecules can attack the silicon atoms in the surfactant thereby degrading the surfactant and lowering its performance weakening the cellular structure of the resulting foam. The above combination of the unwanted reactions can thus result in polyol resin blends that are unstable, and if foams are sprayed using such unstable blends, the foams may not properly rise and can exhibit irregular and inconsistent cell structure.

[0008] Accordingly, there is a continuous need for the development of amine catalysts that can facilitate the rapid reaction between the polyisocyanate and HFO- containing polyol resin blend without significantly affecting the storage stability of the polyol resin blend.

SUMMARY

[0009] The present disclosure generally provides a polyurethane formulation comprising a catalyst having an electron withdrawing compound, a compound containing an isocyanate functional group, an active hydrogen-containing compound and a halogenated olefin.

[0010] According to another embodiment, there is provided a catalyst package for use in forming a polyurethane material, the catalyst package comprising the catalyst having an electron withdrawing group and a second component selected from an amine catalyst containing at least one tertiary amine group, a non-amine catalyst, a halogenated olefin and a mixture thereof.

[0011] In yet another embodiment, there is provided a method for forming a polyurethane material comprising contacting a compound containing an isocyanate functional group, an active hydrogen-containing compound, a halogenated olefin and optionally (i) an amine catalyst containing at least one tertiary amine group or (ii) a nonamine catalyst or (iii) an additive or (iv) a mixture thereof in the presence of the catalyst having an electron withdrawing group.

DETAILED DESCRIPTION

[0012] There are typically two types of reactions taking place during a spray foam reaction: blowing and gelling. The front-end blowing reaction generated between the compound containing an isocyanate functional group and active hydrogen-containing compound present in the polyol resin blend is accelerated by certain polyurethane catalysts and is extremely important for producing a viable spray foam system. It has been surprisingly discovered that a narrow group of amine catalysts containing an electron withdrawing group produce a stable and strong spray thermosetting foam when present in an halogenated olefin-containing polyol resin blend.

[0013] Unless otherwise defined herein, technical terms used in connection with the present disclosure shall have the meanings that are commonly understood by those having ordinary skill in the art.

[0014] The use of the word “a” or “an”, when used in conjunction with the term “comprising”, “including”, “having”, or “containing” (or variations of such terms) may mean “one”, but it is also consistent with the meaning of “one or more”, “at least one”, and “one or more than one”.

[0015] The use of the term “or” is used to mean “and/or” unless clearly indicated to refer solely to alternatives and only if the alternatives are mutually exclusive.

[0016] If the specification states a component or feature “may,” “can,” “could,” or “might” be included or have a characteristic, that particular component or feature is not required to be included or have the characteristic.

[0017] Throughout this disclosure, the term “about” is used to indicate that a value includes the inherent variation of error for the quantifying device, mechanism, or method, or the inherent variation that exists among the subject(s) to be measured. For example, but not by way of limitation, when the term “about” is used, the designated value to which it refers may vary by plus or minus ten percent, or nine percent, or eight percent, or seven percent, or six percent, or five percent, or four percent, or three percent, or two percent, or one percent, or one or more fractions therebetween.

[0018] The use of “at least one” will be understood to include one as well as any quantity more than one, including but not limited to, 1 , 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc. The term “at least one” may extend up to 100 or 1000 or more depending on the term to which it refers. In addition, the quantities of 100/1000 are not to be considered as limiting since lower or higher limits may also produce satisfactory results.

[0019] In addition, the phrase “at least one of X, Y, and Z” will be understood to include X alone, Y alone, and Z alone, as well as any combination of X, Y, and Z. Likewise, the phrase “at least one of X and Y” will be understood to include X alone, Y alone, as well as any combination of X and Y. Additionally, it is to be understood that the phrase “at least one of” can be used with any number of components and have the similar meanings as set forth above.

[0020] As used herein, the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.

[0021] As used herein, the terms “% by weight”, “wt %”, “weight percentage”, or “percentage by weight” are used interchangeably.

[0022] The term “substantially free” refers to a composition in which a particular compound or moiety is present in an amount that has no material effect on the composition. In some embodiments, “substantially free” may refer to a composition in which the particular compound or moiety is present in the composition in an amount of less than 2% by weight, or less than 1 % by weight, or less than 0.5% by weight, or less than 0.1 % by weight, or less than 0.05% by weight, or even less than 0.01 % by weight based on the total weight of the composition, or that no amount of that particular compound or moiety is present in the respective composition.

[0023] The term “alkyl” refers to a straight chain or branched chain saturated hydrocarbon group having from 1 to 10 carbon atoms or from 1 to 8 carbon atoms or from 1 to 6 carbon atoms. In some embodiments, alkyl substituents may be lower alkyl groups. The term “lower” refers to alkyl groups having from 1 to 5 carbon atoms. Examples of “lower alkyl groups” include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, butyl, and pentyl groups.

[0024] The term “cycloalkyl group” means a monocyclic saturated ring with carbon and hydrogen atoms and having no carbon-carbon multiple bonds. Examples of cycloalkyl groups may include, but are not limited to, C3 -C7 cycloalkyl groups, for example a cyclohexyl or cyclopropyl or cyclopentyl group.

[0025] The term “halogenated olefin” refers to an olefin compound or moiety which may include fluorine, chlorine, bromine or iodine.

[0026] The present disclosure is generally directed to a catalyst having an electron withdrawing group and its use in polyurethane formulations including a compound containing an isocyanate functional group, an active hydrogen-containing compound, a halogenated olefin as a blowing agent and optionally (i) an amine catalyst containing at least one tertiary amine group or (ii) a non-amine catalyst or (iii) one or more additives or (iv) a mixture thereof. The present disclosure is also directed to a stable polyol resin blend including the catalyst having an electron withdrawing group, an active-hydrogen containing compound, a halogenated olefin and optionally (i) an amine catalyst containing at least one tertiary amine group or (ii) a non-amine catalyst or (iii) one or more additives or (iv) a mixture thereof. The present disclosure is further directed to a catalyst package for use in forming a polyurethane material including the tertiary amine catalyst containing an electron withdrawing compound as described herein and a second component selected from (i) an amine catalyst containing at least one tertiary amine group (ii) a non-amine catalyst, (iii) a halogenated olefin and (iv) a mixture thereof. The present disclosure is still further directed to rigid or flexible polyurethane foam or other polyurethane material made from a formulation comprising the catalyst having an electron withdrawing compound as described herein, a compound containing an isocyanate functional group, an active hydrogen-containing compound, a halogenated olefin and optionally (i) an amine catalyst compound containing at least one tertiary amine group or (ii) a non-amine catalyst or (iii) one or more additives. The term “polyurethane material” as used herein, is understood to encompass pure polyurethane, polyurethane polyurea, and pure polyurea materials or foam. It has been surprisingly found when the catalyst having an electron withdrawing group of the present disclosure is used in a formulation for the production of the polyurethane material, the formulation exhibits an industrially useful balance of catalyst speed, cream time, and halogenated olefin stability.

[0027] According to one embodiment, the catalyst having an electron withdrawing group is a compound having a general formula

3 where Ri and R2 are independently a lower alkyl group or a cycloalkyl group or R1 and R2 form a C4-C5 cyclic group with nitrogen (i.e., pyrrolidinyl, piperidinyl) or R3 and R4 are independently a lower alkyl group or a cycloalkyl group, EWG is an electron withdrawing group selected from -NO2, -CN, -CF3, -CO2H, -CO2R, -CONH2, -CONHR, -CON(R)₂, -CHO, -C(O)R, -SO2R, -SO2OR, -SO₂CF₃, -SO3H, -NO, -P(O)(R)₂, -P(O)(OR)₂ and -Cs- C14 aryl where R is H, an alkyl group or C5-C14 aryl and a is 1 or 2. [0028] According to one embodiment, Ri and R2 are independently methyl, ethyl, propyl, isopropyl or isobutyl. In another embodiment, R1 and R2 are independently methyl or ethyl.

[0029] According to another embodiment, R3 and R4 are independently H, methyl, ethyl or isopropyl. In still another embodiment, R3 and R4 are independently H, methyl or ethyl.

[0030] According to a further embodiment, the electron withdrawing group is selected from -CO2R, -CO2NH2, -CONHR, -CON(R)2 and -C(O)R where R is a lower alkyl group. In still another embodiment, the electron withdrawing group is selected from -CO2R and -CON(R)2 where R is methyl or ethyl.

[0031] According to some embodiments, the catalyst having an electron withdrawing group may be used alone in forming the polyurethane material. In still other embodiments, the catalyst having an electron withdrawing group may be combined with an amine catalyst containing at least one tertiary amine group or a non-amine catalyst or a mixture thereof in forming the polyurethane material. In embodiments in which the catalyst having an electron withdrawing group is combined with an amine catalyst containing at least one tertiary amine group, or a non-amine catalyst, or a mixture thereof the weight ratio of the catalyst having an electron withdrawing group to the amine catalyst containing at least one amine group, or the non-amine catalyst or mixture thereof is at least 1 :1 , and in some embodiments, at least 1.5:1 and in still other embodiments at least 2:1 and in further embodiments at least 5:1 , while in still further embodiments at least 10:1. In still other embodiments, the weight ratio of the catalyst having an electron withdrawing group to the amine catalyst containing at least one tertiary amine group, or the non-amine catalyst or mixture thereof is from 0.1 :99.9 to 99.9:0.1 , and in still other embodiments from 1 :99 to 99: 1 , and in still other embodiments from 5:95 to 95:5, and in further embodiments from 10:90 to 90:10, while in still further embodiments from 25:75 to 75:25, while in further embodiments from 40:60 to 60:40.

[0032] Representative amine catalysts containing at least one tertiary group include, but are not limited to, bis-(2-dimethylaminoethyl)ether (JEFFCAT® ZF-20 catalyst), N,N,N'-trimethyl-N'-hydroxyethylbisaminoethylether (JEFFCAT® ZF-10 catalyst), N-(3-dimethylaminopropyl)-N,N-diisopropanolamine (JEFFCAT® DPA catalyst), N,N-dimethylethanolamine (JEFFCAT® DMEA catalyst), triethylene diamine (JEFFCAT® TEDA catalyst), blends of N,N-dimethylethanolamine ethylene diamine (such as JEFFCAT® TD-20 catalyst), N,N-dimethylcyclohexylamine (JEFFCAT® DMCHA catalyst), benzyldimethylamine (JEFFCAT® BDMA catalyst), pentamethyldiethylenetriamine (JEFFCAT® PMDETA catalyst), N,N,N',N",N"- pentamethyldipropylenetriamine (JEFFCAT® ZR-40 catalyst), N,N-bis(3- dimethylaminopropyl)-N-isopropanolamine (JEFFCAT® ZR-50 catalyst), N'-(3- (dimethylamino)propyl-N,N-dimethyl-1 ,3-propanediamine (JEFFCAT® Z-130 catalyst), 2-(2-dimethylaminoethoxy)ethanol (JEFFCAT® ZR-70 catalyst), N,N,N- trimethylaminoethyl-ethanolamine (JEFFCAT® Z-110 catalyst), N-ethylmorpholine (JEFFCAT® NEM catalyst), N-methylmorpholine (JEFFCAT® NMM catalyst), 4- methoxyethylmorpholine, N.N'dimethylpiperazine (JEFFCAT® DMP catalyst), 2,2'- dimorpholinodiethylether (JEFFCAT® DMDEE catalyst), 1 ,3,5-tris(3- (dimethylamino)propyl)-hexahydro-s-triazine (JEFFCAT® TR-90 catalyst), 1 - propanamine, 3-(2-(dimethylamino)ethoxy), substituted imidazoles such as 1 ,2- dimethlyimidazol and 1 -methyl-2-hydroxyethylimidazole, bis-substituted piperazines such aminoethylpiperazine, N,N',N'-trimethyl aminoethylpiperazine or bis-(N-methyl piperazine)urea, N-methylpyrrolidines and substituted methylpyrrolidines such as 2- aminoethyl-N-methylpyrrolidine or bis-(N-methylpyrrolidine)ethyl urea, 3- dimethylaminopropylamine, N,N,N",N"-tetramethyldipropylenetriamine, tetramethylguanidine, 1 ,2-bis-diisopropanol. Other examples of such amine catalysts include N-alkylmorpholines, such as N-butylmorpholine and dimorpholinodiethylether, N,N'-dimethylaminoethanol, N,N-dimethylamino ethoxyethanol, bis- (dimethylaminopropyl)-amino-2-propanol, bis-(dimethylamino)-2-propanol, bis-(N,N- dimethylamino)ethylether, N,N,N'-trimethyl-N’hydroxyethyl-bis-(aminoethyl)ether, N,N- dimethyl amino ethyl-N'-methyl amino ethanol, 1-[2-(Dimethylamino)ethyl]piperazine and tetramethyliminobispropylamine. The aforementioned JEFFCAT® catalysts are available from Huntsman Petrochemical LLC, The Woodlands, Texas. [0033] The non-amine catalyst is a compound having catalytic activity for the reaction of an isocyanate group with a polyol or water, but is not a compound falling within the description of the amine catalysts containing at least one tertiary amine above. Examples of such additional non-amine catalysts include, for example: (i) tertiary phosphines, such as trialkylphosphines and dialkylbenzylphosphines; (ii) chelates of various metals, such as those which can be obtained from acetylacetone, benzoylacetone, trifluoroacetyl acetone, ethyl acetoacetate and the like, with metals such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co and Ni; (iii) metal carboxylates such as potassium acetate and sodium acetate; (iv) acidic metal salts of strong acids, such as ferric chloride, stannic chloride, stannous chloride, antimony trichloride, bismuth nitrate and bismuth chloride; (v) strong bases, such as alkali and alkaline earth metal hydroxides, alkoxides and phenoxides; (vi) alcoholates and phenolates of various metals, such as Ti(OR⁶)4, Sn(OR⁶)4and AI(OR⁶)3 where R⁶ is alkyl or aryl, and the reaction products of the alcoholates with carboxylic acids, beta-diketones and 2-(N,N-dialkylamino) alcohols; (vii) alkaline earth metal, Bi, Pb, Sn or Al carboxylate salts; and (viii) tetravalent tin compounds, and tri- or pentavalent bismuth, antimony or arsenic compounds.

[0034] The catalyst having an electron withdrawing group may be used in a catalytically effective amount to catalyze the reaction between a compound containing an isocyanate functional group and an active hydrogen-containing compound for making rigid, flexible or spray polyurethane foam or other polyurethane materials. A catalytically effective amount of the catalyst having an electron withdrawing group may range from about 0.01 -15 parts per 100 parts of active hydrogen-containing compound, and in some embodiments from about 0.05-12.5 parts per 100 parts of active hydrogen-containing compound, and in even further embodiments from about 0.1 -10 parts per 100 parts of active hydrogen-containing compound, and yet in even further embodiments from about 0.3 to 7 parts per 100 parts of active hydrogen-containing compound or 0.5-5 parts per 100 parts of active hydrogen-containing compound. In some embodiments, the catalyst having an electron withdrawing group is the sole catalyst used for making the rigid, flexible or spray polyurethane foam (i.e. the polyurethane formulation is substantially free of the amine catalyst containing at least one tertiary amine group and the non-amine catalyst).

[0035] In one embodiment, the compound containing an isocyanate functional group is a polyisocyanate, an isocyanate-term inated prepolymer or a mixture thereof.

[0036] Polyisocyanates include those represented by the general formula Q(NCO)b where b is a number from 2-5, such as 2-3 and Q is an aliphatic hydrocarbon group containing 2-18 carbon atoms, a cycloaliphatic hydrocarbon group containing 5-10 carbon atoms, an araliphatic hydrocarbon group containing 8-13 carbon atoms, or an aromatic hydrocarbon group containing 6-15 carbon atoms.

[0037] Examples of polyisocyanates include, but are not limited to, ethylene diisocyanate; 1 ,4-tetramethylene diisocyanate; 1 ,6-hexamethylene diisocyanate; 1 ,12- dodecane diisocyanate; cyclobutane-1 ,3-diisocyanate; cyclohexane-1 ,3- and 1 ,4- diisocyanate, and mixtures of these isomers; isophorone diisocyanate; 2,4- and 2,6- hexahydrotoluene diisocyanate and mixtures of these isomers; dicyclohexylmethane- 4,4'-diisocyanate (hydrogenated MDI, or HMDI); 1 ,3- and 1 ,4-phenylene diisocyanate; 2,4- and 2,6-toluene diisocyanate and mixtures of these isomers (TDI); diphenylmethane-2,4'-and/or 4,4'-diisocyanate (MDI); naphthylene-1 ,5-diisocyanate; triphenylmethane-4,4',4"-triisocyanate; polyphenyl-polymethylene-polyisocyanates of the type which may be obtained by condensing aniline with formaldehyde, followed by phosgenation (crude MDI); norbornane diisocyanates; m- and p-isocyanatophenyl sulfonylisocyanates; perchlorinated aryl polyisocyanates; modified polyisocyanates containing carbodiimide groups, urethane groups, allophnate groups, isocyanurate groups, urea groups, or biruret groups; polyisocyanates obtained by telomerization reactions; polyisocyanates containing ester groups; and polyisocyanates containing polymeric fatty acid groups. Those skilled in the art will recognize that it is also possible to use mixtures of the polyisocyanates described above.

[0038] Isocyanate-term inated prepolymers may also be employed in the preparation of the polyurethane. Isocyanate-term inated prepolymers may be prepared by reacting an excess of polyisocyanate or mixture thereof with a minor amount of an active-hydrogen containing compound, such as those further described below, as determined by the well-known Zerewitinoff test (i.e. , a sample is treated with the Grignard reagent, methylmagnesium iodide, which reacts with any acidic hydrogen atom to form methane. This gas can be determined quantitatively by measuring its volume).

[0039] The polyurethane formulation also includes an active hydrogen-containing compound. In one embodiment, the active hydrogen-containing compound is a polyol. Polyols suitable for use in the present disclosure include, but are not limited to, polyalkylene ether polyols, polyester polyols, polymer polyols, a non-flammable polyol such as a phosphorus-containing polyol or a halogen-containing polyol. Such polyols may be used alone or in suitable combination as a mixture.

[0040] Polyalkylene ether polyols include poly(alkylene oxide) polymers, such as poly(ethylene oxide) and polypropylene oxide) polymers, and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols; for example, ethylene glycol, propylene glycol, 1 ,3-butane diol, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane, and similar low molecular weight polyols.

[0041] Polyester polyols include, but are not limited to, those produced by reacting a dicarboxylic acid with an excess of a diol, for example, adipic acid with ethylene glycol or butanediol, or reaction of a lactone with an excess of a diol such as caprolactone with propylene glycol.

[0042] In addition to polyalkylene ether polyols and polyester polyols, polymer polyols are also suitable for use in the present disclosure. Polymer polyols are used in polyurethane materials to increase resistance to deformation, for example, to improve the load-bearing properties of the foam or material. Examples of polymer polyols include, but are not limited to, graft polyols or polyurea modified polyols (Polyharnstoff Dispersion polyols). Graft polyols comprise a triol in which vinyl monomers are graft copolymerized. Suitable vinyl monomers include, for example, styrene, or acrylonitrile. A polyurea modified polyol is a polyol containing a polyurea dispersion formed by the reaction of a diamine and a diisocyanate in the presence of a polyol. A variant of polyurea modified polyols are polyisocyanate poly addition (PIPA) polyols, which are formed by the in situ reaction of an isocyanate and an alkanolamine in a polyol.

[0043] The non-flammable polyol may, for example, be a phosphorus-containing polyol obtainable by adding an alkylene oxide to a phosphoric acid compound. A halogen-containing polyol may, for example, be those obtainable by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide.

[0044] Further examples of active hydrogen-containing compounds include water, hydroxyl-term inated polythioethers, polyamides, polyesteramides, polycarbonates, polyacetals, polyolefins, polysiloxanes, polyamines and polythiols.

[0045] The polyurethane formulation also contains one or more halogenated olefins that serve as a blowing agent. The halogenated olefin comprises at least one haloalkene (e.g.. fluoroalkene or chlorofluoroalkene) comprising from 3 to 4 carbon atoms and at least one carbon-carbon double bond. Suitable compounds may include hydrohaloolefins such as trifluoropropenes, tetrafluoropropenes (e.g., tetrafluoropropene (1234)), pentafluoropropenes (e.g., pentafluoropropene (1225)), chlorotrifloropropenes (e.g., chlorotrifluoropropene (1233)), chlorodifluoropropenes, chlorotrifluoropropenes, chlorotetrafluoropropenes, hexafluorobutenes (e.g., hexafluorobutene (1336)), or combinations thereof. In certain embodiments, the tetrafluoropropene, pentafluoropropene, and/or chlorotrifluoropropene compounds have no more than one fluorine or chlorine substituent connected to the terminal carbon atom of the unsaturated carbon chain (e.g., 1 ,3,3,3-tetrafluoropropene (1234ze); 1 ,1 ,3,3-tetrafluoropropene, 1 ,2,3,3,3-pentafluoropropene (1225ye), 1 ,1 ,1 -trifluoropropene, 1 , 2, 3,3,3- pentafluoropropene, 1 ,1 ,1 ,3,3-pentafluoropropene (1225zc), 1 , 1 ,2, 3,3- pentafluoropropene (1225yc), (Z)- 1 ,1 , 1 ,2,3-pentafluoropropene (1225yez), 1-chloro-3 ,3,3-trifluoropropene (1233zd), 1 ,1 ,1 ,4,4,4-hexafluorobut-2-ene (1336mzzm), or combinations thereof).

[0046] Other blowing agents that may be used in combination with the halogenated olefins described above include air, nitrogen, carbon dioxide, hydrofluorocarbons ("HFCs"), alkanes, alkenes, mono-carboxylic acid salts, ketones, ethers, or combinations thereof. Suitable HFCs include 1 ,1 -difluoroethane (HFC- 152a), 1 , 1 ,1 ,2- tetrafluoroethane (HFC-134a), pentafluoroethane (HFC-125), 1 , 1 ,1 , 3,3- pentafluoropropane (HFC-245fa), 1 ,1 ,1 ,3,3-pentafluorobutane (HFC-365mfc) or combinations thereof. Suitable alkanes and alkenes include n-butane, n-pentane, isopentane, cyclopentane, 1 -pentene, or combinations thereof. Suitable monocarboxylic acid salts include methyl formate, ethyl formate, methyl acetate, or combinations thereof. Suitable ketones and ethers include acetone, dimethyl ether, or combinations thereof.

[0047] In addition, the polyurethane formulation may optionally include one or more additives. Examples of additives include, but are not limited to, a carboxylic acid, cell stabilizers, surfactants, chain extenders, pigments, fillers, flame retardants, thermally expandable microspheres, water, thickening agents, smoke suppressants, reinforcements, antioxidants, UV stabilizers, antistatic agents, infrared radiation absorbers, dyes, mold release agents, antifungal agents, biocides or any combination thereof.

[0048] In one embodiment, the carboxylic acid is a compound having a general formula

where R? is hydrogen, an alkyl group, an alkenyl group, cycloaliphatic group, an aromatic group, or alkylaromatic group, k and m are independently an integer from 0 to 3 with the proviso that k+m>1 and when k=1 and m=0, R is an aromatic group or alkylaromatic group.

[0049] According to one embodiment, the R? alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, propyl, butyl, iso-butyl, n-amyl, n-decyl or 2-ethylhexyl. [0050] Particular compounds that may be used as the carboxylic acid include, but are not limited to, a hydroxyl-carboxylic acid, a di-carboxylic acid, formic acid, acetic acid, malonic acid, glutaric acid, maleic acid, glycolic acid, lactic acid, 2-hydroxybutyric acid, citric acid, AGS acid, phenol, cresol, hydroquinone, or combinations thereof. AGS acid is a mixture of dicarboxylic acids (i. e. , adipic acid, glutaric acid, and succinic acid) that is obtained as a by-product of the oxidation of cyclohexanol and/or cyclohexanone in the adipic acid manufacturing process. Suitable AGS acid that may be used as the carboxylic acid of formula (3) include RHODIACID® acid (available from Solvay S.A.), DIBASIC acid (available from Invista S.a.r.l), FLEXATRAC™-AGS-200 acid (available from Ascend Performance Materials LLC), and glutaric acid, technical grade (AGS) (available from Lanxess A.G.

[0051] Cell stabilizers may include, for example, silicon surfactants or anionic surfactants. Examples of suitable silicon surfactants include, but are not limited to, polyalkylsiloxane, polyoxyalkylene polyol-modified dimethylpolysiloxane, alkylene glycol-modified dimethylpolysiloxane, or any combination thereof.

[0052] Suitable surfactants (or surface-active agents) include emulsifiers and foam stabilizers, such as silicone surfactants known in the art, for example, polysiloxanes, as well as various amine salts of fatty acids, such as diethylamine oleate or diethanolamine stearate, as well as sodium salts of ricinoleic acids.

[0053] Examples of chain extenders include, but are not limited to, compounds having hydroxyl or amino functional groups, such as glycols, amines, diols, and water. Further non-limiting examples of chain extenders include ethylene glycol, propylene glycol, 1 ,4-butanediol, 1 ,3-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,10-decanediol, 1 ,12-dodecanediol, ethoxylated hydroquinone, 1 ,4-cyclohexanediol, N- methylethanolamine, N-methylisopropanolamine, 4-aminocyclo-hexanol, 1 ,2- diaminoethane, or any mixture thereof.

[0054] Pigments may be used to color code the polyurethane materials during manufacture, to identify product grade, or to conceal yellowing. Pigments may include any suitable organic or inorganic pigments. For example, organic pigments or colorants include, but are not limited to, azo/diazo dyes, phthalocyanines, dioxazines, or carbon black. Examples of inorganic pigments include, but are not limited to, titanium dioxide, iron oxides or chromium oxide.

[0055] Fillers may be used to increase the density and load bearing properties of polyurethane foam or material. Suitable fillers include, but are not limited to, barium sulfate, carbon black or calcium carbonate.

[0056] Flame retardants can be used to reduce flammability. For example, such flame retardants include, but are not limited to, chlorinated phosphate esters, chlorinated paraffins or melamine powders.

[0057] Thermally expandable microspheres include those containing a (cyclo)aliphatic hydrocarbon. Such microspheres are generally dry, unexpanded or partially unexpanded microspheres consisting of small spherical particles with an average diameter of typically 10 to 15 micron. The sphere is formed of a gas proof polymeric shell (e.g. consisting of acrylonitrile or PVDC), encapsulating a minute drop of a (cyclo)aliphatic hydrocarbon, e.g. liquid isobutane. When these microspheres are subjected to heat at an elevated temperature level (e.g. 150°C to 200°C) sufficient to soften the thermoplastic shell and to volatilize the (cyclo)aliphatic hydrocarbon encapsulated therein, the resultant gas expands the shell and increases the volume of the microspheres. When expanded, the microspheres have a diameter 3.5 to 4 times their original diameter as a consequence of which their expanded volume is about 50 to 60 times greater than their initial volume in the unexpanded state. Examples of such microspheres are the EXPANCEL®-DU microspheres which are marketed by AKZO Nobel Industries.

[0058] The methods for generally producing a polyurethane material from a polyurethane formulation are described in, for example, U.S. Pat. Nos. 5,420,170, 5,648,447, 6,107,359, 6,552,100, 6,737,471 and 6,790,872, the contents of which are hereby incorporated by reference. Various types of polyurethane materials can be made using the catalyst having an electron withdrawing group, such as rigid foams, flexible foams, semi-flexible foams, microcellular elastomers, backings for textiles, spray elastomers, cast elastomers, polyurethane-isocyanurate foams, reaction injection molded polymers and structural reaction injection molded polymers.

[0059] A non-limiting example of a general flexible polyurethane formulation having a 15-150 kg/m³ density (e.g., automotive seating) containing the catalyst having an electron withdrawing group may comprise the following components in parts by weight (pbw) as shown in Table 1 , below:

Table 1

[0060] A non-limiting example of a general rigid polyurethane formulation having a 15-70 kg/m³ density containing the catalyst having an electron withdrawing group may comprise the following components in parts by weight (pbw), as shown in Table 2, below:

Table 2

[0061] The amount of the compound containing an isocyanate functional group is not limited, but will generally be within those ranges known to one skilled in the art. An exemplary range given above is indicated by reference to Isocyanate Index which is defined as the number of equivalents of isocyanate divided by the total number of equivalents of active hydrogen, multiplied by 100.

[0062] Thus, in yet another embodiment, the present disclosure provides a method for producing a polyurethane material which comprises contacting the compound containing an isocyanate functional group, an active hydrogen-containing compound and halogenated olefin in the presence of the catalyst having an electron withdrawing group and optionally (i) an amine catalyst containing at least one tertiary amine group or (ii) a non-amine catalyst, or (iii) an additive or (iv) a mixture thereof.

[0063] In one particular embodiment, the polyurethane material is a rigid or flexible foam prepared by bringing together at least one compound containing an isocyanate functional group and at least one active hydrogen-containing compound, such as a polyisocyanate and polyol, and a halogenated olefin, in the presence of the catalyst having an electron withdrawing group and optionally (i) an amine catalyst containing at least one tertiary amine group or (ii) a non-amine catalyst or (iii) an additive or (iv) a mixture thereof to form a reaction mixture and subjecting the reaction mixture to conditions sufficient to cause the active hydrogen-containing compound, for e.g., polyol, to react with the compound containing the isocyanate functional group, for e.g., polyisocyanate. The polyisocyanate, polyol, halogenated olefin, catalyst having an electron withdrawing group and optional amine catalyst containing at least one tertiary amine group and/or non-amine catalyst and/or additive(s) may be heated prior to mixing them and forming the reaction mixture. In other embodiments, the polyisocyanate, polyol, catalyst having an electron withdrawing group and optional amine catalyst containing at least one tertiary amine group and/or a non-amine catalyst and/or additive(s) are mixed at ambient temperature (for e.g., from about 15°C-40°C) and heat may be applied to the reaction mixture, but in some embodiments, applying heat may not be necessary. The foam may be made in a free rise (slabstock) process in which the foam is free to rise under minimal or no vertical constraints. Alternatively, molded foam may be made by introducing the reaction mixture in a closed mold and allowing it to foam within the mold. The particular polyisocyanate and polyol are selected with the desired characteristics of the resulting foam. Other additives useful in making foams, such as those described above, may also be included to produce a particular type of foam.

[0064] According to another embodiment, a polyurethane material may be produced in a one-step process in which an A-side reactant is reacted with a B-side reactant. The A-side reactant may comprise the compound containing an isocyanate functional group, for e.g., polyisocyanate while the B-side reactant may comprise the active hydrogen-containing compound, for e.g., polyol, halogenated olefin and the catalyst having an electron withdrawing group and optional amine catalyst containing at least one tertiary amine group and/or a non-amine catalyst. In some embodiments, the A-side and/or B-side may also optionally contain one or more additives described above. Thus, in one embodiment there is provided a polyol resin blend suitable for preparing a thermosetting polyurethane material comprising a polyol, a halogenated olefin, a catalyst having an electron withdrawing group and optionally (i) an amine catalyst containing at least one tertiary amine group or (ii) a non-amine catalyst or (iii) an additive or (iv) a mixture thereof. [0065] The polyurethane materials may be used in a variety of applications, such as, a precoat; a backing material for carpet; building composites; insulation; spray foam insulation; applications requiring use of impingement mix spray guns; urethane/urea hybrid elastomers; vehicle interior and exterior parts such as bed liners, dashboards, door panels, and steering wheels; flexible foams (such as furniture foams and vehicle component foams); integral skin foams; rigid spray foams; rigid pour-in-place foams; coatings; adhesives; sealants; filament winding; and other polyurethane composite, foams, elastomers, resins, and reaction injection molding (RIM) applications.

[0066] In another embodiment, there is provided a method of improving the stability and reactivity of a halogenated olefin-containing polyol resin blend comprising adding a catalyst having an electron withdrawing group comprising a compound having a general formula:

where Ri and R2 are independently a lower alkyl group or a cycloalkyl group or R1 and R2 form a C4-C5 cyclic group with the nitrogen, R3 and R4 are independently a lower alkyl group or a cycloalkyl group, EWG is an electron withdrawing group selected from -NO2, -CN, -CF3, -CO2H, -CO2R, -CONH2, -CONHR, -CON(R)₂, -CHO, -C(O)R, -SO2R, -SO2OR, -SO2CF3, -SO3H, -NO, and -C5-C14 aryl where R is H, an alkyl group or C5-C14 aryl and a is 1 or 2 to the blend.

EXAMPLES

Example 1 - Synthesis of 3-dimethylamino, N,N-dimethylpropanamide

[0067] 1000 grams of methyl acrylate was charged into a reaction vessel. The head space was purged with N2 gas to remove air. 1157 grams dimethyl amine (DMA) was then added into the reaction vessel under agitation and the temperature was held at 40°C. The reaction mixture was first digested at 40°C for 4 hours. The reaction temperature was then raised to 150°C and the reaction mixture was further digested at 150°C for 6 hours. The reaction vessel was cooled down to 100°C and excess DMA was stripped from the crude product by N2 flow. The crude product was further cooled to ambient temperature and then collected. The GC-MS analysis of the crude product showed that 3-dimethylamino, N,N-dimethylpropanamide was present at a purity of about 98%. The crude product was then further distilled to a purity level >99% and blended with para-nonylphenol to 50% concentration for further use.

[0068] 172 grams methyl acrylate was charged into a reaction vessel. The head space was purged with N2 gas to remove air. 95 grams dimethyl amine (DMA) was then added into the reaction vessel under agitation and the temperature was held at 40°C. The reaction mixture was digested at 40°C for 1 hour. The DMA in the crude product was stripped by N2 flow and the crude product was collected. The GC-MS analysis of the crude product showed that methyl (3-dimethylaminopropanoate) was present at a purity of about 100%. Example 3 - Synthesis of ethyl (3-dimethylaminopropanoate)

[0069] 200 grams ethyl acrylate was charged into a reaction vessel. The head space was then purged with N2 gas to remove air. 95 grams dimethyl amine (DMA) was then added into the reactor vessel under the agitation and the temperature was held at 40°C. The reaction mixture was digested at 40°C for 1 hour. The DMA in the crude product was then stripped by N2 flow and the crude product was collected. The GC-MS analysis of the crude product showed that methyl ethyl (3-dimethylaminopropanoate) was present at a purity of about 93%.

[0070] 200 grams methyl methacrylate was charged into a reaction vessel. The head space was purged with N2gas to remove air. 95 grams dimethyl amine (DMA) was then added into the reactor under the agitation and the temperature was held at 40°C. The reaction mixture was digested at 40°C for 1 hour. The DMA in the crude product was stripped by In flow and the crude product was collected. The GC-MS analysis of this crude is showed that methyl ethyl methyl (3-dimethylamino)-2-methylpropanoate was present at a purity of about 68%. The other component present was unconverted methyl methacrylate.

Example 5 - Synthesis of ethane-1 ,2-diyl bis(3-(dimethylamino)-2-methylpropanoate)

[0071] 198 grams ethylene glycol dimethyl acrylate was charged into a reaction vessel. The head space was purged with N2 gas to remove air. 190 grams dimethyl amine (DMA) was then added into the reaction vessel and the temperature was held at 40°C. The reaction mixture was digested at 40°C for 1 hour. The DMA in the crude product was stripped by N2 flow and the crude product was collected. The GC-MS analysis of the crude product showed that methyl ethyl methyl (3-dimethylamino)-2- methylpropanoate was present at a purity of about 30%.

Stability, Cream Time and Catalyst Speed

[0072] Three factors (catalyst speed, stability and cream time) were evaluated for spray polyurethane formulations described herein using inventive catalysts having an electron withdrawing group and two state of the art catalysts (VI) and (VII) having the formulas below.

Catalyst speed was essentially determined by its string gel time. The shorter the string gel time the faster the reactivity. In order to achieve the same initial gel time, a different catalyst loading was used throughout cup foam testing. Stability was determined by storing spray foam formulations containing the catalysts having electron withdrawing groups and the state of the art catalysts (a) and (b) at different % catalyst concentrations for a period of one week at a temperature at 50 °C. The reactivity of the spray foam formulation was measured before and after the one-week period and recorded as a percent drift of the original gel time based on following calculation:

% drift = [(final gel time -initial gel time)/initial gel time] x 100 and the results were used to quantify the stability for each formulation. A higher percentage (larger drift) is less effective than a lower percentage in drift. Cream time was determined by rapidly mixing a blend containing a polyol and a certain percentage of each of the catalysts having an electron withdrawing group and catalysts (a) and (b) with a polyisocyanate in a cup. The cream time was determined as the inflection point where a foam began to rise.

[0073] All spray foam formulations tested were prepared using a master batch, along with the particular catalyst being compared and 1.8 wt.% water which was held constant for every test. The amounts were adjusted by the amount of the particular catalyst used in each test to allow the water level to remain constant and to keep a consistent pour size of 50 grams of a preblended polyol resin B-side and 50 grams of a polyisocyanate A-side, which was RUBINATE® M polymeric MDI. The master batch included the following components, as shown in Table 3, below:

Table 3

[0074] The initial reactivity and % drift after aging at 50°C for one week for spray foam formulations containing the Example I catalyst having an electron withdrawing group and state of the art catalysts (a) and (b) were determined and are shown below in Tables 4 and 5.

Table 4. Initial Reactivity

Example I was used in a 50% blend with nonylphenol Table 5. % Drift After Aging

* Example I was used in a 50% blend with nonylphenol

[0075] From the above description, the present disclosure is well adapted to carry out the object and to attain the advantages mentioned herein as well as those inherent in the present disclosure. While exemplary embodiments of the present disclosure have been described for the purposes of the disclosure, it will be understood that numerous changes may be made which will readily suggest themselves to those skilled in the art which can be accomplished without departing from the scope of the present disclosure and the appended claims.

Claims

What is claimed is:

1. A polyol resin blend suitable for preparing a thermosetting polyurethane material comprising a polyol, a halogenated olefin, and a catalyst having an electron withdrawing group comprising a compound having a general formula:

wherein Ri and R2 are independently a lower alkyl group or a cycloalkyl group or R1 and R2 form a C4-C5 cyclic group, R3 and R4 are independently a lower alkyl group or a cycloalkyl group, EWG is an electron withdrawing group selected from -NO2, -CN, -CF3, -CO2H, -CO2R, -CONH2, -CONHR, -CON(R)₂, -CHO, -C(O)R, -SO2R, -SO2OR, -SO2CF3, -SO3H, -NO, -P(O)(R)2, -P(O)(OR)2 and -C5-C14 aryl where R is H, an alkyl group or C5-C14 aryl and a is 1 or 2.

2. The polyol resin blend of claim 1 , wherein R1 and R2 are independently methyl, ethyl, propyl, isopropyl or isobutyl.

3. The polyol resin blend of claim 1 , wherein R3 and R4 are independently H, methyl, ethyl or isopropyl.

4. The polyol resin blend of claim 1 , wherein the electron withdrawing group is selected from -CO2R, -CO2NH2, -CONHR, -CON(R)2 and -C(O)R where R is a lower alkyl group.

5. The polyol resin blend of claim 1 , further comprising carboxylic acid having a general formula

wherein R7 is hydrogen, an alkyl group, an alkenyl group, cycloaliphatic group, an aromatic group, or alkylaromatic group, k and m are independently an integer from 0 to 3 with the proviso that k+m>1 and when k=1 and m=0, R is an aromatic group or an alkylaromatic group.

6. The polyol resin blend of claim 1 , further comprising a component selected from (i) an amine catalyst containing at least one tertiary amine group, (ii) a non-amine catalyst or (iii) one or more additives and (iv) a mixture thereof.

7. A polyurethane formulation comprising the polyol resin blend of claim 1 and a compound containing an isocyanate functional group.

8. The polyurethane formulation of claim 7, wherein the compound containing an isocyanate functional group comprises a polyisocyanate, an isocyanate-term inated prepolymer or a mixture thereof.

9. A method of improving the stability and reactivity of a halogenated olefin-containing polyol resin blend comprising adding a catalyst having an electron withdrawing group comprising a compound having a general formula:

wherein Ri and R2 are independently a lower alkyl group or a cycloalkyl group or R1 and R2 form a C4-C5 cyclic group, R3 and R4 are independently a lower alkyl group or a cycloalkyl group, EWG is an electron withdrawing group selected from -NO2, -CN, -CF3, -CO2H, -CO2R, -CONH2, -CONHR, -CON(R)₂, -CHO, -C(O)R, -SO2R, -SO2OR, -SO2CF3, -SO3H, -NO, and -C5-C14 aryl where R is H, an alkyl group or C5-C14 aryl and a is 1 or 2 to the blend.

10. A catalyst package for use in forming a polyurethane material comprising: a catalyst having an electron withdrawing group comprising a compound having a general formula:

a wherein R1 and R2 are independently a lower alkyl group or a cycloalkyl group or R1 and R2 form a C4-C5 cyclic group, R3 and R4 are independently a lower alkyl group or a cycloalkyl group, EWG is an electron withdrawing group selected from -NO2, -CN, -CF3, -CO2H, -CO2R, -CONH2, -CONHR, -CON(R)₂, -CHO, -C(O)R, -SO2R, -SO2OR, -SO2CF3, -SO3H, -NO, and -C5-C14 aryl where R is H, an alkyl group or C5-C14 aryl and a is 1 or 2 ; and a second component selected from (i) an amine catalyst containing at least one tertiary amine group (ii) a non-amine catalyst, (iii) a halogenated olefin and (iv) a mixture thereof.

11. A method for producing a polyurethane material comprising contacting the polyol resin blend of claim 1 with a compound containing an isocyanate functional group.

12. A polyurethane material produced according to the method of claim 10.

13. The polyurethane material of claim 11 , wherein the polyurethane material is a spray foam.

14. The polyurethane material of claim 11 , wherein the polyurethane material is a rigid foam or a flexible foam.

15. The polyurethane material of claim 11 for use as a precoat, a backing material for carpet, a building composite, insulation, a spray foam insulation, a urethane/urea hybrid elastomers; in vehicle interior and exterior parts, a flexible foam, an integral skin foam, a rigid spray foam, a rigid pour-in-place foam; a coating; an adhesive, a sealant, or a filament winding.