Correlation transfer active trimerization catalyst salt

Abstract

The present invention provides compositions having a phase transfer trimer catalyst and methods for producing polyisocyanurate / polyurethane foams using such compositions.

Description

Technical Field

[0001] The present invention relates to a composition comprising a catalyst system, a polyisocyanurate / polyurethane (PIR / PUR) foam formulation, and a method for producing a PIR / PUR foam.

Background Art

[0002] Typically, a polyisocyanurate / polyurethane (PIR / PUR) foam is produced by reacting a polyol and a polyisocyanate in the presence of a catalyst. Additional additives may be present. PIR / PUR foam products have excellent thermal stability and flame retardancy. Isocyanurates retain their strength up to a temperature of about 160 °C and are resistant to most organic solvents, acids, alkalis, ultraviolet light, and humidity.

[0003] Certain carboxylates, such as alkali metal carboxylates, are used as catalysts in the production of PIR / PUR foams. However, the use of commercially available alkali metal carboxylate catalysts often leads to undesirable foam processing problems, which are particularly severe in continuous foaming operations. When measuring the profile of the rise rate of the foaming PIR / PUR mixture, a characteristic "step" is observed, which is usually associated with the onset of the trimerization process. This "step" becomes apparent when the height of the PIR / PUR foam is plotted against time. This trimerization "step" causes a significant change in the rise rate of the foam, and essentially, the foam expands at two different rates during the foaming process. In the continuous lamination operation of polyisocyanurate / polyurethane foams, it is difficult to control the speed of the production unit in accordance with the changes in the rise rate of the foam. As a result, overfilling of the foam or backflow of the foam can occur. This undesirable rapid rise in the height of the foam is particularly problematic when processing polyisocyanurate / polyurethane formulations at high isocyanate indices. The reason is that the change in the rise rate of the foam is much more dramatic as the isocyanate index increases. Therefore, when using conventional alkali metal carboxylate catalysts, it is a technical challenge to produce desirable low-flammability foam products at high isocyanate indices.

[0004] Compared with alkali metal carboxylate catalysts, commercially available polyisocyanurate trimerization catalysts based on hydroxyalkylammonium carboxylates exhibit different processabilities in continuous operations. They result in a smoother rate increase profile and have fewer significant trimerization "steps". That is, the foam rise rate is more constant even at higher isocyanate indices. However, commercially available hydroxyalkylammonium carboxylate catalysts, such as trimethyl(2-hydroxypropyl)ammonium-2-ethylhexanoate, can be unstable at temperatures above about 100 °C and decompose into volatile amine by-products, such as trimethylamine, imparting a strong amine odor to the finished foam product. The polymerization reaction for producing PIR / PUR foams is highly exothermic, and the processing temperature of the foam often exceeds 100 °C. Thus, hydroxyalkylammonium carboxylate catalysts can provide more predictable foam processability but at the expense of foam products with an optionally undesirable amine odor.

[0005] Accordingly, there is a need for catalyst compositions and foam formulations that can provide a smooth rise profile (foam height versus time) for producing PIR / PUR foams in continuous operations. Further, there is a need for catalyst compositions that function well in foam formulations at high isocyanate indices (e.g., indices from about 100 to about 800). At the same time, such catalyst compositions should provide equivalent or faster curing (faster tack-free time as defined in the experimental examples) compared to commercially available catalyst systems so that foam products produced using such catalyst compositions can have reduced surface friability (e.g., improved hardness) and enhanced surface adhesion during the production of finished products such as laminated foam panels. Optionally, depending on the choice of catalyst components, the catalyst composition can be thermally stable at the temperatures typically encountered during the production of PIR / PUR foams and can produce foams that are substantially free of volatile amines and / or amine odor.

[0006] U.S. Patent No. 4,503,226 (US4503226) relates to a method for synthesizing a polyisocyanurate composition from an organic polyisocyanate using a selection of quaternary ammonium carboxylates and carboxylic acid halides or anhydrides. The disclosure focuses on the synthesis of organic compounds having isocyanurate functional groups. Some compositions are disclosed including tetramethylammonium acetate, tetraethylammonium acetate, tetramethylammonium propionate, tetramethylammonium octanoate, tetramethylammonium 2-ethylhexanoate, tetrabutylammonium 2-ethylhexanoate, benzyltrimethylammonium acetate, phenyltrimethylammonium 2-ethylhexanoate, tetrabutylammonium benzoate and the like. However, the disclosure focuses on the synthesis of isocyanurate compounds and does not relate to methods for producing PIR / PUR polymers or foamed polymers.

[0007] U.S. Patent No. 4,771,025 (US4771025) relates to a catalyst system useful in the production of PIR / PUR rigid foams, comprising a) an alkali metal or tetraalkylammonium carboxylate, b) a carboxylate of a Group IIA metal, and optionally c) an amine co-catalyst. Examples of acids used in the patent disclosure for mixed metal salt catalysts include hexanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, cyclohexylacetic acid, trimethylacetic acid, isovaleric acid and butyric acid. Examples of tetraalkylammonium salts include tetrabutylammonium salts. The method requires the use of carboxylates of Group IIA metals, such as calcium and strontium salts, but also includes other metals, such as magnesium, zinc and barium salts, and expands the polymer material using a chlorofluorocarbon blowing agent, such as trichlorofluoromethane, to produce a foam. The carboxylates of Group IIA metals are also more insoluble in typical organic solvents used in polyurethane applications and require the use of special solvents or aqueous media, limiting the use of this approach.

[0008] U.S. Patent No. 5,321,050 (US5321050) discloses a method for producing a modified PIR foam by reacting an organic polyisocyanate, a polyol, and water in the presence of a trimerization catalyst composed of a hydroxyalkyl quaternary ammonium compound and a carbodiimide catalyst composed of a phospholene oxide. The trimerization catalyst has the general formula (R 1 R 2 R 3 N-CH2-CHOH-R 4 )(OOC-R 5 ), where R 1 , R 2 , R 3 independently represent alkyl, aralkyl, cycloalkyl, allyl or hydroxyalkyl, and R 4 and R 5 each independently represent a hydrogen atom, an alkyl, phenyl, alkenyl, hydroxyalkyl or ketoalkyl group. The method forms a PIR foam without the need for blowing agents such as CFCs, HCFCs, HFCs and methylene chloride, and requires the use of water as a blowing agent in the presence of a carbodiimide catalyst based on phospholene oxide. Preferred examples of the trimer catalyst include trimethyl-(2-hydroxypropyl)ammonium formate and trimethyl-(2-hydroxypropyl)ammonium 2-ethylhexanoate. In addition to the requirements for the phospholene oxide compound, the technique is most preferably used in formulations foamed with water, which leads to the formation of foamed materials with a higher content of closed cells that have an adverse effect on thermal insulation.

[0009] U.S. Patent No. 4,040,992 (US4040992) relates to a method for producing a PIR foam using an N-hydroxyalkyl quaternary ammonium carboxylate. Preferred catalysts are N-hydroxypropyl-trimethylammonium salts of carboxylic acids such as formic acid, acetic acid, hexanoic acid, and octanoic acid. For the quaternary ammonium salts, various amines are included, such as trimethylamine, N,N-dimethyl-N-(hydroxyethyl)-amine, N-benzyl-N,N-dimethylamine, and others, which can react with ethylene oxide or propylene oxide in the presence of a carboxylic acid to yield the corresponding N,N-dimethyl-N-hydroxyalkyl-ammonium carboxylate. These catalysts are used in the production of foams blown with water and CFCs, such as GENETRON® 11SBA (monochlorotrifluoroethane) and Freon® 11 (trichlorofluoromethane). These blowing agents are well-known ozone-depleting substances, and their commercial use is prohibited. The combined use of these catalysts with CFC-based blowing agents is characterized by a very delayed non-stick time, as shown in the experimental examples, which affects the curing of the foam surface and its adhesion to the substrate. Therefore, these polyurethane foam formulations have multiple limitations, such as environmental impact, delayed non-stick time, slow surface curing, and resulting poor adhesion, restricting their applicability in manufacturing operations that require rapid surface curing, such as intermittent mold filling or continuous lamination operations.

[0010] U.S. Patent No. 3,954,684 (US3954684) discloses a catalyst combination for trimerizing polyisocyanates to polyisocyanurates and uses a catalyst combination comprising a tertiary amine trimerization catalyst and a quaternary ammonium salt of an alkanoic acid. The catalyst is typically produced by neutralizing a carboxylic acid with a quaternary ammonium hydroxide. Examples of carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, neopentanoic acid, and the like. Examples of quaternary ammonium hydroxides are tetramethylammonium, tetraethylammonium, tetrabutylammonium, tetraoctylammonium, trimethylethylammonium, tributylethylammonium, triethylbutylammonium, benzyltrimethylammonium, dibenzyldimethylammonium, tribenzylmethylammonium and the like. The use of this catalyst combination allows the foaming rate to be varied as needed without collapsing the foam. A typical blowing agent disclosed is a CFC, such as trichlorofluoromethane. However, the use of those catalysts in the presence of the blowing agents described, such as Freon® R11, results in a delayed non-stick time, as shown in the experimental examples, which affects the curing of the foam surface, the surface hardness, and adhesion.

[0011] U.S. Patent No. 5,470,889 (US5470889) is a method for manufacturing a rigid closed-cell polyisocyanurate foam, comprising reacting a polyisocyanate and a polyester polyol or a mixture of a polyester polyol and at least one other isocyanate-reactive compound in the presence of 1) a hydrogen-containing blowing agent and at least one auxiliary blowing agent, and 2) a catalyst mixture comprising i) a carboxylate of an alkali metal or alkaline earth metal or a mixture thereof, ii) a tertiary amine, and iii) a quaternary ammonium carboxylate, wherein the molar ratio of the metal carboxylate / tertiary amine is less than about 2:1 and the total number of moles of the quaternary ammonium carboxylate is less than the combined number of moles of the metal carboxylate and the tertiary amine. The recommended blowing agents include partially halogenated hydrocarbons, ethers, and esters, hydrocarbons, ethers, esters, and the like. Useful hydrogen-containing halogenated carbons are HCFCs, such as 1,1-dichloro-1-fluoroethane (HCFC-141b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), monochlorodifluoromethane (HCFC-22), 1-chloro-1,1-difluoroethane (HCFC-142b), 1,1-difluoroethane (HCFC-152a), and 1,1,1,2-tetrafluoroethane (HFC-134a). According to the disclosure, other blowing agents can also be used, including water, air, nitrogen, carbon dioxide, and other volatile organic substances and / or compounds that decompose to release gases. This invention teaches the use of various blowing agents, but 1) requires a metal carboxylate, the metal preferably being an alkali or alkaline earth (e.g., potassium), and in the presence of a tertiary amine and a quaternary ammonium salt, the conditions are [RCO2M] / [R3N]<2 and [RCO2Q]<[RCO2M]+[R3N]. However, the presence of a metal carboxylate that follows this ratio has an adverse effect of inducing the trimerization step in the foam rise profile, causing the foaming material to rise at two different rates during the expansion of the polymer, leading to problems such as overfilling of the foam in continuous operations and making processing on a continuous line more difficult.

[0012] U.S. Patent No. 3,989,651 (US3989651) relates to a method for producing a spray foam of polyisocyanurate using a catalyst combination comprising i) N,N-dimethylcyclohexylamine and ii) a tetra(lower alkyl) quaternary ammonium salt of an alkanoic acid. The catalyst combination enables the spraying of polyisocyanurate foam under conditions of low ambient temperature on a cold substrate and achieves good adhesion between the foam and the substrate. The quaternary ammonium salt is produced by the reaction of the corresponding alkanoic acid with a suitable quaternary ammonium hydroxide. The alkanoic acid is represented by the general formula R 1 -CO2H [wherein R 1 represents hydrogen or a C 1~7 -alkyl group], while the quaternary hydroxide compound is represented by the general formula [R 2 4N + OH - [wherein R 2 represents hydrogen or a C 1~7 -alkyl group], and where R 1 and R 2 are the same or different. The blowing agent used is trichlorofluoromethane. The typical blowing agents disclosed are CFCs, such as trichlorofluoromethane. However, the use of a quaternary ammonium salt as a single catalyst in the presence of the described blowing agents containing various CFCs results in a delayed non-stick time, which affects the curing of the foam surface, the hardness of the foam, and the adhesion.

Prior Art Documents

Patent Documents

[0013]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

[0014] The present invention solves the above-identified problems associated with conventional catalysts and formulations disclosed in the prior art and provides a novel formulation for producing PIR / PUR foams, which comprises at least one anion source in the form of a carboxylate anion in combination with at least one cation source having phase transfer trimerization activity, and at least one blowing agent being a hydrocarbon or hydrofluorocarbon (HFC) or hydrofluoroolefin (HFO) or hydrochlorofluoroolefin (HCFO) or hydrochlorofluorocarbon (HCFC) or formic acid or water, provided that the at least one blowing agent is not a chlorofluorocarbon (CFC).

[0015] The resulting compositions and formulations contain phase transfer trimerization active carboxylates that can provide PIR / PUR foamed materials with a high isocyanurate content.

[0016] Accordingly, the present invention relates to a method for producing PIR / PUR rigid foams, which comprises contacting at least one polyisocyanate with a polyol premix containing a polyol or a mixture of polyols, a catalyst composition containing at least one phase transfer trimerization catalyst, and at least one blowing agent, provided that the at least one blowing agent is not a chlorofluorocarbon. The at least one phase transfer trimerization catalyst is a. When the blowing agent contains formic acid, of the general formula A-CO2 - · + NR 1R 2 R 3 R 4 [wherein A = H, and R 1 , R 2 , R 3 and R 4 are each independently methyl, ethyl, propyl, butyl or -CH2-Ar, and Ar is an aryl group, and preferably -C6H5, or A = H, R 1 = -CH2-CH2OH or -CH2-CH(OH)-CH3, R 2 = -CH2-Ar, and R 3 and R 4 are each independently methyl, ethyl, propyl or butyl, and Ar is an aryl group, and preferably -C6H5] of the phase transfer trimer catalyst, or b. When the blowing agent contains a C5-hydrocarbon blowing agent, the general formula A-CO2 - · + NR 1 R 2 R 3 R 4 [wherein A = H or methyl, and preferably methyl, R 1 = -CH2-CH2OH or -CH2-CH(OH)-CH3, R 2 = -CH2-Ar, and Ar is an aryl group, and preferably -C6H5, and R 3 and R 4 are each independently methyl, ethyl, propyl or butyl, or A = H or methyl, R 1 and R 2 and R 3 are each independently methyl, ethyl, propyl or butyl, and R 4 = -CH2-Ar, and Ar is an aryl group, and preferably -C6H5, or A = H or methyl, and preferably methyl, and R 1 , R2 and R 3 and R 4 are each independently a C1-C4 alkyl group] phase transfer trimer catalyst of, or c. When the blowing agent contains a C5-hydrocarbon blowing agent, general formula A-CO2 - · + NR 1 R 2 R 3 R 4 [wherein, A = ethyl, and R 1 , R 2 , R 3 and R 4 are each independently methyl, ethyl, propyl, butyl or -CH2-Ar, and Ar is an aryl group, and preferably -C6H5] phase transfer trimer catalyst of, or d. When the blowing agent contains a C5-hydrocarbon blowing agent, general formula A-CO2 - · + NR 1 R 2 R 3 R 4 [wherein, A = propyl, and R 1 , R 2 , R 3 and R 4 are each independently methyl, ethyl, propyl, butyl or -CH2-Ar, and Ar is an aryl group, and preferably -C6H5] includes a phase transfer trimer catalyst of.

[0017] In another aspect, the present invention provides a composition comprising the contact product of at least one active hydrogen-containing compound, a catalyst composition comprising at least one phase transfer trimer catalyst, and at least one blowing agent, provided that the at least one blowing agent is not a chlorofluorocarbon (CFC). Further, the present invention provides a composition comprising the contact product of at least one polyisocyanate, at least one active hydrogen-containing compound, a catalyst composition comprising at least one phase transfer trimer catalyst containing a primary hydroxyl group, a secondary hydroxyl group, a primary amine group, a secondary amine group, a urea group or an amide group, and at least one blowing agent, provided that the at least one blowing agent is not a chlorofluorocarbon (CFC).

[0018] The present invention also provides a method for producing a polyisocyanurate / polyurethane (PIR / PUR) foam. This method involves contacting at least one polyisocyanate and at least one active hydrogen-containing compound in the presence of at least one blowing agent (provided that the at least one blowing agent is not a CFC) and an effective amount of a catalyst composition comprising at least one phase transfer trimer catalyst.

[0019] The catalyst composition of the present invention provides a substantially constant increase in foam height over time even at a high isocyanate index, and during the production of PIR / PUR foams, it can provide a delay in cream time and unexpectedly rapid surface curing or a shorter non-stick time compared to conventional carboxylates. In another aspect of the present invention, the catalyst composition can be thermally stable at standard foam processing temperatures for producing PIR / PUR foams and is substantially free of volatile amines and / or amine odor.

[0020] The various aspects and embodiments in the present application can be used alone or in combination with each other. BRIEF DESCRIPTION OF THE DRAWINGS

[0021]

Figure 1

Figure 2

Figure 3

DETAILED DESCRIPTION OF THE INVENTION

[0022] Definitions The following definitions are provided to assist those skilled in the art in understanding the detailed description of the present invention. PIR: Polyisocyanurate. PUR: Polyurethane. Isocyanate index: The actual amount of polyisocyanate used, divided by the stoichiometrically required amount of polyisocyanate for reacting with all the active hydrogens in the reaction mixture, and multiplied by 100. Also known as (equivalent of NCO / equivalent of active hydrogen) × 100. pphp: Parts per 100 parts by mass of polyol. The DABCO® K15 catalyst manufactured by Evonik Corporation is a 70% solution in diethylene glycol of an alkali metal carboxylate, potassium 2-ethylhexanoate (also known as potassium octoate). The Polycat® 5 catalyst made by Evonik Corporation is a urethane catalyst and is chemically known as pentamethyldiethylenetriamine. The chemical name of Freon® R11 is trichlorofluoromethane. It is a chlorofluorocarbon foaming agent that destroys the ozone layer and is currently prohibited from commercial use.

[0023] Detailed Description of the Invention The present invention relates to a novel composition comprising at least one phase transfer trimerization catalyst in combination with a PUR / PIR system using a blowing agent, provided that the blowing agent is not a CFC or a mixture of CFCs. This novel catalyst system can be used as a polyisocyanate trimerization catalyst system for producing polyisocyanurate / polyurethane (PIR / PUR) foams. Further, the present invention relates to a novel composition comprising a contact product of at least one active hydrogen-containing compound, at least one blowing agent, and a catalyst composition comprising at least one phase transfer trimerization catalyst, provided that the blowing agent is not a chlorofluorocarbon. Further, the present invention relates to a novel composition comprising a contact product of at least one polyisocyanate, at least one blowing agent, and a catalyst composition comprising at least one phase transfer trimerization catalyst, provided that the blowing agent is not a chlorofluorocarbon. Further, the present invention relates to a novel composition comprising a contact product of at least one polyisocyanate, at least one blowing agent, and a catalyst composition comprising at least one phase transfer trimerization catalyst, provided that the blowing agent is not a chlorofluorocarbon. These novel compositions can be used together with additional components for producing PIR / PUR foams.

[0024] The present invention also provides a method for producing a PIR / PUR foam, which comprises contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of an effective amount of a catalyst composition comprising at least one blowing agent and at least one phase transfer trimerization catalyst, provided that the blowing agent is not a chlorofluorocarbon. Furthermore, using the novel catalyst system and catalyst composition of the present invention, rigid PIR / PUR foams can be produced by several methods known in the art.

[0025] The isocyanate can be trimerized to produce isocyanurate using a catalyst system comprising at least one phase transfer trimerization catalyst. Preferably, any amount of at least one phase transfer trimerization catalyst can be used in the compositions of the present invention. When actually used, the catalyst system for PIR / PUR foams typically comprises, for example, a solution of a carboxylate in a diluent such as ethylene glycol, diethylene glycol, polyethylene glycol, dimethyl sulfoxide (DMSO), pyrrolidone, propylene glycol, dipropylene glycol, and polypropylene glycol. Preferably, the amount of the diluent may range from about 5% to about 90%, about 10% to about 80%, and optionally about 20% to about 70% by mass of the catalyst. Thus, as an example, when a 50% solution of benzyltrimethylammonium acetate catalyst in ethylene glycol is used in an amount of 10 grams for a particular application, the amount of the benzyltrimethylammonium acetate catalyst is equal to 5 grams. Thus, 5 grams of that catalyst component are used in the calculation of, for example, the mass ratio of that component to the amount of the active hydrogen-containing compound or the amount of the polyol.

[0026] In the present invention, several types of ranges are disclosed. They include, without limitation, ranges of temperature, ranges of atomic numbers, ranges of foam density, ranges of isocyanate index, and ranges in pphp for catalyst compositions including blowing agents, water, surfactants, flame retardants, and at least one phase transfer trimer catalyst. Each possible number that such a range can reasonably encompass, as well as any sub-range encompassed therein, and combinations of sub-ranges are the subject of the present invention. For example, for a chemical moiety having a specific number of carbon atoms, such a range can be encompassed, and any possible number consistent with the disclosure of the present application is the subject of the present invention. For example, the disclosure that " 1 " may be an alkyl group having up to 18 carbon atoms, or in other words a C1 - C 18 -alkyl group, when used within the present application, relates to an alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, and a " 1 " group that can be independently selected from any range between two of those numbers (e.g., a C1 - C8-alkyl group), and any combination of ranges between two of those numbers (e.g., a C3 - C5-alkyl group and a C7 - C 10 -alkyl group) is also included. This applies to all other carbon ranges disclosed within the present application, such as the C1 - C 2 and C1 - C 3 for 18 and ranges such as an alkoxy group having up to 10 carbon atoms.

[0027] Similarly, additional representative examples follow for the parts by mass of a catalyst composition comprising at least one phase transfer trimer catalyst per 100 parts by mass of at least one active hydrogen-containing compound in a composition or foam formulation. When the at least one active hydrogen-containing compound is at least one polyol, the parts by mass per 100 parts by mass of polyol are abbreviated as pphp. Thus, by the disclosure that a catalyst composition comprising at least one phase transfer trimer catalyst is present in an amount of about 0.05 to about 10 pphp, for example, the pphp is preferably selected from about 0.05, about 0.06, about 0.07, about 0.08, about 0.09, about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10. All other ranges disclosed within this application should be interpreted in the same manner as these two examples.

[0028] Individual elements of any such group may be excluded, including any subrange or combination of subranges within said group. Further, any individual substituent, analog, compound, ligand, structure, or group thereof, or any element of the claimed group may be excluded.

[0029] Another aspect of the present invention also provides a thermally stable catalyst system. When used to describe this feature, a compound is defined as being thermally stable at a given temperature if it does not decompose or emit volatile amines and / or related amine odors at that given temperature. A particular feature of the catalyst composition of the present invention is that it is thermally stable up to a temperature of about 120°C. In a further aspect, the catalyst system of the present invention has thermal stability up to about 175°C, about 200°C, about 220°C, about 240°C, or about 250°C.

[0030] In one embodiment of the present invention, preferably, the phase transfer trimer catalyst includes, without limitation, at least one element selected from the group consisting of salts having thermal stability, including tetramethylammonium formate, tetramethylammonium acetate, tetraethylammonium formate, tetraethylammonium acetate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrabutylammonium formate, tetrabutylammonium acetate, benzyltrimethylammonium formate, benzyltrimethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetraethylammonium propionate, tetraethylammonium butyrate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrabutylammonium propionate, tetrabutylammonium butyrate, benzyltrimethylammonium propionate, benzyltrimethylammonium butyrate, benzyltrimethylammonium pivalate, benzyl-(2-hydroxypropyl)-dimethylammonium acetate, benzyl-(2-hydroxypropyl)-dimethylammonium formate, benzyl-(2-hydroxyethyl)-dimethylammonium acetate, benzyl-(2-hydroxyethyl)-dimethylammonium formate, benzyl-(2-hydroxypropyl)-dimethylammonium propionate, benzyl-(2-hydroxypropyl)-dimethylammonium butyrate, benzyl-(2-hydroxypropyl)-dimethylammonium pentanoate, benzyl-(2-hydroxypropyl)-dimethylammonium hexanoate, benzyl-(2-hydroxypropyl)-dimethylammonium heptanoate, benzyl-(2-hydroxypropyl)-dimethylammonium octanoate, benzyl-(2-hydroxypropyl)-dimethylammonium 2-ethylhexanoate and the like. Such salts can be used individually or in any combination thereof.

[0031] The phase transfer trimer catalyst can preferably be used in combination with a tertiary amine. The tertiary amine is preferably a normal tertiary amine, such as triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethyl-imidazole, N-methylmorpholine (commercially available as DABCO® NMM), N-ethylmorpholine (commercially available as DABCO® NEM), triethylamine (commercially available as DABCO® TETN), N,N'-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine (commercially available as Polycat® 41), 2,4,6-tris(dimethylaminomethyl)phenol (commercially available as DABCO TMR® 30), N-methyldicyclohexylamine (commercially available as Polycat® 12), pentamethyldipropylenetriamine (commercially available as Polycat® 77), N-methyl-N'-(2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyldiethylenetriamine (commercially available as Polycat® 5), hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexylamine (commercially available as Polycat® 8), triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl)ether (commercially available as DABCO® BL19), tris(3-dimethylaminopropyl)amine (commercially available as Polycat® 9), 1,8-diazabicyclo[5.4.0]undecene (commercially available as DABCO® DBU), or an acid-blocked derivative thereof, and the like, and any mixture thereof may be used. Particularly useful as a urethane catalyst for the foam applications according to the present invention is Polycat® 5, which is chemically known as pentamethyldiethylenetriamine. The phase transfer trimer catalyst can also be used together with a tertiary amine having at least one isocyanate-reactive group containing a primary hydroxyl group, a secondary hydroxyl group, a primary amine group, a secondary amine group, a urea group, or an amide group.Preferred examples of the tertiary amine catalyst having an isocyanate group include, without limitation, N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, N,N-dimethylaminoethyl-N'-methylethanolamine, N,N,N'-trimethylaminopropylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dimethyl-N',N'-(2-hydroxypropyl)-1,3-propylenediamine, dimethylaminopropylamine, (N,N-dimethylaminoethoxy)ethanol, N-methyl-N'-(2-hydroxyethyl)-piperazine, bis(N,N-dimethyl-3-aminopropyl)amine, N,N-dimethylaminopropylurea, N,N-diethylaminopropylurea, N,N'-bis(3-dimethylaminopropyl)urea, bis(dimethylamino)-2-propanol, 6-dimethylamino-1-hexanol, N-(3-aminopropyl)imidazole), N-(2-hydroxypropyl)imidazole, and N-(2-hydroxyethyl)imidazole, 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, N,N-dimethylaminoethyl-N'-methyl-N'-ethanol, dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-3-aminopropyl-bis(aminoethyl)ether, or combinations thereof.

[0032] The tertiary amine used in combination with the phase transfer trimer catalyst may be acid-blocked with an acid including a carboxylic acid (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic) sulfonic acid, or other organic or inorganic acid. Preferred examples of carboxylic acids include monobasic, dibasic or polybasic acids with or without isocyanate-reactive groups. Preferred examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, neopentanoic 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, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, salicylic acid, and the like.

[0033] In one aspect of the present invention, the catalyst composition includes at least one phase transfer trimer catalyst having thermal stability up to about 150 °C, where no volatile amine compound is released or is substantially not released. The typical foam temperature resulting from the exothermic reaction during the processing of the PIR / PUR foam can be in the range of about 80 °C to about 150 °C. In a further aspect, the catalyst system of the present invention has thermal stability up to about 175 °C, about 200 °C, about 220 °C, about 240 °C, or about 250 °C.

[0034] The above-mentioned phase transfer trimer catalyst can be produced, for example, by the reaction of an organic acid and an alkali hydroxide. In another aspect of the present invention, the phase transfer trimer catalyst can be produced by the reaction of an organic acid and a tetraalkylammonium hydroxide, or by the reaction of an organic acid and a tertiary amine followed by the reaction with an epoxy compound. Alternatively, the phase transfer trimer catalyst can be produced, for example, by reacting a tertiary amine with an alkyl halide or an arylalkyl halide to form a quaternary ammonium halide, and then treating this with an alkali or alkaline earth hydroxide to yield the corresponding phase transfer trimer catalyst. The reaction of an epoxy with the reaction of an organic acid and a tertiary amine can lead to a hydroxyalkyl quaternary compound, for example, a benzyl-(2-hydroxypropyl)dimethyl-ammonium salt.

[0035] Preferred examples of the phase-transfer trimeric catalyst salts include, without limitation, tetramethylammonium formate, tetramethylammonium acetate, tetraethylammonium formate, tetraethylammonium acetate, tetrapropylammonium formate, tetrapropylammonium acetate, tetrabutylammonium formate, tetrabutylammonium acetate, benzyltrimethylammonium formate, benzyltrimethylammonium acetate, tetramethylammonium propionate, tetramethylammonium butyrate, tetraethylammonium propionate, tetraethylammonium butyrate, tetrapropylammonium propionate, tetrapropylammonium butyrate, tetrabutylammonium propionate, tetrabutylammonium butyrate, benzyltrimethylammonium propionate, benzyltrimethylammonium butyrate, benzyltrimethylammonium pivalate, benzyl-(2-hydroxypropyl)-dimethylammonium acetate, benzyl-(2-hydroxypropyl)-dimethylammonium formate, benzyl-(2-hydroxyethyl)-dimethylammonium acetate, benzyl-(2-hydroxyethyl)-dimethylammonium formate, benzyl-(2-hydroxypropyl)-dimethylammonium propionate, benzyl-(2-hydroxypropyl)-dimethylammonium butyrate, benzyl-(2-hydroxypropyl)-dimethylammonium pentanoate, benzyl-(2-hydroxypropyl)-dimethylammonium hexanoate, benzyl-(2-hydroxypropyl)-dimethylammonium heptanoate, benzyl-(2-hydroxypropyl)-dimethylammonium octanoate, benzyl-(2-hydroxypropyl)-dimethylammonium 2-ethylhexanoate and the like, or any combination thereof.

[0036] The amounts of other catalyst materials and salts may range from about 0.01 pphp to about 20 pphp, from about 0.1 pphp to about 15 pphp, and optionally from about 0.5 pphp to about 10 pphp.

[0037] Also included within the scope of the catalyst compositions of the present invention are mixtures or combinations of more than one phase transfer trimer catalyst. Further, the catalyst systems or novel catalyst compositions of the present invention can further include at least one urethane catalyst that does not have an isocyanate-reactive group.

[0038] The term "contact product" is used within this application to describe compositions in which the components are contacted together in any order, in any manner, and for any length of time. For example, the components can be contacted by blending or mixing. Further, the contacting of any component can be carried out in the presence or absence of any other component of the compositions or foam formulations described within this application. Combining additional catalyst components can be carried out by any method known to those skilled in the art. For example, in one embodiment of the present invention, a catalyst composition can be produced by combining or contacting at least one phase transfer trimer catalyst with an alkali metal carboxylate. This typically occurs in solution form. In other embodiments, the catalyst composition can be produced by first mixing the respective carboxylic acids, subsequently neutralizing to form the corresponding salts, and subsequently combining or contacting with a tertiary amine having at least one isocyanate.

[0039] The compositions and methods are described in terms of "comprising" various components or steps, while the compositions and methods can also "consist essentially of" or "consist of" those various components or steps.

[0040] Phase transfer trimer catalyst The catalyst composition of the present invention comprises at least one phase transfer trimer catalyst. Said at least one phase transfer trimer catalyst is particularly useful for manufacturing PIR / PUR foams. Accordingly, the present invention relates to a method for manufacturing PIR / PUR rigid foams, comprising contacting at least one polyisocyanate, a polyol premix comprising a polyol or a polyol mixture, a catalyst composition comprising at least one phase transfer trimer catalyst, and a blowing agent, provided that said at least one blowing agent is not a chlorofluorocarbon.

[0041] In one embodiment, preferably when said at least one phase transfer trimer catalyst, the blowing agent comprises formic acid, the general formula A-CO2 - · + NR 1 R 2 R 3 R 4 [wherein, A = H, and R 1 , R 2 , R 3 and R 4 are independently of each other methyl, ethyl, propyl, butyl or -CH2-Ar, and Ar is an aryl group, and preferably -C6H5, or A = H, R 1 = -CH2-CH2OH or -CH2-CH(OH)-CH3, R 2 = -CH2-Ar, and R 3 and R 4 are independently of each other methyl, ethyl, propyl or butyl, and Ar is an aryl group, and preferably -C6H5] having.

[0042] In other embodiments, preferably when said at least one phase transfer trimer catalyst, the blowing agent comprises a C5-hydrocarbon blowing agent, the general formula A-CO2 - · + NR 1 R 2 R 3 R 4 [wherein, A = H or methyl, and preferably methyl, R 1 = -CH2-CH2OH or -CH2-CH(OH)-CH3, R 2 = -CH2-Ar, and Ar is an aryl group, and preferably -C6H5, and R 3 and R 4 are independently of each other methyl, ethyl, propyl or butyl, or A = H or methyl, R 1 and R 2 and R 3 are independently of each other methyl, ethyl, propyl or butyl, and R 4 = -CH2-Ar, and Ar is an aryl group, and preferably -C6H5, or A = H or methyl, and preferably methyl, and R 1 , R 2 , R 3 and R 4 are independently of each other C1-C4-alkyl groups] has.

[0043] In other embodiments, preferably when the blowing agent contains a C5-hydrocarbon blowing agent, the at least one phase transfer trimer catalyst has the general formula A-CO2 - · + NR 1 R 2 R 3 R 4 [wherein, A = ethyl, and R 1 , R 2 , R 3 and R 4 are independently of each other methyl, ethyl, propyl, butyl or -CH2-Ar, and Ar is an aryl group, and preferably -C6H5] has.

[0044] In another embodiment, preferably, when the blowing agent contains a C5-hydrocarbon blowing agent, the at least one phase transfer trimer catalyst has the general formula A-CO2 - · + NR 1 R 2 R 3 R 4 [wherein, A = propyl and R 1 、R 2 、R 3 and R 4 are independently of one another methyl, ethyl, propyl, butyl or -CH2-Ar, and Ar is an aryl group and preferably -C6H5] has.

[0045] Unless otherwise specified, the alkyl and alkenyl groups described in the present application are intended to include all structural isomers of a given structure, whether straight-chain or branched-chain, for example all enantiomers and all diastereomers are included within this definition. As an example, unless otherwise specified, the term propyl means including n-propyl and iso-propyl, while the term butyl means including n-butyl, iso-butyl, t-butyl, sec-butyl, etc. Similarly, the substituted alkyl, alkenyl, aryl and aralkyl groups described in the present application are intended to include substituted analogs of a given structure. For example, the substituents on the alkyl, alkenyl, aryl and aralkyl groups can include, without limitation, halides, hydroxyl groups, amino groups, alkoxy, alkylamino or dialkylamino groups having up to 10 carbon atoms, or combinations thereof.

[0046] Non-limiting examples of alkyl groups that can be present in said at least one phase transfer trimer catalyst preferably include, without limitation, methyl, ethyl, propyl, butyl, pentyl, hexyl, and the like. Examples of alkenyl groups within the scope of the present invention preferably include, without limitation, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and the like. Aryl and aralkyl (aralkyl is defined as aryl-substituted alkyl or arylalkyl) groups preferably include phenyl, alkyl-substituted phenyl, naphthyl, alkyl-substituted naphthyl, and the like. For example, non-limiting examples of aryl and aralkyl groups useful in the present invention preferably include, without limitation, phenyl, tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl, phenylpropyl, phenylbutyl, propyl-2-phenylethyl, and the like.

[0047] In one embodiment of the present invention, R 1 、R 2 、R 3 and R 4 are independently selected from methyl, ethyl, propyl, butyl and benzyl. In another embodiment, R 1 、R 2 、R 3 and R 4 are independently selected from methyl, ethyl, propyl and butyl.

[0048] In other embodiments, the quaternary ammonium ions useful in the present invention are preferably, without limitation, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, dimethyldiallylammonium, benzyltrimethylammonium, di(benzyl)dimethylammonium, triethyl(2-hydroxypropyl)ammonium, tripropyl(2-hydroxypropyl)ammonium, tributyl(2-hydroxypropyl)ammonium, triethyl(2-hydroxyethyl)ammonium, tripropyl(2-hydroxyethyl)ammonium, tributyl(2-hydroxyethyl)ammonium, dimethylbenzyl(2-hydroxypropyl)ammonium, dimethylbenzyl(2-hydroxyethyl)ammonium, and the like, or any combination thereof.

[0049] In another embodiment of the present invention, at least one phase transfer trimer catalyst used in combination with at least one tertiary amine having at least one isocyanate-reactive group is an alkali metal carboxylate or a quaternary ammonium carboxylate or a combination thereof.

[0050] The selection of a suitable phase transfer trimer catalyst of the present invention must be carried out according to the type of blowing agent used. Preferred examples of the phase transfer trimer catalyst include tetramethylammonium formate, tetraethylammonium formate, tetrapropylammonium formate, tetrabutylammonium formate, benzyltrimethylammonium formate, benzyldimethyl-(2-hydroxypropyl)ammonium formate, and benzyldimethyl-(2-hydroxyethyl)ammonium formate when the blowing agent is formic acid. Preferred examples of the phase transfer trimer catalyst include tetramethylammonium acetate, tetraethylammonium acetate, tetrapropylammonium acetate, tetrabutylammonium acetate, tetrabutylammonium formate, benzyltrimethylammonium formate, benzyltrimethylammonium acetate, benzyldimethyl-(2-hydroxypropyl)ammonium acetate, and benzyldimethyl-(2-hydroxyethyl)ammonium acetate when the blowing agent is a C5-hydrocarbon.

[0051] In another aspect of the present invention, at least one phase transfer trimer catalyst used in combination with at least one tertiary amine having at least one isocyanate-reactive group is a tetraalkylammonium carboxylate. In another aspect, at least one phase transfer trimer catalyst used in combination with at least one tertiary amine having at least one isocyanate-reactive group is benzyldimethyl-(2-hydroxypropyl)ammonium formate when the blowing agent is formic acid. In another aspect, at least one phase transfer trimer catalyst used in combination with at least one tertiary amine having at least one isocyanate-reactive group is benzyldimethyl-(2-hydroxypropyl)ammonium acetate when the blowing agent is a C5-hydrocarbon.

[0052] In a further aspect, at least one phase transfer trimer catalyst used in combination with at least one tertiary amine having at least one isocyanate-reactive group is a salt of a carboxylic acid, such as a quaternary ammonium salt of a carboxylic acid. Carboxylic acids suitable within the scope of the present invention preferably include, without limitation, formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, pivalic acid or pivalic acid, triethylacetic acid, hexanoic acid, neohexanoic acid, heptanoic acid, neoheptanoic acid, octanoic acid, neooctanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, and the like, mixtures thereof, or any combination thereof, but preferably formic acid and acetic acid.

[0053] In a further aspect, the phase transfer trimer catalyst is used in combination with at least one tertiary amine having at least one isocyanate-reactive group including a primary hydroxyl group, a secondary hydroxyl group, a primary amine group, a secondary amine group, a urea group, or an amide group. Preferred examples of the tertiary amine catalyst having an isocyanate group include, without limitation, N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, N,N-dimethylaminoethyl-N'-methylethanolamine, N,N,N'-trimethylaminopropylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dimethyl-N',N'-(2-hydroxypropyl)-1,3-propylenediamine, dimethylaminopropylamine, (N,N-dimethylaminoethoxy)ethanol, N-methyl-N'-hydroxyethyl-piperazine, bis(N,N-dimethyl-3-aminopropyl)amine, N,N-dimethylaminopropylurea, diethylaminopropylurea, N,N'-bis(3-dimethylaminopropyl)urea, N,N'-bis(3-diethylaminopropyl)urea, bis(dimethylamino)-2-propanol, 6-dimethylamino-1-hexanol, N-(3-aminopropyl)imidazole), N-(2-hydroxypropyl)imidazole, and N-(2-hydroxyethyl)imidazole, 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, N,N-dimethylaminoethyl-N'-methyl-N'-ethanol, dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-3-aminopropyl-bis(aminoethyl)ether, or combinations thereof.

[0054] Polyisocyanate Polyisocyanates useful in the method of forming PIR / PUR foams preferably include, without limitation, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, toluene diisocyanate (TDI), diphenylmethane diisocyanate isomers (MDI), hydrogenated MDI, and 1,5-naphthalene diisocyanate. For example, 2,4-TDI, 2,6-TDI, and mixtures thereof can be immediately used in the present invention. Preferred examples of polyisocyanates include toluene diisocyanate and diphenylmethane diisocyanate, and isomers thereof. Other suitable mixtures of diisocyanates include, without limitation, those known in the art as crude MDI or PAPI, which contain 4,4'-diphenylmethane diisocyanate together with other isomers and similar higher polyisocyanates. In another aspect of the present invention, prepolymers of polyisocyanates comprising a partially pre-reacted mixture of polyisocyanates and polyether or polyester polyols are suitable. In still another aspect, the polyisocyanate comprises MDI or consists essentially of MDI or a mixture of MDI.

[0055] The catalyst system, composition, and method for producing PIR / PUR foams of the present invention can be used to produce many types of foams. This catalyst system is useful, for example, in the formation of foam products for rigid and flame-retardant applications that typically require a high isocyanate index. As defined above, the isocyanate index is obtained by dividing the actual amount of polyisocyanate used by the stoichiometrically required amount of polyisocyanate theoretically necessary to react with all of the active hydrogens in the reaction mixture and multiplying by 100. For the purposes of the present invention, the isocyanate index is represented by the formula: Isocyanate Index = (Equivalent of NCO / Equivalent of Active Hydrogen) × 100, where the equivalent of NCO is the number of NCO functional groups in the polyisocyanate and the equivalent of active hydrogen is the number of equivalent active hydrogen atoms.

[0056] Foam products produced with an isocyanate index of from about 80 to about 800 are within the scope of the present invention. According to another aspect of the present invention, the isocyanate index ranges from about 100 to about 700, from about 150 to about 800, from about 200 to about 600, or from about 250 to about 500.

[0057] Polyol The active hydrogen-containing compound for use with the aforementioned polyisocyanate in the formation of the polyisocyanurate / polyurethane foam of the present invention may be any organic compound having at least two hydroxyl groups, such as a polyol. The polyols typically used in the method for forming PIR / PUR foams preferably include polyalkylene ethers and polyester polyols. The polyalkylene ether polyols are poly(alkylene oxide) polymers, such as poly(ethylene oxide) and poly(propylene oxide) polymers and copolymers, and include those having terminal hydroxyl groups derived from polyhydric compounds including diols and triols. They preferably include, without limitation, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylolpropane, cyclohexanediol, and saccharides such as sucrose, and those such as low molecular weight polyols.

[0058] Amine polyether polyols can be used in the present invention. They can be produced by reacting amines such as ethylenediamine, diethylenetriamine, tolylenediamine, diphenylmethanediamine or triethanolamine with ethylene oxide or propylene oxide.

[0059] In another aspect of the present invention, a single high molecular weight polyether polyol, or a mixture of high molecular weight polyether polyols, such as a mixture of materials of different polyfunctionalities and / or different molecular weights or different chemical compositions, can be used.

[0060] In still other embodiments of the present invention, a polyester polyol can be used that includes what is produced when a dicarboxylic acid reacts with an excess of diol. Non-limiting examples include adipic acid or phthalic acid or phthalic anhydride that react with ethylene glycol or butanediol. Polyols useful in the present invention can be produced by reacting a lactone with an excess of diol, for example, by reacting caprolactone with propylene glycol. In a further embodiment, active hydrogen-containing compounds, such as polyester polyols and polyether polyols, and combinations thereof are useful in the present invention.

[0061] The polyol can have a hydroxyl value of about 5 to about 600, about 100 to about 600, and optionally about 50 to about 100, and a functionality of about 2 to about 8, about 3 to about 6, and optionally about 4 to about 6.

[0062] The amount of polyol can range from about 0 pphp to about 100 pphp, about 10 pphp to about 90 pphp, and optionally about 20 pphp to about 80 pphp.

[0063] Blowing agent According to the compositions, foam formulations, and methods of manufacturing PIR / PUR foams within the scope of the present invention, suitable blowing agents that can be used alone or in combination preferably include, without limitation, hydrocarbons, formic acid, water, hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), hydrofluorochloroolefins (HFCOs), hydrochlorofluorocarbons (HCFCs), and formates. Preferred examples of HFCs include, without limitation, HFC-245fa, HFC-134a, and HFC-365. Preferred examples of HCFCs include, without limitation, HCFC-141b, HCFC-22, and HCFC-123. Preferred examples of hydrocarbons include, without limitation, n-pentane, iso-pentane, cyclopentane, and the like, or any combination thereof. In one aspect of the present invention, the blowing agent or mixture of blowing agents includes at least one hydrocarbon. In other aspects, the blowing agent includes n-pentane. Further, in other aspects of the present invention, the blowing agent consists essentially of n-pentane, or a mixture of n-pentane and one or more blowing agents. In other aspects, the blowing agent includes cyclopentane. Further, in other aspects of the present invention, the blowing agent consists essentially of cyclopentane, or a mixture of cyclopentane and one or more blowing agents. In other aspects, the blowing agent includes a mixture of n-pentane and cyclopentane. Further, in other aspects of the present invention, the blowing agent consists essentially of a mixture of n-pentane and cyclopentane and one or more blowing agents. In other aspects, the blowing agent includes a mixture of any isomers of pentane. Further, in other aspects of the present invention, the blowing agent consists essentially of a mixture of any isomers of pentane and one or more blowing agents.

[0064] Preferred examples of hydrohaloolefin blowing agents are HFO-1234ze (trans-1,3,3,3-tetrafluoroprop-1-ene), HFO-1234yf (2,3,3,3-tetrafluoropropene), and HFCO-1233zd (1-propene,1-chloro-3,3,3-trifluoro), especially HFO.

[0065] Due to the discovery that chlorofluorocarbons (CFCs) destroy ozone in the stratosphere, this type of blowing agent is not desirable for use in the present invention. Furthermore, CFC blowing agents also exhibit performance drawbacks as shown in the experimental examples. Chlorofluorocarbons (CFCs) are alkanes in which all hydrogen atoms are replaced by chlorine and fluorine atoms. Examples of CFCs include trichlorofluoromethane and dichlorodifluoromethane. Therefore, the compositions according to the present invention contain only blowing agents that are not CFCs.

[0066] The amount of blowing agent used can vary, for example, based on the intended use and application of the foam product, and the desired rigidity and density of the foam. In the compositions, foam formulations, and methods for producing the polyisocyanurate / polyurethane foams of the present invention, the blowing agent is present in an amount of about 0.5 to about 80 parts by weight per 100 parts by weight of at least one active hydrogen-containing compound. In other embodiments, the blowing agent is present in an amount of about 1 to about 60, about 4 to about 50, or about 8 to about 40 parts by weight per 100 parts by weight of at least one active hydrogen-containing compound. When the at least one active hydrogen-containing compound is at least one polyol, the blowing agent is present in an amount of about 0.5 to about 80 parts per 100 parts by weight of polyol (pphp), about 4 to about 60 pphp, about 8 to about 50 pphp, or about 10 to about 40 pphp.

[0067] When water is present in the formulation as a blowing agent or for other uses, water is present in an amount of up to about 15 parts by weight per 100 parts by weight of at least one active hydrogen-containing compound. Also, when the at least one active hydrogen-containing compound is at least one polyol, water can be in the range of 0 to about 15 pphp. In other embodiments, water can be in the range of 0 to about 10 pphp, 0 to about 8 pphp, 0 to about 6 pphp, or 0 to about 4 pphp.

[0068] Urethane catalyst Using a conventional urethane catalyst that does not have an isocyanate-reactive group, the reaction for forming polyurethane can be promoted, and it can be used as a further component of the catalyst system and composition of the present invention to produce a polyisocyanurate / polyurethane foam. Suitable urethane catalysts for use in the present application are preferably, without limitation, metal salt catalysts such as organotin, and amine compounds such as triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethyl-imidazole, N-methylmorpholine (commercially available as DABCO® NMM catalyst), N-ethylmorpholine (commercially available as DABCO® NEM catalyst), triethylamine (commercially available as DABCO® TETN catalyst), N,N'-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine (commercially available as Polycat® 41 catalyst), 2,4,6-tris(dimethylaminomethyl)phenol (commercially available as DABCO TMR® 30 catalyst), N-methyldicyclohexylamine (commercially available as Polycat® 12 catalyst), pentamethyldipropylenetriamine (commercially available as Polycat® 77 catalyst), N-methyl-N'-(2-dimethylaminoethyl)-piperazine, tributylamine, pentamethyldiethylenetriamine (commercially available as Polycat® 5 catalyst), hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexyl-amine (commercially available as Polycat® 8 catalyst), pentamethyldipropylenetriamine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl)ether (commercially available as DABCO® BL19 catalyst), bis(morpholinoethyl)ether (also known as di-morpholino-diethyl ether or DMDEE), tris(3-dimethylaminopropyl)amine (commercially available as Polycat® 9 catalyst), 1,8-diazabicyclo[5.4.0]undecene (commercially available as DABCO® DBU catalyst), or its acid-blocked derivatives and those of its kind, and any mixtures thereof.Particularly useful as a urethane catalyst for form applications according to the present invention is the Polycat® 5 catalyst, which is chemically known as pentamethyldiethylenetriamine.

[0069] Other urethane catalysts can also be used in combination with at least one tertiary amine having at least one isocyanate-reactive group containing a primary hydroxyl group, a secondary hydroxyl group, a primary amine group, a secondary amine group, a urea group, or an amide group. Preferred examples of the tertiary amine catalysts having an isocyanate group include, but are not limited to, N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, N,N-dimethylaminoethyl-N'-methylethanolamine, N,N,N'-trimethylaminopropylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dimethyl-N',N'-(2-hydroxypropyl)-1,3-propylenediamine, dimethylaminopropylamine, (N,N-dimethylaminoethoxy)ethanol, N-methyl-N'-hydroxyethyl-piperazine, bis(N,N-dimethyl-3-aminopropyl)amine, N,N-dimethylaminopropylurea, diethylaminopropylurea, N,N'-bis(3-dimethylaminopropyl)urea, N,N'-bis(3-diethylaminopropyl)urea, bis(dimethylamino)-2-propanol, 6-dimethylamino-1-hexanol, N-(3-aminopropyl)imidazole), N-(2-hydroxypropyl)imidazole, and N-(2-hydroxyethyl)imidazole, 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, N,N-dimethylaminoethyl-N'-methyl-N'-ethanol, dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-3-aminopropyl-bis(aminoethyl)ether, or combinations thereof.

[0070] To produce the polyisocyanurate / polyurethane foam of the present invention, the urethane catalyst is present in the formulation at 0 to about 10 pphp, 0 to about 8 pphp, 0 to about 6 pphp, 0 to about 4 pphp, 0 to about 2 pphp, or 0 to about 1 pphp. In other embodiments, the urethane catalyst is present at 0 to about 0.8 pphp, 0 to about 0.6 pphp, 0 to about 0.4 pphp, or 0 to about 0.2 pphp.

[0071] Other additives Depending on the requirements during the production of the foam or for the final end use of the foam product, various additives can be used within the PIR / PUR foam formulation to adjust specific properties. They preferably include, without limitation, a foam stabilizer, a flame retardant, a chain extender, an epoxy resin, an acrylic resin, a filler, a pigment, or any combination thereof. Other mixtures or materials known in the art may be included in the foam formulation and are to be understood to be within the scope of the present invention.

[0072] The foam stabilizer includes surfactants, such as organopolysiloxanes. The silicone surfactant may be present in the foam formulation in an amount of about 0.5 to about 10 pphp, about 0.6 to about 9 pphp, about 0.7 to about 8 pphp, about 0.8 to about 7 pphp, about 0.9 to about 6 pphp, about 1 to about 5 pphp, or about 1.1 to about 4 pphp. Useful flame retardants include halogenated organic phosphorus compounds and non-halogenated compounds. Non-limiting examples of halogenated flame retardants are trichloropropyl phosphate (TCPP). For example, triethyl phosphate ester (TEP) and dimethyl-methyl-phosphonate (DMMP) are non-halogenated flame retardants. Depending on the end use of the final foam, the flame retardant may be present in the foam formulation in an amount of 0 to about 50 pphp, 0 to about 40 pphp, 0 to about 30 pphp, or 0 to about 20 pphp. In other embodiments, there is a flame retardant in an amount of 0 to about 15 pphp, 0 to about 10 pphp, 0 to about 7 pphp, or 0 to about 5 pphp. Chain extenders, such as ethylene glycol and butanediol, can also be used in the present invention. For example, ethylene glycol can also be present in the formulation as a diluent or solvent for the carboxylate catalyst of the present invention.

[0073] Polyisocyanurate / Polyurethane Foam Formulations and Methods One aspect of the present invention provides a composition comprising a contact product of a contact product with a catalyst composition comprising at least one active hydrogen-containing compound, at least one blowing agent, and at least one phase transfer trimer catalyst used in combination with at least one tertiary amine having at least one isocyanate-reactive group. Another aspect provides a composition comprising a contact product of a contact product with a catalyst composition comprising at least one polyisocyanate, at least one blowing agent, and at least one phase transfer trimer catalyst used in combination with at least one tertiary amine having at least one isocyanate-reactive group. In both of these two compositions, the composition may further comprise at least one urethane catalyst having no isocyanate-reactive groups. Further, the composition may further comprise at least one additive selected from at least one foam stabilizer, at least one flame retardant, at least one chain extender, at least one crosslinking agent, at least one emulsifier, at least one blowing agent compatibilizer, at least one cell opening agent, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.

[0074] The present invention provides a method for producing a polyisocyanurate / polyurethane (PIR / PUR) foam, which includes contacting at least one polyisocyanate and at least one active hydrogen-containing compound in the presence of an effective amount of a catalyst composition comprising at least one blowing agent and at least one phase transfer trimer catalyst. According to the method of the present invention, a PIR / PUR foam having a density of about 8 Kg / m 3 to about 250 Kg / m 3 (about 1.25 lb / ft 3 to about 15.5 lb / ft 3 ) or about 24 Kg / m 3 to about 60 Kg / m 3 (about 1.5 lb / ft 3 to about 3.75 lb / ft 3 ) can be produced.

[0075] The present invention can be used in a wide variety of methods for manufacturing rigid foams of closed or open cells. Examples of suitable methods are molding, spraying, and include in particular methods for manufacturing rigid foams. In one aspect, the method of the present invention relates to a method for manufacturing laminated foams.

[0076] In other aspects, the method of the present invention results in a substantially constant increase in foam height over time even at high isocyanate indices, which is highly desirable in continuous foam manufacturing operations. The method for manufacturing the PIR / PUR foam can also provide surface curing that is equal to or faster than other commercially available catalyst systems, so that the PIR / PUR foam has enhanced surface adhesion and is useful for manufacturing articles such as laminated foam panels.

[0077] Optionally, in still further aspects, the method of the present invention can produce PIR / PUR foams that do not have, or have substantially no, an undesirable amine odor. Depending on the selection of specific at least one phase transfer trimer catalyst, this method can provide thermal stability at the temperatures typically encountered during the manufacture of PIR / PUR foams, even when those foams are formulated with high isocyanate indices. In a further aspect, the method for manufacturing the PIR / PUR foam has thermal stability up to about 150 °C, or about 175 °C, or about 200 °C, or about 220 °C, or about 240 °C, or about 250 °C. In yet a further aspect, the method of the present invention produces PIR / PUR foams that are substantially free of volatile amines and / or amine odor.

[0078] A catalyst composition comprising at least one phase transfer trimer catalyst should be present in the foam formulation in a catalytically effective amount. In the PIR / PUR foam formulation of the present invention, the catalyst composition is present in an amount of about 0.05 to about 10 parts by mass per 100 parts by mass of at least one active hydrogen-containing compound, excluding the contribution of the mass of the catalyst system diluent. In other embodiments, the catalyst composition is present in an amount of about 0.4 to about 9 parts by mass, or about 0.8 to about 8 parts by mass, per 100 parts by mass of at least one active hydrogen-containing compound. When the at least one active hydrogen-containing compound is at least one polyol, the catalyst composition is present in an amount of about 0.05 to about 10 parts per 100 parts by mass (pphp) of the polyol. In other embodiments, the catalyst composition is present in an amount of about 0.2 to about 9.5 pphp, about 0.4 to about 9 pphp, about 0.6 to about 8.5 pphp, or about 0.8 to about 8 pphp.

[0079] According to one aspect of the method of the present invention, the components of the foam formulation are contacted substantially simultaneously. For example, at least one polyisocyanate, at least one active hydrogen-containing compound, at least one blowing agent, and an effective amount of a catalyst composition comprising at least one phase transfer trimer catalyst are contacted together. Considering the number of components included in the PIR / PUR formulation, there are many different combinations of components in different orders, and those skilled in the art will understand that changing the order of addition of the components is within the scope of the present invention. It should be noted that for each of the different combination orders of the above-mentioned components of the foam formulation, the foam formulation of the present invention may further comprise at least one urethane catalyst. Further, the method for producing the PIR / PUR foam may further include the presence of at least one additive selected from at least one foam stabilizer, at least one emulsifier, at least one flame retardant, at least one chain extender, at least one crosslinking agent, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof. In one aspect of the present invention, all of the above components including optional components are contacted substantially simultaneously.

[0080] In another aspect of the present invention, a premix of components other than at least one polyisocyanate is first contacted, and subsequently at least one polyisocyanate is added. For example, at least one active hydrogen-containing compound, at least one blowing agent, and the catalyst composition of the present invention are first contacted to form a premix. Then, the premix is contacted with at least one polyisocyanate to produce a PIR / PUR foam according to the method of the present invention. In a further aspect of the present invention, the same method can be used when the premix contains at least one urethane catalyst. Further, the premix may further contain at least one additive selected from at least one foam stabilizer, at least one crosslinking agent, at least one flame retardant, at least one chain extender, at least one emulsifier, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.

[0081] One aspect of the present invention is a method for producing a polyisocyanurate / polyurethane foam, comprising: (a) the following: i) at least one polyol, ii) about 1 to about 80 parts by weight per 100 parts by weight (pphp) of the polyol of a blowing agent, iii) about 0.5 to about 10 pphp of a silicone surfactant, iv) 0 to about 10 pphp of water, v) 0 to about 50 pphp of a flame retardant, vi) 0 to about 10 pphp of a urethane catalyst, and vii) a catalyst composition containing about 0.05 to about 10 pphp of at least one phase transfer trimer catalyst to form a premix containing, and (b) contacting the premix with at least one polyisocyanate at an isocyanate index of about 80 to about 800 to provide the method as described above. As indicated above, the blowing agent is not a chlorofluorocarbon (CFC).

[0082] The following is a list of preferred items of the present invention: Item 1. A composition comprising a contact product of (a) at least one active hydrogen-containing compound, (b) a catalyst composition comprising at least one phase transfer trimer catalyst, and (c) at least one blowing agent, provided that the at least one blowing agent is not a chlorofluorocarbon, said composition.

[0083] Item 2. The at least one phase transfer trimer catalyst has the general formula A-CO2 - · + NR 1 R 2 R 3 R 4 [wherein, A is H, and R 1 , R 2 , R 3 and R 4 are independently of each other methyl, ethyl, propyl, butyl or -CH2-Ar, and Ar is an aryl group, or A is H, R 1 is -CH2-CH2OH or -CH2-CH(OH)-CH3, R 2 is -CH2-Ar, and R 3 and R 4 are independently of each other methyl, ethyl, propyl or butyl, and Ar is an aryl group] and the blowing agent contains formic acid, the composition of Item 1.

[0084] Item 3. The at least one phase transfer trimer catalyst has the general formula A-CO2 - · + NR 1 R 2 R 3 R 4 [wherein, A is H or methyl, R 1 is -CH2-CH2OH or -CH2-CH(OH)-CH3, R 2 is -CH2-Ar, and Ar is an aryl group, and R3 and R 4 are independently methyl, ethyl, propyl or butyl, or A is H or methyl, and R 1 and R 2 and R 3 are independently methyl, ethyl, propyl or butyl, and R 4 is -CH2-Ar, and Ar is an aryl group, or A is H or methyl, and R 1 and R 2 and R 3 and R 4 are independently C1-C4-alkyl groups] having the blowing agent containing a C5-hydrocarbon blowing agent, the composition of item 1.

[0085] Item 4. The at least one phase transfer trimer catalyst has the general formula A-CO2 - · + NR 1 R 2 R 3 R 4 [wherein, A is ethyl, and R 1 , R 2 , R 3 and R 4 are independently methyl, ethyl, propyl, butyl or -CH2-Ar, and Ar is an aryl group] having the blowing agent containing a C5-hydrocarbon blowing agent, the composition of item 1.

[0086] Item 5. The at least one phase transfer trimer catalyst has the general formula A-CO2 - · + NR 1 R 2 R 3 R 4 [wherein, A is propyl, and R 1 , R 2 , R 3 and R 4are independently of each other methyl, ethyl, propyl, butyl or -CH2-Ar, and Ar is an aryl group The composition according to item 1, which has and wherein the blowing agent comprises a C5-hydrocarbon blowing agent.

[0087] Item 6. The composition according to any one of items 2 to 5, wherein Ar is -C6H5.

[0088] Item 7. The composition according to item 2, wherein the at least one phase transfer trimer catalyst comprises at least one component selected from the group consisting of tetramethylammonium formate, tetraethylammonium formate, tetrapropylammonium formate, tetrabutylammonium formate, benzyltrimethylammonium formate, benzyltrimethylammonium formate, benzyl-(2-hydroxypropyl)-dimethylammonium formate and benzyl-(2-hydroxyethyl)-dimethylammonium formate.

[0089] Item 8. The composition according to item 3, wherein the at least one phase transfer trimer catalyst comprises at least one component selected from the group consisting of tetramethylammonium acetate, tetraethylammonium acetate, tetrapropylammonium acetate, tetrabutylammonium acetate, tetrabutylammonium formate, benzyltrimethylammonium formate, benzyltrimethylammonium acetate, benzyl-(2-hydroxypropyl)-dimethylammonium acetate and benzyl-(2-hydroxyethyl)-dimethylammonium acetate.

[0090] Item 9. The composition according to item 4, wherein the at least one phase transfer trimer catalyst comprises at least one component selected from the group consisting of tetramethylammonium propionate, tetraethylammonium propionate, tetrapropylammonium propionate, tetrabutylammonium propionate and benzyltrimethylammonium propionate.

[0091] Item 10. The composition of Item 5, wherein the at least one phase transfer trimer catalyst comprises at least one component selected from the group consisting of tetramethylammonium butyrate, tetraethylammonium butyrate, tetrapropylammonium butyrate, tetrabutylammonium butyrate, and benzyltrimethylammonium butyrate.

[0092] Item 11. The composition of any one of Items 1 to 10, further comprising a tertiary amine having or not having an isocyanate-reactive group.

[0093] Item 12. The composition of any one of Items 1 to 11, further comprising at least one additive selected from at least one foam stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.

[0094] Item 13. A method for producing a polyisocyanurate / polyurethane foam, comprising contacting at least one polyisocyanate with at least one active hydrogen-containing compound in the presence of a catalyst composition comprising at least one blowing agent and at least one phase transfer trimer catalyst, wherein the at least one blowing agent is not a chlorofluorocarbon.

[0095] Item 14. The at least one phase transfer trimer catalyst has the general formula A-CO2 - · + NR 1 R 2 R 3 R 4 [wherein, A is H, and R 1 , R 2 , R 3 and R 4 are independently of each other methyl, ethyl, propyl, butyl or -CH2-Ar, and Ar is an aryl group, or A is H, and R 1 is -CH2-CH2OH or -CH2-CH(OH)-CH3, and R 2 is -CH2-Ar, and R 3 and R 4 are independently of each other methyl, ethyl, propyl or butyl, and Ar is an aryl group] having, and the blowing agent contains formic acid, the method of item 13.

[0096] Item 15. The at least one phase transfer trimer catalyst has the general formula A-CO2 - · + NR 1 R 2 R 3 R 4 [wherein, A is H or methyl, and R 1 is -CH2-CH2OH or -CH2-CH(OH)-CH3, and R 2 is -CH2-Ar, and Ar is an aryl group, and R 3 and R 4 are independently of each other methyl, ethyl, propyl or butyl, or A is H or methyl, and R 1 and R 2 and R 3 are independently of each other methyl, ethyl, propyl or butyl, and R 4 is -CH2-Ar, and Ar is an aryl group, or A is H or methyl, and R 1 and R 2 and R 3 and R 4 are independently of each other C1-C4-alkyl groups] having, and the blowing agent contains a C5-hydrocarbon blowing agent, the method of item 13.

[0097] Item 16. The at least one phase transfer trimer catalyst has the general formula A-CO2 - · + NR 1 R 2 R3 R 4 [wherein, A is ethyl and R 1 , R 2 , R 3 and R 4 are each independently methyl, ethyl, propyl, butyl or -CH2-Ar, and Ar is an aryl group] having and the blowing agent contains a C5-hydrocarbon blowing agent, the method of item 13.

[0098] Item 17. The at least one phase transfer trimer catalyst has the general formula A-CO2 - · + NR 1 R 2 R 3 R 4 [wherein, A is propyl and R 1 , R 2 , R 3 and R 4 are each independently methyl, ethyl, propyl, butyl or -CH2-Ar, and Ar is an aryl group] having and the blowing agent contains a C5-hydrocarbon blowing agent, the method of item 13.

[0099] Item 18. The method according to any one of items 13 to 17, wherein Ar is -C6H5.

[0100] Item 19. The method of item 14, wherein the at least one phase transfer trimer catalyst contains at least one component selected from the group consisting of tetramethylammonium formate, tetraethylammonium formate, tetrapropylammonium formate, tetrabutylammonium formate, benzyltrimethylammonium formate, benzyltrimethylammonium formate, benzyl-(2-hydroxypropyl)-dimethylammonium formate and benzyl-(2-hydroxyethyl)-dimethylammonium formate.

[0101] Item 20. The method of Item 15, wherein the at least one phase transfer trimer catalyst comprises at least one component selected from the group consisting of tetramethylammonium acetate, tetraethylammonium acetate, tetrapropylammonium acetate, tetrabutylammonium acetate, tetrabutylammonium formate, benzyltrimethylammonium formate, benzyltrimethylammonium acetate, benzyl-(2-hydroxypropyl)-dimethylammonium acetate, and benzyl-(2-hydroxyethyl)-dimethylammonium acetate.

[0102] Item 21. The method of Item 16, wherein the at least one phase transfer trimer catalyst comprises at least one component selected from the group consisting of tetramethylammonium propionate, tetraethylammonium propionate, tetrapropylammonium propionate, tetrabutylammonium propionate, and benzyltrimethylammonium propionate.

[0103] Item 22. The method of Item 17, wherein the at least one phase transfer trimer catalyst comprises at least one component selected from the group consisting of tetramethylammonium butyrate, tetraethylammonium butyrate, tetrapropylammonium butyrate, tetrabutylammonium butyrate, and benzyltrimethylammonium butyrate.

[0104] Item 23. The method according to any one of Items 13 to 22, wherein the catalyst composition is present in combination with a tertiary amine having or not having an isocyanate-reactive group.

[0105] Item 24. (a) The following: i) At least one polyol, ii) A blowing agent in an amount of about 1 to about 80 parts by mass per 100 parts by mass (pphp) of the polyol, iii) A silicone surfactant in an amount of about 0.5 to about 10 pphp, iv) Water in an amount of 0 to about 10 pphp, v) 0 to approximately 50 pphp of a flame retardant, vi) 0 to approximately 10 pphp of a urethane catalyst, and vii) a catalyst composition comprising at least one phase transfer trimer catalyst of from approximately 0.05 to approximately 10 pphp to form a premix comprising, and (b) contacting the premix with at least one polyisocyanate at an isocyanate index of from approximately 80 to approximately 800 A method according to any one of items 13 to 23.

Examples

[0106] These examples are provided to demonstrate specific aspects of the invention and are not intended to limit the appended claims.

[0107] A polyol (a polyester polyol having a hydroxyl value of 230 - 250 and an equivalent weight = 234, supplied by Stepanpol), a flame retardant (TCPP; tris(1-chloro-2-propyl) phosphate), a surfactant (Dabco® DC5598 for pentane foaming and DABCO® SI3201 for formic acid / pentane foaming, both silicone surfactants supplied by Evonik Corporation), a blowing agent (typically n-pentane, or a mixture in water of n-pentane and 85% formic acid), and alternatively a water mixture, were used to produce a foam by adding a catalyst to the premix in a 1759 mL beaker. This composition was mixed for about 5 seconds at about 5000 RPM (or 3000 rpm if specified) using an overhead stirrer equipped with a 6.2 cm diameter stirring paddle. Then an isocyanate was added to achieve a desired isocyanate index, typically in the range of 270 - 300. The premix was then mixed well for about 5 seconds at about 5000 RPM using the same stirrer. The 1759 mL beaker was placed under a FORMAT sonicator device. This allowed the foam to expand and move upward within the 1759 mL beaker because the walls of the beaker restricted the lateral expansion of the foaming material. At the end of the foaming process, the height of the foam was about 10 cm above the end of the 1759 mL beaker. The string gelation time (defined as the time in seconds at which the material during polymerization can form a polymer string when touched with a wooden tongue depressor) and the tack-free time (TFT; defined as the time in seconds at which the surface reaches a sufficiently firm state or cures and no damage or sticking occurs on the surface when touched with a wooden tongue depressor) were measured using a chronometer and manually identified using a tongue depressor. The start time was defined as the time in seconds when the foaming material began to expand.

[0108]

Table 1

[0109]

Table 2

[0110] The PIR / PUR foams of the present invention were produced using various types and amounts of catalysts. The components of typical laminated PIR foam formulations and their respective amounts used in those examples for pentane foamed foams and for pentane / formic acid foamed foams are listed in Table I and Table II.

[0111] Example 1 Comparison between various catalysts with correlated moving cations and a standard PIR catalyst, using formulations B and C foamed with a mixture of pentane and formic acid Table III shows the dynamics data of foam rise and other respective properties of the polyurethane foam material, including the string gelation time and non-stick time defined above, for PIR foam using a mixture of formic acid and pentane as the blowing agent. All catalysts are formates, except for TMAA (tetramethylammonium acetate) having various cations that can act as a phase transfer trimerizing agent to improve the contact between the anionic species of the catalyst and the isocyanate phase. By setting approximately the same string gelation time (SGT), the improvement in non-stick time when exchanging from potassium formate to tetramethylammonium formate can be known. The exchange from potassium formate to tetramethylammonium formate changes the non-stick time from about 85 seconds to about 75 seconds, or more than 10%. The increase in the hydrophobicity of the cation and the exchange from potassium formate to tetrabutylammonium formate do not result in an effective improvement (decrease) in non-stick time. This is unexpected because the tetrabutylammonium cation is known to facilitate the ion transport from the polar phase (formic acid / water) to the organic phase (isocyanate). When using benzyltrimethylammonium formate, much better results are obtained, showing an improvement of about 10% compared to potassium formate in non-stick time. However, the best results are obtained with BDMHPF (benzyldimethyl-(2-hydroxypropyl)ammonium formate), in which case the non-stick time is reduced to only 67 seconds and shows an improvement of about 20% compared to potassium formate. This improvement is shown to occur without a significant change in the initial stage (cream time) of the polymerization reaction, which is important for maintaining the flow of the injected material. Tetramethylammonium acetate is the catalyst with the worst performance.Therefore, when a mixture of formic acid and pentane is used as the blowing agent, BDMHPF (benzyl dimethyl-(2-hydroxypropyl)ammonium formate) is the most preferred catalyst, while TMAF (tetramethylammonium formate) and BTMAF (benzyltrimethylammonium formate) are preferred catalysts, and TBAF (tetrabutylammonium formate) is less preferred, and TMAA (tetramethylammonium acetate) is an unfavorable catalyst.

[0112]

Table 3

[0113] DABCO® TMR25 is a 35% solution of potassium formate in ethylene glycol; 1 TMAF = tetramethylammonium formate in ethylene glycol; 2 TBAF = tetrabutylammonium formate in ethylene glycol; 3 BTMAF = benzyltrimethylammonium formate in ethylene glycol; 4 BDMHPF = benzyl dimethyl-(2-hydroxypropyl)ammonium formate in ethylene glycol; 5 TMAA = tetramethylammonium acetate in ethylene glycol.

[0114]

Table 4

[0115] Table IV shows the data on the form crushability for various catalysts, and the results indicate that there is no significant difference when the catalysts are exchanged.

[0116]

Table 5

[0117] Table V shows data on the profiles of the curing forms for various catalysts, and the results indicate that for the most preferred catalyst, BDMHPF, the initial curing is slightly lower compared to potassium formate, but the curing at the final stage is better. On the other hand, TMAF showed a curing profile similar to the standard based on potassium formate.

[0118] Example 2 Comparison between various catalysts with correlated migrating trimers and the standard PIR catalyst using formulations A and C foamed with pentane Table VI shows the data on the dynamics of foam rise and other respective properties of the polyurethane foam material, including the string gelation time and non-stick time defined above, for PIR foam using pentane as the blowing agent. The tested catalysts in Table VI show the data for the standard commercially available DABCO® K15 used in the lamination of PIR and the group of catalysts of the present invention, and all measurements were carried out at a string gelation time of about 59 seconds. The data shows a substantial improvement in the non-stick time when exchanging from DABCO® K15 to BDMHPAA or BTMAF. The exchange from DABCO® K15 to BDMHPAA or BTMAF shortens the non-stick time from about 156 seconds to about 67 - 68 seconds for BDMHPAA and 60 seconds for BTMAF, or in each case, improves by more than 50%. In addition to the advantage of the improved non-stick time, BDMHPAA results in a further delay at the initial stage of about 12 - 13 seconds compared to the DABCO® K15 standard (the cream time for BDMHPAA = 25 seconds while the cream time for DABCO® K15 = 12 seconds), which improves the flow of the polymerizing mixture, helps minimize the knit line in the production of continuous laminated panels, and improves the mold filling efficiency in an intermittent production line, reducing waste and optimizing the material usage. Surprisingly, the delay in the cream time occurs at the same string gelation time, and even more surprisingly, the catalysts of the present invention can further result in a much shorter non-stick time. However, this dual effect of the initial stage delay (longer cream time) and short non-stick time is not seen in BTMAF. BDMHPF also shows a substantial extension of the cream time by about 8 seconds longer than the standard DABCO® K15. However, BDMHPF has a much lower foam height and the cell structure and foam quality are very poor.

[0119]

Table 6

[0120] 1 Dabco® K15 is a 70% solution of potassium 2-ethylhexanoate in diethylene glycol (supplied by Evonik Corporation); 2 BDMHPAA = solution of benzyldimethyl-(2-hydroxypropyl)-ammonium-acetate in ethylene glycol; BDMHPF = benzyldimethyl-(2-hydroxypropyl)-ammonium formate; BTMAA = solution of benzyltrimethylammonium acetate in ethylene glycol; BTMAF = solution of benzyltrimethylammonium formate in ethylene glycol; TMAA = solution of tetramethylammonium acetate in ethylene glycol; mix at 3000 rpm for 5 seconds.

[0121] Similarly, as shown in Table VII (mixing was carried out at 3000 rpm for 3 seconds), when exchanging from DABCO® K15 to other trimer catalyst salts having cations that can act as phase transfer trimers, a decrease in non-stick time is observed. Thus, the exchange from DABCO® K15 to BTMAA shortens the non-stick time from about 158 seconds to about 105 seconds, or improves by more than 30%. Similar effects are observed for other catalysts, and the shortest non-stick time corresponds to BTMAF, which has 80 seconds or about a 50% reduction in non-stick time. The catalysts in Table VII also show a delay in the initial stage, as measured by the cream time, but their values are much more modest than those measured for BDMHPAA (benzyl dimethyl-(2-hydroxypropyl)ammonium acetate) shown in Table VI. Surprisingly, these advantages do not substantially affect other properties, such as foam density. Thus, when pentane is the sole blowing agent, BDMHPAA (benzyl dimethyl-(2-hydroxypropyl)ammonium acetate) is the most preferred catalyst, while BTMAF (benzyltrimethylammonium formate), BTMAA (benzyltrimethylammonium acetate), tetrabutylammonium acetate, tetramethylammonium acetate, and tetrabutylammonium formate are preferred catalysts, while BDMHPF (benzyl dimethyl-(2-hydroxypropyl)ammonium formate) is not preferred.

[0122]

Table 7

[0123] 1 Dabco® K15 is a 70% solution of potassium 2-ethylhexanoate in diethylene glycol (supplied by Evonik Corporation); 2 BTMAA = benzyltrimethylammonium acetate; 3 TBAA = tetrabutylammonium acetate; 4TBAF = Tetrabutylammonium formate; 5 BTMAF = Benzyltrimethylammonium formate; Mix for 3 seconds at 3000 rpm.

[0124] Table VIII shows the data on the foam crushability for various catalysts, and the results show a very significant improvement for the most preferred catalyst BDMHPAA. Other catalysts showed higher crushability than the standard DABCO® K15.

[0125] [Table 8]

[0126] Table IX shows the curing profiles of various catalysts, showing some initial slower curing that levels off after about 12 minutes and showing equivalent compressive strengths in all cases.

[0127] [Table 9]

[0128] Example 3 Comparison of various catalyst salts having a correlated migrating trimer cation and pivalate anion using PIR formulations A and C foamed with pentane Table X shows the non-stick times for various catalysts based on potassium pivalate, tetramethylammonium, and benzyltrimethylammonium cations. For this group of catalysts, no substantial increase in cream time was observed compared to the standard DABCO® K15. Nevertheless, for benzyltrimethylammonium pivalate, a substantial shortening of the non-stick time was seen while the foam density remained substantially unchanged.

[0129] [Table 10]

[0130] 1 Dabco® K15 is a 70% solution of potassium 2-ethylhexanoate in diethylene glycol (supplied by Evonik Corporation); 2 KP is a 50% solution of potassium pivalate in ethylene glycol; 3 TMAP is a 50% solution of tetramethylammonium in 50% ethylene glycol; 4 BTMAP = benzyltrimethylammonium pivalate.

[0131] Table XI shows data on the form friability for various pivalate catalysts, and the results show the same degradation for all pivalate catalysts. BTMAP did not show an improvement over TMAP, but its performance was slightly inferior to that of DABCO® K15.

[0132]

Table 11

[0133] Table XII shows the curing profiles of various catalysts, showing some initial slower curing that levels off after about 12 minutes and showing equivalent compressive strengths for all cases.

[0134]

Table 12

[0135] Example 4 Performance of standard catalysts using PIR formulations with Freon gas Table XIII shows formulations E, F, and G, where 17 parts of pentane were replaced by 17, 25, and 30 parts of the Freon blowing agent R11. The objective of the new formulations is to produce a foam with the same foam height and volume with the same amount of raw materials, or at least a foam as close as possible to that produced using 17 parts of pentane. In this regard, it is expected that equivalent foam volumes will be produced using the same amount of raw materials.

[0136]

Table 13

[0137] As shown in Figure 1, when producing a foam using Formulation E, it was found that the height of the foam was much lower than that of the foam produced using pentane, and thus its volume was much smaller.

[0138] As shown in Figure 2, when the amount of Freon (registered trademark) R11 was increased to 28.93 pphp, the height and volume of the foam improved, but it still did not reach the foam height corresponding to the pentane foam.

[0139] As shown in Figure 3, when the amount of Freon (registered trademark) R11 was finally increased to 34.7 pphp, the height of the foam improved and the volume of the foam reached a foam height similar to that of the pentane foam.

[0140] The kinetic data of the foam and other parameters using DABCO (registered trademark) K15 as the trimer catalyst in all cases can be summarized in Table XIV. Therefore, compared to the pentane foam, a much higher usage level of Freon (registered trademark) R11 is required to obtain a similar foam height.

[0141]

Table 14

[0142] Example 5 Comparison of the performance of catalysts in various experiments with a correlated moving trimer cation using a PIR formulation foamed with Freon gas and pentane at the same string gelation time Table XV shows the performance of various carboxylates using various phase transfer trimer catalysts, and their performance using the blowing agent Freon® R11 used in the prior art, and a comparison at the same string gelation time with the same catalyst in an n-pentane foamed formulation. Table XV also shows the performance of the standard catalyst DABCO® K15, which is widely used in the industry when using Freon® R11, and its comparison with a pentane blowing agent.

[0143]

Table 15

[0144] 1 Dabco® K15 is a 70% solution of potassium 2-ethylhexanoate in diethylene glycol (supplied by Evonik Corporation); 2 BDMHPAA = benzyldimethyl-(2-hydroxypropyl)-ammonium-acetate; mixed at 3000 rpm for 5 seconds.

[0145] Table XV shows a comparison at the same string gelation time of foam samples produced using pentane and Freon® R11 with a standard alkali metal carboxylate, such as potassium 2-ethylhexanoate (DABCO® K15). For the said standard, there is no substantial difference in the non-stick time when Freon® R11 is replaced with a pentane blowing agent (157 seconds for pentane and 164 seconds for R11).

[0146] Replacing the potassium 2-ethylhexanoate of the catalyst with tetramethylammonium acetate (TMAA) results in a shorter non-stick time than the standard potassium salt. However, the TFT becomes substantially worse for the pentane foam (122 seconds) than for the R11 foam (91 seconds). However, as shown by foam samples 41 - 46, the situation is reversed when the tetramethyl cation is replaced with a more effective phase transfer trimer cation. Thus, when replacing Freon® R11 with pentane, a substantial improvement in TFT is observed for formulations using benzyltrimethylammonium acetate (BTMAA), BDMHPAA (benzyldimethylhydroxypropylammonium acetate) and tetrabutylammonium acetate (TBAA). Therefore, using a trimerization catalyst having a phase transfer trimer cation in the presence of pentane or a similar hydrocarbon blowing agent results in a foam with a faster non-stick time and much improved surface hardening. The improvement in TFT is important in the processing of the foam because it directly affects the hardening of the foam surface as well as the adhesion to the substrate.

Claims

1. (d) at least one active hydrogen-containing compound, (e) a catalyst composition comprising at least one phase transfer trimer catalyst, (f) at least one blowing agent A composition comprising a contact product thereof, provided that the at least one blowing agent is not a chlorofluorocarbon, The at least one phase transfer trimer catalyst has the general formula A-CO2-·+NR1R2R3R4 [wherein, A is H, R1 is -CH2-CH2OH or -CH2-CH(OH)-CH3, R2 is -CH2-Ar, and R3 and R4 are independently of each other methyl, ethyl, propyl or butyl, and Ar is an aryl group] having, and the blowing agent comprises formic acid, or The at least one phase transfer trimer catalyst has the general formula A-CO2-·+NR1R2R3R4 [wherein, A is H or methyl, R1 is -CH2-CH2OH or -CH2-CH(OH)-CH3, R2 is -CH2-Ar, and Ar is an aryl group, and R3 and R4 are independently of each other methyl, ethyl, propyl or butyl, or A is H or methyl, R1 and R2 and R3 are independently of each other methyl, ethyl, propyl or butyl, and R4 is -CH2-Ar, and Ar is an aryl group] having, and the blowing agent comprises a C5-hydrocarbon blowing agent, The composition.

2. Ar is -C 6 H 5 The composition according to claim 1, wherein

3. The composition according to claim 1, wherein the at least one phase transfer trimer catalyst comprises at least one component selected from the group consisting of benzyltrimethylammonium formate, benzyl-(2-hydroxypropyl)-dimethylammonium formate, benzyl-(2-hydroxyethyl)-dimethylammonium formate, benzyltrimethylammonium acetate, benzyl-(2-hydroxypropyl)-dimethylammonium acetate and benzyl-(2-hydroxyethyl)-dimethylammonium acetate.

4. The composition according to claim 1, further comprising a tertiary amine having or not having an isocyanate-reactive group.

5. The composition according to claim 1, further comprising at least one additive selected from at least one bubble stabilizer, at least one flame retardant, at least one chain extender, at least one epoxy resin, at least one acrylic resin, at least one filler, at least one pigment, or any combination thereof.

6. A method for producing a polyisocyanurate / polyurethane foam, comprising contacting at least one polyisocyanate and at least one active hydrogen-containing compound in the presence of a catalyst composition comprising at least one blowing agent and at least one phase transfer trimerization catalyst, wherein the at least one blowing agent is not a chlorofluorocarbon, wherein the at least one phase transfer trimerization catalyst has the general formula A-CO2-·+NR1R2R3R4 [wherein, A is H, R1 is -CH2-CH2OH or -CH2-CH(OH)-CH3, R2 is -CH2-Ar, and R3 and R4 are independently methyl, ethyl, propyl or butyl, and Ar is an aryl group] and the blowing agent comprises formic acid, or wherein the at least one phase transfer trimerization catalyst has the general formula A-CO2-·+NR1R2R3R4 [wherein, A is H or methyl, R1 is -CH2-CH2OH or -CH2-CH(OH)-CH3, R2 is -CH2-Ar, and Ar is an aryl group, and R3 and R4 are independently methyl, ethyl, propyl or butyl, or A is H or methyl, R1 and R2 and R3 are independently methyl, ethyl, propyl or butyl, and R4 is -CH2-Ar, and Ar is an aryl group] and the blowing agent comprises a C5-hydrocarbon blowing agent, the method.

7. Ar is -C 6 H 5 The method according to claim 6, wherein

8. The method according to claim 6, wherein the at least one phase transfer trimer catalyst comprises at least one component selected from the group consisting of benzyltrimethylammonium formate, benzyl-(2-hydroxypropyl)-dimethylammonium formate, benzyl-(2-hydroxyethyl)-dimethylammonium formate, benzyltrimethylammonium acetate, benzyl-(2-hydroxypropyl)-dimethylammonium acetate and benzyl-(2-hydroxyethyl)-dimethylammonium acetate.

9. The method according to claim 6, wherein the catalyst composition is present in combination with a tertiary amine having or not having an isocyanate-reactive group.

10. A process for producing a polyisocyanurate / polyurethane foam, comprising: a) the following: i) at least one polyol, ii) 1 to 80 parts by weight (pphp) of a blowing agent per 100 parts by weight of the polyol, provided that the blowing agent is not a chlorofluorocarbon, iii) 0.5 to 10 pphp of a silicone surfactant, iv) 0 to 10 pphp of water, v) 0 to 50 pphp of a flame retardant, vi) 0 to 10 pphp of a urethane catalyst, and vii) a catalyst composition comprising 0.05 to 10 pphp of at least one phase transfer trimer catalyst to form a premix, and b) contacting the premix with at least one polyisocyanate at an isocyanate index of 80 to 800. comprising, wherein the at least one phase transfer trimer catalyst has the general formula A-CO2-·+NR1R2R3R4 [wherein, A is H, R1 is -CH2-CH2OH or -CH2-CH(OH)-CH3, R2 is -CH2-Ar, and R3 and R4 are independently methyl, ethyl, propyl or butyl, and Ar is an aryl group] and the blowing agent comprises formic acid, or wherein the at least one phase transfer trimer catalyst has the general formula A-CO2-·+NR1R2R3R4 [wherein, A is H or methyl, R1 is -CH2-CH2OH or -CH2-CH(OH)-CH3, R2 is -CH2-Ar, and Ar is an aryl group, and R3 and R4 are independently of each other methyl, ethyl, propyl or butyl, or A is H or methyl, R1, R2 and R3 are independently of each other methyl, ethyl, propyl or butyl, and R4 is -CH2-Ar, and Ar is an aryl group] and the blowing agent contains a C5-hydrocarbon blowing agent, the method.

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