WO2025045680A1

WO2025045680A1 - Method to make bicyclic guanidines

Info

Publication number: WO2025045680A1
Application number: PCT/EP2024/073406
Authority: WO
Inventors: Thomas Dugan Jr.; Juan Jesus Burdeniuc; Jingguo Shen; Jared Denis Bender; Renee Jo Keller
Original assignee: Evonik Operations GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2023-08-25
Filing date: 2024-08-21
Publication date: 2025-03-06
Anticipated expiration: 2026-02-25

Abstract

The present invention relates to a method to make bicyclic guanidine salts, useful as catalysts in various polyurethane applications.

Description

METHOD TO MAKE BICYCLIC GUANIDINES

FIELD OF THE INVENTION

[0001] The instant invention relates to a method to make bicyclic guanidine salts, useful as catalysts in various polyurethane applications.

BACKGROUND OF THE INVENTION

[0002] Highly basic bicyclic and tricyclic guanidine compounds have found applications in the field of organic synthesis and polymer additives. Some methods for synthesizing these compounds either produce noxious byproducts such as hydrogen sulfide or require very harsh conditions. Bicyclic guanidines such as 1 ,5,7-triazabicyclo[4.4.0]dec-5-ene have been prepared by using triamines in combination with reagents such as carbon disulfide, dialkyl carbonates and guanidines. In the case of carbon disulfide, hydrogen sulfide (H₂S), a poisonous gas, is released upon reaction which requires special handling and disposal. In the case of dialkyl carbonates the process requires very high temperatures to effect the condensation with water removal. Water removal is important to prevent TBD hydrolysis, and high boiling drying agents are used to assist with water removal. However, additional steps are required for drying agent removal during product isolation. In the case of using non-cyclic guanidines as raw material, ammonia is released during the process with the reaction taking place at more moderate conditions but the batch addition of the triamine to the guanidine typically yields a significant concentration of monocyclic and acyclic guanidine species which are very difficult to separate from the mixture. The presence of monocyclic and acyclic guanidines in the final product is highly undesirable because they can negatively impact the performance of the bicyclic guanidine when used in application including its use as catalyst to promote polymerization reactions such as polyurethane reactions.

[0003] The CS₂ route is described in U.S. Pat. No. 4797487. This route has the benefit of using inexpensive starting materials and providing high yields. However, it also produces large amounts of the poisonous and malodorous compound hydrogen sulfide (H₂S) as a reaction byproduct. The generation of H₂S requires additional safety precautions as well as the use of expensive scrubbers to prevent its release into the environment.

[0004] A more recent approach is described in US Patent Publication 2009/0281314 and PCT publication W02009/137728. The route disclosed therein uses cyclic urea as the one carbon source. This is an improvement over the CS₂ route since no H₂S is produced; however, the chemistry requires a multi-step process and harsh reaction conditions needed to facilitate the dehydration of the urea-intermediates.

[0005] US 8642771 describes a method for contacting a guanidine salt with dipropylene triamine but the process does not address the necessary conditions for a procedure that can result in minimization of impurities present in the TBD such as ureas, monocyclic and acyclic guanidine intermediates, and residual dipropylene triamine that are very detrimental for its use in polyurethane applications. The presence of these impurities and its minimization, removal or avoidance during manufacturing is essential because these compounds are known to cause premature cell opening in polyurethane foam manufacturing considerably reducing the processing latitude or even causing collapse of polyurethane reactive mixtures. The method described may be performed either in the presence of a solvent, or with a neat mixture of the reagents. The solvents include hydrocarbons, ethers, esters, nitriles, sulfoxides, amides, chlorinated hydrocarbons and/or mixtures of two or more of any one of the above solvents. The invention is preferably performed without these added solvents. However, the presence or absence of these solvents do not provide a means to eliminate the formation of ureas, monocyclic and acyclic guanidine intermediates, and residual dipropylene triamine that are detrimental to the performance in various applications. In addition, the absence of solvents yields TBD as a high melting point solid which makes product isolation more challenging.

[0006] Accordingly, there remains a need for an economically feasible method to manufacture cyclic guanidines such as TBD oramino-alkyl-TBD with sufficiently high purity that can qualify them as suitable catalyst for urethane polymer manufacturing.

BRIEF SUMMARY OF THE INVENTION

[0007] In one aspect, the present invention provides a convenient method for the manufacturing of highly pure polycyclic guanidine compounds and in particular of bicyclic guanidines. [0008] In another aspect, the present invention provides a manufacturing process for making bicyclic guanidine and its salts in a reactor system comprising the steps of: a) reacting a compound having the formula CX2Y, wherein X = NH2 and Y = NH, O, or S and preferably X = NH2 and Y = NH in the presence of an acid with a pKa < 2 with at least one reactive glycol represented by the formula H(OC_nH2n-x)(OH)_x+i where n = 2-6 and x = 0-10 at a temperature in the range of 50°C and up to 190°C to release ammonia and produce a reaction product that is a clear homogeneous solution; b) loading the reaction product of a) to a feeding pump; c) connecting the feeding pump to a reactor vessel loaded with dipropylene triamine of formula H₂N-(CH2)3-NH-(CH₂)3-NH2 or dialkylene triamines of formula H₂N-(CH2)m-NH-(CH2)_n-NH-R where m and n are independently 2 to 5 and preferably 2 to 3 and more preferably 3 and R = CM₈ alkyl, alkyl-cycloalkyl, OH-alkyl (hydroxyalkyl), H₂N-alkyl (amino-alkyl), alkenyl, aryl, arylalkyl, or substituted arylalkyl group and preferably R is aminopropyl, aminoethyl, hydroxyethyl and hydroxypropyl and more preferably aminopropyl; and d) feeding the reaction product of a) into the reactor vessel, wherein the temperature in the reactor vessel is in the range of 160-200°C to yield a solution of the bicyclic guanidine salt in high yields (85 % or higher), high dipropylene triamine conversion (greater than 99%), and minimal or no presence of undesired urea impurities.

[0009] In one aspect embodiment, the bicyclic guanidine salt can then be recovered as a free base by neutralization with a solution of sodium methoxide or potassium methoxide in methanol after solid salt removal by filtration using standard procedures. The bicyclic guanidine base can further be converted into salts of carboxylic acids including mono-, di- and polycarboxylic acids.

[0010] In another aspect, the present invention provides a method to make bicyclic guanidines in high yields and conversions with minimal or absence of undesired urea and monocyclic and acyclic guanidine impurities.

[0011] In another aspect, the present invention provides a method to control the yields and purity of the bicyclic guanidines by the proper selection of reactant.

[0012] The present invention also provides a method to control the yields and purity of the bicyclic guanidines either in the form of salts and/or free bases by the proper selection of reactants to minimize decomposition of the bicyclic guanidines during purification and isolation procedures. [0013] In a further aspect, the present invention provides a method to control the yields and purity of the bicyclic guanidines either in the form of salts and/or free bases by the proper selection of reactants to minimize the formation of impurities during manufacturing. [0014] The present invention provides bicyclic guanidines such as TBD in high purity suitable for use as a curing agent in silyl-terminated polyurethane applications (STPU). [0015] The present invention provides for a method of preparing a silyl-terminated polyurethane application (STPU) comprising a curing agent, wherein the curing agent comprises at least one bicyclic guanidine in high purity.

[0016] Furthermore, the present invention provides bicyclic guanidines such as TBD in high purity suitable for use as catalyst or as co-catalysts in polyurethane applications including flexible, semi-flexible, rigid, semi-rigid and CASE polyurethane applications.

[0017] Bicyclic guanidines made according to the invention are also useful catalysts for moisture-cure silyl modified polymers (SMP). In this application, bicyclic guanidine is part of a one component (1 K) silane-terminated polyurethane (STPU) that is cured by moisture.

[0018] In another aspect, the present invention provides bicyclic guanidines such as TBD in high purity suitable for use as a curing agent in Silane Modified Polymer (SMP) systems. SMP, for the purpose of the present invention, refers to polymers functionalized with at least two alkoxysilane groups, usually at terminal chain ends. In the presence of water, typically in the form of environmental moisture, alkoxysilanes are hydrolyzed to form silanol-containing species, which then undergo polycondensation reactions to build up molecular weight and/or crosslinking density of the polymers and thereby cures/hardens the system. The hydrolysis/condensation cure process in SMP systems are relatively slow but can be accelerated with catalysts such as organotin compounds. It was found that TBD produced according to the invention is also a highly efficient catalyst in curing such silane modified polymers, in particular for SMP functionalized with the even less reactive ethoxysilyl groups instead of the methoxysilyl groups. The present invention provides for a method of preparing a Silane Modified Polymer (SMP) system comprising a curing agent, wherein the curing agent comprises at least one bicyclic guanidine in high purity.

[0019] Silane-Terminated Polyurethane (STPU) system is a representative subtype of the SMP systems that is gaining quick and wide adoptions in Coatings, Adhesives, Sealants & Elastomers (CASE) applications, as it benefits from both polyurethane performance and isocyanate-free processing. STPU prepolymers are the main components in such SMP formulations, and they are typically made from two different approaches: In one process STPU prepolymers are prepared by the reaction of polyols, such as polyester or polyether polyols, with a y-isocyanatopropylalkoxysilane. A second preparation process for STPU prepolymers starts from polyols, such as from polyether or polyester polyols, which in a first reaction step are reacted with an excess of a di- or polyisocyanate. Subsequently the resultant isocyanate-terminated prepolymers are reacted with a y-aminopropyl-functional alkoxysilane to give the desired alkoxysilane- terminated prepolymer. In addition to STPU prepolymers, depending on the end-use application, various types of functional additives may be employed in such SMP formulations, such as fillers, pigments, catalysts, moisture scavengers, UV absorbers & stabilizers, adhesion promoters, wetting agents, defoamers etc.

[0020] The typical measure to assess the reactivity of the SMP formulations is tack- free time, or skinning time. Tack-free time refers to the time period that elapses following the application of the SMP formulation until the polymer surface has cured to the extent, at which touching the surface of the curing mixture with a gloved finger no longer causes material to be transferred onto the glove.

[0021] In another aspect, the present invention provides bicyclic guanidines such as TBD in high purity suitable for use as polyurethane foam catalysts.

BRIEF SUMMARY OF THE DRAWINGS

[0022] Fig. 1 is a rate of rise diagram for example 16.

[0023] Fig. 2 is a picture of foam made with Polycat®8 and a foam made with TBD. [0024] Fig. 3 is a rate of rise diagram for example 17.

[0025] Fig. 4 are pictures of a foam made with DABCO®K15 and a foam made with 33.9% TBD in EG.

[0026] Fig. 5 is a rise profile of succinic acid blocked TBD in high density spray foam formulation.

[0027] Fig. 6 is a picture of a sample of hand mixed foam.

DETAILED DESCRIPTION OF THE INVENTION

[0028] The instant invention relates to a process for making bicyclic guanidine and its salts in a reactor system comprising the steps of a) reacting a compound having the formula CX₂Y, wherein X = NH₂ and Y = NH, O, or S in the presence of an acid with a pKa < 2 with at least one reactive glycol represented by the formula H(OC_nH_2n.x)(OH)_x+i where n = 2-6 and x = 0-10 at a temperature in the range of 50°C and up to 190°C to release ammonia and produce a reaction product that is a clear homogeneous solution; b) loading the reaction product of a) to a feeding pump; c) connecting the feeding pump to a reactor vessel loaded with dipropylene triamine of formula H₂N-(CH₂)₃-NH-(CH₂)₃-NH₂ or dialkylene triamines of formula H₂N-(CH₂)_m-NH-(CH₂)_n-NH-R where m and n are independently 2 to 5 and R = CMS alkyl, alkyl-cycloalkyl, OH-alkyl (hydroxyalkyl), H₂N-alkyl (amino-alkyl), alkenyl, aryl, arylalkyl or substituted arylalkyl group; and d) feeding the reaction product of a) into the reactor vessel, wherein the temperature in the reactor vessel is in the range of 160-200°C to yield a solution of the bicyclic guanidine salt in high yields, high dipropylene triamine conversion, and minimal or no presence of undesired urea impurities.

[0029] In one preferred embodiment the compound having the formula CX₂Y, wherein X = NH₂ and Y = NH, O, or S in the presence of an acid with a pKa < 2 is reacted with glycol represented by the formula H(OC_nH_2n-x)(OH)_x+i where n = 2-6 and x = 0-10 at a temperature in the range of 50°C and up to 100°C to release ammonia and produce a reaction product comprising a carbamimidate of formula:

and a dioxolan of formula:

wherein the amount of carbamimidate in the reaction product is greater than the amount of dioxolan in the reaction product.

[0030] In one preferred embodiment the carbamimidate is 2-hydroxyethyl carbamimidate and the dioxolan is 1 ,3-dioxolan-2-imine when X = NH₂, Y = NH, n = 2 and x = 0.

[0031] In another preferred embodiment the compound having the formula CX₂Y, wherein X = NH₂ and Y = NH, O, or S in the presence of an acid with a pKa < 2 is reacted with glycol represented by the formula H(OC_nH_2n-x)(OH)x+i where n = 2-6 and x = 0-10 at a temperature in the range of 100°C and up to 190°C to release ammonia and produce a reaction product comprising a carbamimidate of formula:

and dioxolan of formula:

wherein the amount of dioxolan in the reaction product is greater than the amount of carbamimidate in the reaction product.

[0032] In one preferred embodiment the carbamimidate is 2-hydroxyethyl carbamimidate and the dioxolan is 1 ,3-dioxolan-2-imine when X = NH₂, Y = NH, n = 2 and x = 0.

[0033] Preferably in one embodiment, the reactive glycol is represented by the formula H(OC_nH2n-x)(OH)x+i where n = 2-6 and x = 0-10.

[0034] More preferably in another embodiment, the reactive glycol is represented by the formula H(OC_nH_2n-x)(OH)x+i where n = 2-4 and x = 0-1 .

[0035] Preferably in another embodiment, the OH groups for the reactive glycol of formula H(OC_nH₂n-x)(OH)x+i with x = 0 and n = 2-4 with OH-groups at the terminal carbons. [0036] In another preferred embodiment the reactive glycol is ethylene glycol, 1 ,3- propane diol, 1 ,4-tetramethylene glycol, glycerol, diglycerol, MP-diol (2-methyl-1 ,3- propanediol) or any combination thereof. In another preferred embodiment the reactive glycol is diglycerol and/or MP-diol (2-methyl-1 ,3-propanediol). In another most preferred embodiment the reactive glycol is glycerol.

[0037] Preferably in one embodiment, the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, and phosphoric acid.

[0038] Preferably in another embodiment, m and n are independently 2 to 3 for the dialkylene triamines of formula H₂N-(CH2)m-NH-(CH₂)n-NH-R. Preferably in another embodiment, m and n are independently 3 for the dialkylene triamines of formula H₂N- (CH₂)m-NH-(CH₂)n-NH-R. Preferably in another embodiment, R is aminopropyl, aminoethyl, hydroxyethyl and hydroxypropyl for the dialkylene triamines of formula H₂N- (CH₂)m-NH-(CH₂)n-NH-R.

[0039] Preferably in another embodiment, the bicyclic guanidine salt as a solution with high yields is 85 % or higher. Preferably in another embodiment, the bicyclic guanidine salt as a solution with high dipropylene triamine conversion is greater than 99%.

[0040] The bicyclic guanidine salt can then be recovered as a free base by neutralization with a solution of sodium methoxide or potassium methoxide in methanol after solid salt removal by filtration using standard procedures. The bicyclic guanidine base can further be converted into salts of carboxylic acids including mono-, di- and polycarboxylic acids.

[0041] In one preferred embodiment, the process further comprises the step of neutralization with a solution of sodium methoxide or potassium methoxide in methanol after solid salt removal by filtration.

[0042] In one preferred embodiment, bicyclic guanidines are made using a combination of guanidine with various acids to make the corresponding salts. Preferred examples of guanidine salts include, guanidine sulfate, guanidine p-toluene sulfonate, guanidine hydrochloride, guanidine phosphate, guanidine triflate and most preferably guanidine hydrochloride.

[0043] In a preferred embodiment, the reactive glycol is a biobased glycol. Preferably, in this embodiment the guanidine salts are made in sustainable glycols such as biobased glycerol obtained from the hydrolysis of oil and fats.

[0044] In another preferred embodiment, the guanidine salts are made using biobased 1 ,3-propanediol which is obtained by fermentation of biomass in which case the resulting solutions are characterized in having ¹⁴C radiocarbon isotope in their composition as measured by the ASTM D6866 method.

[0045] In another preferred embodiment, the bicyclic guanidine salt as a solution in biobased glycol contains 95 to 60 wt. % biobased content. In another preferred embodiment, the bicyclic guanidine salt as a solution in biobased glycol contains 80 to 60 wt. % of biobased content. In another preferred embodiment, the bicyclic guanidine salt as a solution in biobased glycol contains 70 to 60 wt. % biobased content.

[0046] In another preferred embodiment, bicyclic guanidines salts are made according to the method of the invention using dialkylene triamines of formula H₂N-(CH₂)_m -NH- (CH₂)_n-NH-R where m and n are independently 2 to 5 and preferably 2 to 3 and more preferably 3 and R = hydrogen or CMS alkyl or alkyl-cycloalkyl, OH-alkyl (hydroxyalkyl), H2N-alkyl (amino-alkyl), alkenyl, aryl, arylalkyl or substituted arylalkyl group. In a preferred embodiment, R is hydrogen, aminopropyl, aminoethyl, hydroxyethyl and hydroxypropyl. In another preferred embodiment, R is aminopropyl.

[0047] In another preferred aspect of the invention, bicyclic guanidine salts made according to the invention permits improved control of ammonia emissions during the reaction. The control of ammonia emissions is important to reduce the risk of ammonia release into the environment and the related consequences. Ammonia released when reacting the glycol with the guanidine can be trapped in an emissions control device. The rate of ammonia formation in the semi-batch step is related to the feed rate of the reactive glycol product. Ammonia formation can be reduced quickly by stopping the feeding pump. In contrast, the reaction temperature is the only way to control ammonia for the batch process. Rapid and uncontrolled ammonia formation could result in an ammonia generation rate greater than the emission control device is capable of handling. Also, ammonia formation could not be easily stopped in the event of emissions control device failure.

[0048] In another preferred aspect of the invention, bicyclic guanidine salts and bicyclic guanidines made according to the invention provide nearly quantitative conversion of dialkylene triamines. Dialkylene triamines are an undesirable component in the bicyclic guanidines due to formation of ureas in the presence of isocyanates and degradation of hydrofluoroolefin blowing agents. Dipropylene triamine is a particularly undesirable component in the TBD product mixture due to the hazard classifications of dipropylene triamine. Specifically, germ cell mutagenicity (category 2) and specific target organ toxicity (repeated exposure) which need to be classified when present in the product mixture at or above 1 .0%. Especially, skin sensitization which needs to be classified when present in the product mixture at or above 0.1 %.

[0049] In another preferred aspect of the invention, bicyclic guanidine salts made according to the invention improve process safety by preventing unintentional solid formation during a process shutdown.

[0050] The reaction of guanidine salt with a glycol ensures that the reaction mixture is always liquid. In contrast, the batch process is a two-phase reaction mixture until guanidine salt dissolves at reaction temperatures above 60°C. [0051] In one preferred aspect the invention provides bicyclic guanidines that are useful in the production of polyurethane foam including rigid, flexible and semiflexible with optimum physical properties, regular cell structure, low odor and no emissions. Such polyurethane materials can be prepared with bicyclic guanidines made according to the method of this invention where the concentration of impurities such as ureas, cyclic ureas and guanidines can be minimized as they are detrimental to the cell structure of foamed polyurethanes.

[0052] In another preferred embodiment, the present invention provides bicyclic guanidines such as TBD in high purity suitable for use as a curing agent in silyl- terminated polyurethane applications (STPU). The present invention provides for a method of preparing a silyl-terminated polyurethane application (STPU) comprising a curing agent, wherein the curing agent comprises at least one bicyclic guanidine in high purity.

[0053] In another preferred embodiment, the present invention provides bicyclic guanidines such as TBD in high purity suitable for use as a curing agent in silane modified polymers (SMP) systems. Silane Modified Polymers (SMP), for the purpose of the present invention, refers to polymers functionalized with at least two alkoxysilane groups. In the presence of water, typically in the form of environmental moisture, alkoxysilanes are hydrolyzed to form silanol-containing species, which then undergo polycondensation reactions to build up molecular weight and/or crosslinking density of the polymers and therefore cures/hardens the system. The hydrolysis/condensation cure process can be accelerated with catalysts such as tin-based salts. The present invention provides for a method of preparing a Silane Modified Polymer (SMP) system comprising a curing agent, wherein the curing agent comprises at least one bicyclic guanidine in high purity.

[0054] In another preferred embodiment, the inventive method provides bicyclic guanidines comprising at least one member selected from the group consisting of 1 ,5,7- triazabicyclo[4.4.0]dec-5-ene (TBD, triazabicyclodecene), 1 ,5,7-triazabicyclo[4.3.0]non-6- ene (TBN, triazabicyclononane), 1 ,6,8-triazabicyclo[5.3.0]dec-7-ene, 1 ,6,8- triazabicyclo[5.4.0]undec-7-ene, 7-(3-aminopropyl)-1 ,5,7-triazabicyclo[4.4.0]dec-5-ene (aminopropyl-TBD, aminopropyl-triazabicyclodecene), 7-(3-aminopropyl)-1 ,5,7- triazabicyclo[4.3.0]non-6-ene (aminopropyl-TBN, aminopropyl-triazabicyclononane) as well as their corresponding salts of the following acids: hydrochloric acid, sulfuric acid, and phosphoric acid.

[0055] In another preferred embodiment, the inventive method provides a process to prepare solutions of bicyclic guanidine salts with at least one organic carboxylic di-acid, tri-acid or poly-acid component where such salts are useful catalysts in spray foam applications that use blowing agents such as hydrofluorocarbons, hydrochlorocarbon, hydrochloroolefin, hydrofluoroolefins, hydrofluorochloroolefins, fluoroolefin, chloroolefin and hydrochlorofluorocarbons.

[0056] In another preferred embodiment, a polyurethane composition comprises at least one polyol component, a catalyst and at least one isocyanate component. The catalyst composition comprises at least one salt of organic carboxylic di-acid , tri-acid or poly-acid made with bicyclic guanidines.

[0057] In another preferred embodiment, the present invention relates to a method to make a PIR/PUR rigid foam which comprises contacting at least one bicyclic guanidine with polyisocyanate comprising at least one of toluene diisocyanate and diphenyl methane diisocyanate and their isomers with a polyol premix at an isocyanate index of 120-800 where the polyol premix comprises a polyol or polyol mixture, surfactant, flame retardant, amine catalysts, water, miscellaneous additives such as fillers, chain extenders, cross-linkers and colorants and other additives and a blowing agent.

[0058] The catalyst composition of the present invention offers a substantially consistent foam height rise versus time even at a high isocyanate index which provides processing advantages in high-speed PIR lamination processes.

[0059] In another preferred aspect of the present invention, the catalyst made according to the inventions can be thermally stable at standard foam processing temperatures, producing PIR/PUR foams which are substantially free of volatile amines and/or amine odors.

[0060] In another preferred aspect, bicyclic guanidines made according to the invention can be used depending on the type of application together with other additives comprising tertiary amines having or not isocyanate reactive groups, metal catalysts, trimer catalysts, chain extenders, crosslinkers, fillers and other miscellaneous additives known in the art.

[0061] Preferred examples of tertiary amines that can be used with the bicyclic guanidines comprise conventional tertiary amines such as triethylenediamine (TEDA), N- methylimidazole, 1 ,2-dimethyl-imidazole, N-methylmorpholine (commercially available as DABCO® NMM), N-ethylmorpholine (commercially available as DABCO® NEW), 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), pentamethyldipropylene triamine (commercially available as Polycat® 77), N-methyl-N’- (2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyl-diethylenetriamine (commercially available as Polycat® 5), hexamethyl-triethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexyl-amine (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] 12ndecane (commercially available as DABCO® DBU) or its acid blocked derivatives, and the like, as well as any mixture thereof. Particularly useful as a urethane catalyst for foam applications related to the present invention is Polycat® 5, which is known chemically as pentamethyldiethylenetriamine.

[0062] Preferably, the bicyclic guanidines can also be used with tertiary amines having at least one isocyanate reactive group comprising a primary hydroxyl group, a secondary hydroxyl group, a primary amine group, a secondary amine group, a urea group or an amide group.

[0063] Preferred examples of tertiary amine catalyst having an isocyanate reactive group include, but are not limited to N, N-bis(3-dimethylaminopropyl)-N- isopropanolamine, N, N-dimethylaminoethyl-N’-methyl ethanolamine, 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- dimethylaminopropyl urea, N, N-diethylaminopropyl urea, N, N’-bis(3- dimethylaminopropyl)urea, bis(dimethylamino)-2-propanol, 6-dimethylamino-1 -hexanol, N-(3-aminopropyl) imidazole), N-(2-hydroxypropyl) imidazole, 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 a combination thereof.

[0064] In one preferred embodiment, the bicyclic guanidines can also be used with tertiary amines that are acid blocked with an acid including carboxylic acids (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic), sulfonic acids or any other organic or inorganic acid. Preferred examples of carboxylic acids include mono-acids, diacids or poly-acids with or without isocyanate reactive groups. Preferred examples of carboxylic acids include formic acid, acetic acid, propionic acid, butanoic 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.

[0065] In one preferred embodiment, the bicyclic guanidines can also be used in conjunction with a metal catalyst. For example, in one preferred embodiment, the tertiary amine catalyst component is used with an organotin compound, tin (I I) carboxylate salts, bismuth(lll) carboxylate salts, or combinations thereof. Preferred examples of transition metal catalysts such as organotin compounds or bismuth carboxylates can comprise at least one member selected from the group consisting of dibutylin dilaureate, dimethyltin dilaureate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilaurylmercaptide, dibutyltin dilaurylmercaptide, dimethyltin diisooctylmaleate, dibutyltin diisooctylmaleate, dimethyltin bi(2-ethylhexyl mercaptacetate), dibutyltin bi(2-ethylhexyl mercaptacetate), stannous octoate, other suitable organotin catalysts, or a combination thereof. Other metals can also be included, such as, for example, bismuth (Bi). Suitable bismuth carboxylate salts includes salts of 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, and other suitable carboxylic acids. Other salts of transition metals of lead (Pb), iron (Fe), zinc (Zn) with pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids may also be included.

[0066] Preferably, the bicyclic guanidine of the present invention can further comprise other catalytic materials such as carboxylate salts in any amount. Illustrative examples of alkali metal, alkaline earth metal, and quaternary ammonium carboxylate salts include, but are not limited to, potassium formate, potassium acetate, potassium propionate, potassium butanoate, potassium pentanoate, potassium hexanoate, potassium heptanoate, potassium octoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonanoate, potassium stearate, sodium octoate, lithium stearate, sodium caprate (sodium n-decanoate), lithium octoate, 2-hydroxypropyltrimethylammonium octoate solution, and the like, or any combination thereof.

[0067] Preferably, the amount of the other catalytic materials and salts can range from about 0 pphp to about 20 pphp, about 0.1 pphp to about 15 pphp and in some cases about 0.5 pphp to about 10 pphp.

Preparation of Foams

[0068] Foams of any of the various types known in the art may be made using the methods of this invention, using typical polyurethane formulations to which have been added the appropriate amount of bicyclic guanidine as illustrated in the examples below. [0069] For example, flexible polyurethane foams with the excellent characteristics described herein will typically comprise the components shown below in Table A, in the amounts indicated. The components shown in Table A will be discussed in detail later below.

Table A: Polyurethane Components

[0070] The amount of polyisocyanate used in polyurethane formulations according to the invention is not limited, but it will typically be within those ranges known to those of skill in the art. An exemplary range is given in Table A, indicated by reference to “NCO Index" (isocyanate index). As is known in the art, the NCO index is defined as the number of equivalents of isocyanate, divided by the total number of equivalents of active hydrogen, multiplied by 100. The NCO index is represented by the following formula.

NCO index = [NCO/(OH+NH)]*100

[0071] Flexible foams typically use copolymer polyols as part of the overall polyol content in the foam composition, along with base polyols of about 4000-5000 weight average molecular weight and hydroxyl number of about 28-35. Base polyols and copolymer polyols will be described in detail later herein.

[0072] The polyols can have a functionality of about 2 to about 8, about 2 to about 6 and in some cases about 2 to about 4. The polyols can also have a hydroxyl number from about 10 to about 900, and typically about 15 to about 600 and more typically about 20 to about 200.

Catalysts

[0073] Preferably, the amount of the bicyclic guanidine can range from about 0.01 pphp to about 20 pphp, about 0.05 pphp to about 10 pphp and in some cases about 0.1 pphp to about 5 pphp. Preferably, the amount of other catalytically active ingredients can range from about 0 pphp to about 19 pphp, about 0 pphp to about 15 ppm and in some cases about 0 pphp to about 10 pphp.

[0074] Preferred examples of blowing co-catalysts containing isocyanate reactive groups that can be used in combination with the above mentioned catalysts include N,N,N’- trimethyl-N’-3-aminopropyl-bis(aminoethyl) ether, 2-[N- (dimethylaminoethoxyethyl)-N-methylamino]ethanol and N,N,N’-trimethyl-N’-(2- hydroxyethyl)-bis(aminoethyl) ether. Preferably, the amount of blowing co-catalyst can range from about 0 pphp to about 5 pphp, about 0.01 pphp to about 2 pphp and in some cases about 0.05 to about 1 pphp.

[0075] Preferably, the catalyst compositions may also include other components, for example transition metal catalysts such as organotin compounds or bismuth carboxylates for example when the desired polyurethane foam is a flexible slab stock. Metal catalyst can also comprise at least one member selected from the group consisting of dialkyltin carboxylates such as dibutyltin dilaureate, dimethyltin dilaureate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilaurylmercaptide, dibutyltin dilaurylmercaptide, dimethyltin diisooctylmaleate, dibutyltin diisooctylmaleate, dimethyltin bis(2-ethylhexyl mercaptoacetate), dibutyltin bis(2-ethylhexyl mercapotacetate), dimethyltinneodecanoate, dibutyltinneodecanoate, dimethyltinisononanoate, dibutyltinisononanoate, stannous octoate, stannous neodecanoate, stannous isononanoate or other suitable organotin catalysts or other suitable stannous carboxylate salts or a combination thereof. Other metals and salts thereof can also be included, such as, for example, bismuth (Bi). Suitable metal salts include carboxylate salts including salts of acetic acid, propanoic acid, butanoic 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, 16ndecane16nic acid, heptadecanoic acid, octadecanoic acid and other suitable carboxylic acids. Other salts of transition metals of lead (Pb), iron (Fe), or zinc (Zn), with pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexyl carboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids may also be included.

Preferably, the amount of the foregoing metal catalyst can range from about 0 pphp to about 20 pphp, about 0 pphp to about 10 pphp and in some cases about 0 pphp to about

O.01 pphp.

[0076] The bicyclic guanidine can also be acid blocked with an acid including carboxylic acids (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic) sulfonic acids or any other organic or inorganic acid. Examples of carboxylic acids include mono-acids, di-acids or poly-acids with or without isocyanate reactive groups. Preferred examples of carboxylic acids include formic acid, acetic acid, propionic acid, butanoic 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.

[0077] While the bicyclic guanidine of the invention can be used with amines listed above and typically the total loading of the tertiary amine catalyst(s) (i.e., inventive bicyclic guanidine plus any co-gelling catalysts) for making foam according to the invention will be in the range of about 0.1 to about 20 pphp, more typically about 0.1 to about 10 pphp, and most typically about 0.1 to about 5 pphp. However, any effective amount may be used. The term “pphp" means parts per hundred parts polyol.

Organic Isocyanates

[0078] Preferred suitable organic isocyanate compounds include, but are not limited to, hexamethylene diisocyanate (HDI), phenylene diisocyanate (PDI), toluene diisocyanate (TDI), and 4,4’-diphenylmethane diisocyanate (MDI). In one aspect of the invention, 2,4-TDI, 2,6-TDI, or any mixture thereof is used to produce polyurethane foams. Other suitable isocyanate compounds are diisocyanate mixtures known commercially as “crude MDI.” One example is marketed by Dow Chemical Company under the name PAPI, and contains about 60% of 4,4’-diphenylmethane diisocyanate along with other isomeric and analogous higher polyisocyanates. While any suitable isocyanate can be used, an example of such comprises isocyanate having an index range from about 60 to about 200 and typically from about 90 to about 120. The amount of isocyanate typically ranges from about 95 to about 105 and in one aspect of the invention the isocyanate index ranges from about 60 to about 65. Polyol Component

[0079] Polyurethanes are produced by the reaction of organic isocyanates with the hydroxyl groups of polyol, typically a mixture of polyols. The polyol component of the reaction mixture includes at least a main or “base" polyol. Base polyols suitable for use in the invention include, as non-limiting examples, polyether polyols. Polyether polyols include poly(alkylene oxide) polymers such as polyethylene oxide) and polypropylene oxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols, triols and higher alcohols. Preferred examples of diols and triols for reaction with the ethylene oxide or propylene oxide include ethylene glycol, propylene glycol, 1 ,3-butanediol, 1 ,4-butanediol, 1 ,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane, and similar low molecular weight polyols. Other base polyol examples known in the art include polyhydroxy-terminated acetal resins, hydroxyl-terminated amines and hydroxyl-terminated polyamines. Examples of these and other suitable isocyanatereactive materials may be found in U.S. Pat. No. 4,394,491 ; hereby incorporated by reference. Suitable polyether polyols also include those containing tertiary amine groups than can catalyze the gelling and the blowing reaction of polyurethanes, for example those described in US 8367870; WO 03/016373 A1 , WO 01/58976 A1 ;

W02004/060956 Al; W003/016372 A1 ; and W003/055930 Al; the disclosure of the foregoing US and WO publications is hereby incorporated by reference. Other useful polyols may include polyalkylene carbonate-based polyols and polyphosphate-based polyols.

[0080] In one aspect of the invention, a single high molecular weight polyether polyol may be used as the base polyol. Alternatively, a mixture of high molecular weight polyether polyols, for example, mixtures of di- and tri-functional materials and/or different molecular weight or different chemical composition materials may be used. Such di- and tri-functional materials include, but are not limited to polyethylene glycol, polypropylene glycol, glycerol-based polyether triols, trimethylolpropane-based polyether triols, and other similar compounds or mixtures.

[0081] In addition to the base polyols described above, or instead of them, materials commonly referred to as “copolymer polyols" may be included in a polyol component for use according to the invention. Copolymer polyols may be used in polyurethane foams to increase the resistance to deformation, for example to improve the load-bearing properties. Depending upon the load-bearing requirements, copolymer polyols may comprise from about 0 to about 80 percent by weight of the total polyol content.

[0082] Preferred examples of copolymer polyols include, but are not limited to, graft polyols and polyurea modified polyols, both of which are known in the art and are commercially available.

[0083] Graft polyols are prepared by copolymerizing vinyl monomers, typically styrene and acrylonitrile, in a starting polyol. The starting polyol is typically a glycerol-initiated triol, and is typically end-capped with ethylene oxide (approximately 80-85% primary hydroxyl groups). Some of the copolymer grafts to some of the starting polyol. The graft polyol also contains homopolymers of styrene and acrylonitrile and unaltered starting polyol. The styrene/acrylonitrile solids content of the graft polyol typically ranges from 5 wt% to 45 wt%, but any kind of graft polyol known in the art may be used.

[0084] Polyurea modified polyols are formed by the reaction of a diamine and a diisocyanate in the presence of a starting polyol, with the product containing polyurea dispersion. A variant of polyurea modified polyols, also suitable for use, are polyisocyanate poly addition (PIPA) polyols, which are formed by the in-situ reaction of an isocyanate and an alkanolamine in a polyol.

[0085] Other suitable polyols that can be used according to the invention include natural oil polyols or polyols obtained from renewable natural resources such as vegetable oils. Polyols useful in the preparation of polyurethane foam from inexpensive and renewable resources are highly desirable to minimize the depletion of fossil fuel and other non-sustainable resources. Natural oils consist of triglycerides of saturated and unsaturated fatty acids. One natural oil polyol is castor oil, a natural triglyceride of ricinoleic acid which is commonly used to make polyurethane foam even though it has certain limitations such as low hydroxyl content. Other natural oils need to be chemically modified to introduce sufficient hydroxyl content to make them useful in the production of polyurethane polymers. There are two chemically reactive sites that can be considered when attempting to modify natural oil or fat into a useful polyol: 1) the unsaturated sites (double bonds); and 2) the ester functionality. Unsaturated sites present in oil or fat can be hydroxylated via epoxidation followed by ring opening or hydroformylation followed by hydrogenation. Alternatively, trans-esterification can also be utilized to introduce OH groups in natural oil and fat. The chemical process for the preparation of natural polyols using epoxidation route involves a reaction mixture that requires epoxidized natural oil, a ring opening acid catalyst and a ring opener. Epoxidized natural oils include epoxidized plant-based oils (epoxidized vegetable oils) and epoxidized animal fats. The epoxidized natural oils may be fully or partially epoxidized and these oils include soybean oil, corn oil, sunflower oil, olive oil, canola oil, sesame oil, palm oil, rapeseed oil, tung oil, cotton seed oil, safflower oil, peanut oil, linseed oil and combinations thereof. Animal fats include fish, tallow and lard. These natural oils are triglycerides of fatty acids which may be saturated or unsaturated with various chain lengths from C12 to C24. These acids can be: 1) saturated: lauric, myristic, palmitic, steric, arachidic and lignoceric; 2) monounsaturated: palmitoleic, oleic, 3) polyunsaturated: linoleic, linolenic, arachidonic. Partially or fully epoxidized natural oil may be prepared when reacting peroxyacid under suitable reaction conditions. Examples of peroxyacids utilized in the epoxidation of oils have been described in WO 2006/116456 Al; hereby incorporated by reference. Ring opening of the epoxidized oils with alcohols, water and other compounds having one or multiple nucleophilic groups can be used. Depending on the reaction conditions oligomerization of the epoxidized oil can also occur. Ring opening yields natural oil polyol that can be used for the manufacture of polyurethane products. In the hydroformylation/hydrogenation process, the oil is hydroformylated in a reactor filled with a hydrogen/carbon monoxide mixture in the presence of a suitable catalyst (typically cobalt or rhodium) to form an aldehyde which is hydrogenated in the presence of cobalt or nickel catalyst to form a polyol. Alternatively, polyol from natural oil and fats can be produced by trans-esterification with a suitable poly-hydroxyl containing substance using an alkali metal or alkali earth metal base or salt as a trans-esterification catalyst. Any natural oil or alternatively any partially hydrogenated oil can be used in the transesterification process. Examples of oils include but are not limited to soybean, corn, cottonseed, peanut, castor, sunflower, canola, rapeseed, safflower, fish, seal, palm, tung, olive oil or any blend. Any multifunctional hydroxyl compound can also be used such as lactose, maltose, raffinose, sucrose, sorbitol, xylitol, erythritol, mannitol, or any combination.

[0086] Polyols amounts are defined by pphp. There are 3 types of polyols above defined: standard polyol or polyether polyol which can be used in the range of about 100 pphp (the only polyol) to about 10 pphp. The copolymer polyol (CPP) can be used in the range of about 0 to about 80 pphp. Finally, the NOP (natural oil polyol) which typically can be present from about 0 to about 40 pphp.

[0087] Polyols can have an OH number from 10 to about 900 and a functionality from about 2 to 8. The polyol OH number and functionality are selected in order to obtain a foam having desired physical properties.

[0088] Open cell flexible molded foams typically use a main or “base" polyether polyol. Polyether polyols include poly(alkylene oxide) polymers such as polyethylene oxide) and polypropylene oxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols. These polyols can have a functionality of about 2 to about 8, about 2 to about 6 and typically about 2 to about 4. The polyols can also have a hydroxyl number from about 10 to about 900, and typically about 15 to about 600 and more typically about 20 to about 50. Flexible molded foams also use copolymer polyols as part of the overall polyol content in the foam composition with OH numbers typically in the range of 15 to 50, MW ranges typically from 1200 to 8000 and more typically 2000 to 6000 and % solids from 10 % to 60 %. Open cell low density spray foam typically use a polyether polyol with an average MW from 1500 to 6000 and OH number from 15 to 50. Polyols amounts are defined by pphp. There are 4 types of polyols above defined: standard polyol or polyether polyol which can be used in the range of about 100 pphp (the only polyol) to about 10 pphp. The copolymer polyol (CPP) can be used in the range of about 0 to about 80 pphp. The NOP (natural oil polyol) can be present from about 0 to about 40 pphp. Finally, the Mannich polyol is used in combination with other polyol and in a range from 0 pphp to 80 pphp, about 0 pphp to about 50 pphp and in some cases about 0 pphp to about 20 pphp.

[0089] Other polyols that are typically used in PIR/PUR foam formation processes include polyalkylene ether and polyester polyols. The polyalkylene ether polyol includes the poly(alkyleneoxide) polymers such as polyethylene oxide) and polypropylene oxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols, These include, but are not limited to, ethylene glycol, propylene glycol, 1 ,3-butane diol, 1 ,4-butane diol, 1 ,6-hexane diol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane, cyclohexane diol, and sugars such as sucrose and like low molecular weight polyols. [0090] Amine polyether polyols can be used in the present invention. These can be prepared when an amine such as, for example, ethylenediamine, diethylenetriamine, tolylenediamine, diphenylmethanediamine, or triethanolamine is reacted with ethylene oxide or propylene oxide.

[0091] 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 mixtures of different multifunctional materials and/or different molecular weight or different chemical composition materials can be used.

[0092] In yet another aspect of the present invention, polyester polyols can be used, including those produced when a dicarboxylic acid is reacted with an excess of a diol. Non-limiting examples include adipic acid or phthalic acid or phthalic anhydride reacting with ethylene glycol or butanediol. Polyols useful in the present invention can be produced by reacting a lactone with an excess of a diol, for example, caprolactone reacted with propylene glycol. In a further aspect, active hydrogen-containing compounds such as polyester polyols and polyether polyols, and combinations thereof, are useful in the present invention.

[0093] Preferably, the polyol can have an OH number of about 5 to about 600, about 100 to about 600 and in some cases about 50 to about 100 and a functionality of about 2 to about 8, about 3 to about 6 and in some cases about 4 to about 6.

[0094] Preferably, the amount of polyol can range from about 0 pphp to about 100 pphp about 10 pphp to about 90 pphp and in some cases about 20 pphp to about 80 pphp.

Blowing Agents

[0095] Polyurethane foam production may be aided by the inclusion of a blowing agent (BA) to produce voids in the polyurethane matrix during polymerization. Any suitable blowing agent may be used. Suitable blowing agents include compounds with low boiling points which are vaporized during the exothermic polymerization reaction. Such blowing agents are mostly inert, or they have low reactivity and therefore it is likely that they will not decompose or react during the polymerization reaction. Preferred examples of low reactivity blowing agents include, but are not limited to, carbon dioxide, chlorofluorocarbons (CFCs), hydrofluorocarbons (MFCs), hydrochlorofluorocarbons (HCFCs), fluoroolefins (Fos), chlorofluoroolefins (CFOs), hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), acetone, and low-boiling hydrocarbons such as cyclopentane, isopentane, n-pentane, and their mixtures. The amount of BA is typically from about 0 (for example when water is used to blow the polyurethane polymer) to about 80 pphp. Other suitable blowing agents include compounds, for example water, that react with isocyanate compounds to produce a gas. Water (which reacts with isocyanate making CO₂) can be present in the range from about 0 (if a BA is included) to about 60 pphp (a very low density foam) and typically from about 1 .0 pphp to about 10 pphp and, in some cases, from about 2.0 pphp to about 5 pphp.

[0096] Preferred examples of MFCs include, but are not limited to, HFC-245fa, HFC- 134a, and HFC-365; illustrative examples of HCFCs include, but are not limited to, HCFC-141 b, HCFC-22, and HCFC-123.

[0097] Exemplary hydrocarbons include, but are not limited to, 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 comprises at least one hydrocarbon. In another aspect, the blowing agent comprises n-pentane.

[0098] Yet, in another aspect of the present invention, the blowing agent consists essentially of n-pentane or mixtures of n-pentane with one or more blowing agents. [0099] 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), HFO-1336mzz I (trans- 1 ,1 ,1 ,4,4,4- hexafluoro-2-butene) among other HFOs.

Other Optional Components

[00100] A variety of other ingredients may be included in the formulations for making foams according to the invention. Preferred examples of optional components include, but are not limited to, cell stabilizers, crosslinking agents, chain extenders, pigments, fillers, flame retardants, auxiliary urethane gelling catalysts, auxiliary urethane blowing catalysts, transition metal catalysts, alkali and alkali earth carboxylate salts and combinations of any of these.

[00101] Preferred cell stabilizers may include, for example, silicone surfactants as well as organic anionic, cationic, zwiterionic or nonionic surfactants. Preferred examples of suitable silicone surfactants include, but are not limited to, polyalkylsiloxanes, polyoxyalkylene polyol modified dimethylpolysiloxanes, alkylene glycol-modified dimethylpolysiloxanes, or any combination thereof. Preferred suitable anionic surfactants include, but are not limited to, salts of fatty acids, salts of sulfuric acid esters, salts of phosphoric acid esters, salts of sulfonic acids, and combinations of any of these. Preferred suitable cationic surfactants include, but are not limited to quaternary ammonium salts (pH dependent or permanently charged) such as cetyl trimethylammonium chloride, cetyl pyridinium chloride, polyethoxylated tallow amine, benzalkonium chloride, benzethonium chloride and the like. Preferred suitable zwiterionic or amphoteric surfactants include but are not limited to sultaines, aminoacids, imino acids, betaines and phosphates. Preferred suitable non-ionic surfactants include but are not limited to fatty alcohols, polyoxyethylene glycol alkyl ethers, polyoxypropylene glycol alkyl ethers, glucosides (such as decyl, lauryl and octyl glucosides), polyoxyethylene glycol alkyl phenol ethers, glycol alkyl esters, and the like. Preferably, cell stabilizers can be used in an amount from about 0.1 to about 20 pphp and typically from about 0.1 to about 10 pphp and, in some cases, from about 0.1 to about 5.0 pphp . Preferably, fire retardants can be used in an amount from about 0 to about 20 pphp and from about 0 to about 10 pphp and from about 0 to about 5 pphp.

[00102] Crosslinking agents include, but are not limited to, low-molecular weight compounds containing at least two moieties selected from hydroxyl groups, primary amino groups, secondary amino groups, and other active hydrogen-containing groups which are reactive with an isocyanate group. Preferred crosslinking agents include, for example, polyhydric alcohols (especially trihydric alcohols, such as glycerol and trimethylolpropane), polyamines, and combinations thereof. Non-limiting examples of polyamine crosslinking agents include diethyltoluenediamine, chlorodiaminobenzene, diethanolamine, diisopropanolamine, triethanolamine, tripropanolamine, 1 ,6- hexanediamine, and combinations thereof. Typical diamine crosslinking agents comprise twelve carbon atoms or fewer, more commonly seven or fewer. Preferably, crosslinking agents can be used in an amount from about 0.1 to about 20 pphp and typically from about 0.1 to about 10 pphp and, in some cases, from about 0.1 to about 5.0 pphp. [00103] Preferred examples of chain extenders include, but are not limited to, compounds having a hydroxyl or amino functional group, such as glycols, amines, diols, and water. Specific non-limiting examples of chain extenders include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1 ,4-butanediol, 1 ,3- butanediol, 1 ,5-pentanediol, neopentyl glycol, 1 ,6-hexanediol, 1 ,10-decanediol, 1 ,12- dodecanediol, ethoxylated hydroquinone, 1 ,4-cyclohexanediol, N-methylethanolamine, N-methylisopropanolamine, 4-aminocyclohexanol, 1 ,2-diaminoethane, 2,4- toluenediamine, or any mixture thereof. Preferred chain extenders can be used in an amount from about 0.1 to about 100 pphp and typically from about 0.1 to about 50 pphp and, in some cases, from about 0.1 to about 5.0 pphp.

[00104] Pigments may be used to color code the polyurethane foams during manufacture, for example to identify product grade or to conceal yellowing. Pigments may include any suitable organic or inorganic pigments known in the polyurethane art. For example, organic pigments or colorants include, but are not limited to, azo/diazo dyes, phthalocyanines, dioxazines, and carbon black. Examples of inorganic pigments include, but are not limited to, titanium dioxide, iron oxides, or chromium oxide.

Preferably, the amount of pigment can range from about 0 pphp (no pigments added) to about 40 pphp.

[00105] Fillers may be used to increase the density and load bearing properties of polyurethane foams. Suitable fillers include, but are not limited to, barium sulfate or calcium carbonate. Preferably, the amount of fillers can range from about 0 pphp (no fillers added) to about 40 pphp.

[00106] Flame retardants may be used to reduce the flammability of polyurethane foams. For example, suitable flame retardants include, but are not limited to, chlorinated phosphate esters, chlorinated paraffins, or melamine powders.

Preferably, flame retardants can be used in an amount from about 0 to about 20 pphp and from about 0 to about 10 pphp and from about 0 to about 5 pphp.

[00107] In one aspect of the invention, the inventive bicyclic guanidines can be used with amine catalysts having no isocyanate groups typically know as fugitive catalysts. Preferred examples of fugitive amine catalysts within this category include triethylenediamine (TEDA), N-methylimidazole, 1 ,2-dimethyl-imidazole, N- methylmorpholine, N-ethylmorpholine, triethylamine, N,N’-dimethyl-piperazine, 1 ,3,5- tris(dimethylaminopropyl)hexahydrotriazine, 2,4,6-tris(dimethylamino-methyl)phenol,

N-methyldicyclohexylamine, pentamethyldipropylene triamine, N-methyl-N’-(2- dimethylamino)-ethyl-piperazine, tributylamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexylamine, bis(dimethylaminoethyl)ether, tris(3- dimethylamino)propylamine, 1 ,8-diazabicyclo[5.4.0] 26ndecane, or its acid blocked derivatives, and the like, as well as any mixture thereof.

[00108] Certain aspects of the invention are illustrated by the following Examples. These Examples are illustrative only and shall not limit the scope of any claims appended hereto. Foams were evaluated by using Handmix Evaluations or Machine Evaluations as described below.

EXAMPLES

EXAMPLE 1 Inventive

Preparation of Reaction Product Made from Guanidine and Ethylene Glycol

[00109] Guanidine hydrochloride (95.5 g, 1.00 mol) was suspended in 143 g of ethylene glycol in a 250 mL, 3-neck RB flask. The reactor assembly was purged with nitrogen for at least 5 minutes. A scrubber loaded with glacial acetic acid and DI water was connected via tubing to the reactor to capture evolving ammonia. The suspension was heated up to about 50°C with ammonia evolution and it was stirred until the mixture became clear. The

IR spectrum of the reactants and products was recorded. The reaction was monitored by IR. Changes in the IR spectra occurred particularly at the C=NH stretching frequency which substantially showed the disappearance of guanidinium chloride (u = 1625 cm^-1 and 1590 cm^-1) and the appearance of the new product (u = 1655 cm^-1). The shift to higher frequency is consistent with the formation of 2-hydroxyethyl-carbamimidate and its equilibrium product 1 ,3-dioxolan-2-imine. The reacted mixture was not purified, and it was used as obtained in the next step.

2-Hydroxyethyl carbamimidate 1 ,3-Dioxolan-2-imine

The FTIR sprecta of guanidine hydrochloride and the product of Example 1 are shown in Fig. 7.

26

RECTIFIED SHEET (RULE 91 ) ISA/EP EXAMPLE 2 Inventive

Preparation of Reaction Product Made from Guanidine and Ethylene Glycol

[00110] Guanidine hydrochloride (95.5 g, 1.00 mol) was suspended in 143 g of ethylene glycol in a 250 mL, 3-neck RB flask. The reactor assembly was purged with nitrogen for at least 5 minutes. A scrubber loaded with glacial acetic acid and DI water was connected via tubing to the reactor to capture evolving ammonia. The suspension was heated up to about 170°C with ammonia evolution and it was stirred until the mixture became clear. The ammonia released was trapped in an acid scrubber. The IR spectrum of the reactants and products was recorded with a change in the IR spectra particularly the C=NH stretching indicating the formation of products as described in example 1. The reacted mixture was not purified, and it was used as obtained in the next step.

EXAMPLE 3 Inventive

Reaction of Product Mixture from Example 1 with DPTA

[00111] The product obtained in Example 1 was charged into an addition funnel. Dipropylenetriamine (DPTA, 131.2 g, 1.00 mol) and a magnetic stir bar were charged into the reaction flask. The reaction apparatus was essentially a three neck round bottom flask containing DPTA and connected to a reflux condenser, a thermocouple and an addition funnel having the reaction product of Example 1 . The reactor assembly was purged with nitrogen for at least 5 minutes. A scrubber loaded with glacial acetic acid and DI water was connected via tubing to the reactor to capture evolving ammonia. DPTA was heated to 170°C with stirring. Then the reaction product of Example 1 was slowly added at which point ammonia evolution was detected. Heating was continued up to about 5.5 hours until ammonia evolution ceased. The reaction flask was cooled to room temperature. The flask contents weighed about 320 g, and a GO sample was prepared in MeOH with added 1 M KOH in MeOH to generate the free base. Unreacted DPTA was not observed in the GC chromatogram. TBD was the largest component in the GC chromatogram excluding EG. DPTA conversion (quantitative) and TBD salt yield (91%) were calculated from the NMR results.

27

RECTIFIED SHEET (RULE 91 ) ISA/EP

EXAMPLE 4 Inventive

Preparation of Reaction Product Made from Guanidine and 1,3-Propanediol

[00112] Guanidine hydrochloride (95.5 g, 1.00 mol) was suspended in 223 g of 1 ,3- propanediol in a 250 mL, 3-neck RB flask. The reactor assembly was purged with nitrogen for at least 5 minutes. A scrubber loaded with glacial acetic acid and DI water was connected via tubing to the reactor to capture evolving ammonia. The suspension was heated up to about 50°C with ammonia evolution and it was stirred until the mixture became clear. The IR spectrum of the reactants and products was recorded. Upon reaction, change in the IR spectra occurred particularly at the C=NH stretching frequency which substantially showed the disappearance of the guanidinium chloride. The reacted mixture was not purified, and it was used as obtained in the next step. The FTIR spectra of guanidine hydrochloride and the product of Example 4 are shown in Fig. 8.

EXAMPLE 5 Inventive

Reaction Between Product Mixture of Example 4 with DPTA

[00113] The product obtained in Example 4 was charged into an addition funnel. Dipropylenetriamine (DPTA, 131.2 g, 1.00 mol) and a magnetic stir bar were charged into the reaction flask (500 mL, 3-neck RB). The reaction apparatus was assembled and was purged with nitrogen for at least 5 minutes. The reaction apparatus was connected to the acid scrubber via tubing, and the entire apparatus was purged with nitrogen for at least 5 minutes. DPTA was heated to 170°C with stirring, and the product of example 4 was slowly added at 170°C. Heating was continued up to about 7 hours until ammonia evolution ceased. The reaction flask was cooled to room temperature, and a yellow liquid was observed. The flask contents weighed about 387 g, and a GC sample was prepared in MeOH with added 1 M KOH in MeOH to generate the free base. Unreacted DPTA was not observed in the GC chromatogram. TBD was the largest component in the GC

28

RECTIFIED SHEET (RULE 91 ) ISA/EP chromatogram excluding propanediol (PDO). DPTA conversion (quantitative) and TBD salt yield (90%) were calculated from the NMR results.

EXAMPLE 6 Inventive

Preparation of TBD*HCI in biobased 1 ,3-Propanediol

[00114] The procedure outlined in examples 4 and 5 were repeated but instead of using 1 ,3-propanediol derived from fossil-based materials the reaction was carried out using biobased PDO commercially available as SUSTERRA®. DPTA conversion (quantitative) and TBD salt yield (89%) were calculated from the NMR results.

EXAMPLE 7 Inventive

Preparation of TBD Sulfate in Ethylene Glycol (EG)

[00115] Guanidine sulfate (16.2 g, 0.075 mol) was suspended in 25 g of ethylene glycol in a 100 mL, 3-neck RB flask. The reactor assembly was purged with nitrogen for at least 5 minutes. A scrubber loaded with glacial acetic acid and DI water was connected via tubing to the reactor to capture evolving ammonia. The suspension was reacted as described in example 1. The reaction mixture was cooled down and placed in an addition funnel. Dipropylenetriamine (DPTA, 19.7 g, 0.150 mol) and a magnetic stir bar were charged into the reaction flask (100 mL, 3-neck RB). EG (19 g) was also charged into the reaction flask to give a DPTA solution in EG (52 wt.%). The reaction apparatus was assembled and was purged with nitrogen for at least 5 minutes. DPTA solution was heated to 170°C with stirring, and the above reaction product was slowly added at 170°C. Heating was continued up to about 5 hours until ammonia evolution ceased. The reaction flask was cooled to room temperature, and a golden yellow liquid was observed. The flask contents weighed about 72 g, and a GC sample was prepared in MeOH with added 1 M KOH in MeOH to generate the free base. Unreacted DPTA were not observed in the GC chromatogram. TBD was the largest component in the GC chromatogram excluding EG. DPTA conversion (quantitative) and TBD salt yield (97%) were calculated from the NMR results.

EXAMPLE 8 Inventive

Preparation of TBD Methanesulfonate in Ethylene Glycol

29

RECTIFIED SHEET (RULE 91 ) ISA/EP [00116] Guanidine methanesulfonate was prepared separately from guanidine carbonate and methanesulfonic acid. Guanidine methanesulfonate (11.6 g, 0.075 mol) was suspended in 60 g of EG. The reactor assembly was purged with nitrogen for at least 5 minutes. A scrubber loaded with glacial acetic acid and DI water was connected via tubing to the reactor to capture evolving ammonia. The suspension was reacted as described previously to give a methane sulfonate salt mixture as described in example 1. Dipropylenetriamine (DPTA, 9.84 g, 0.0750 mol) and a magnetic stir bar were charged into the reaction flask (100 mL, 3-neck RB). The reaction apparatus was assembled and was purged with nitrogen for at least 5 minutes. DPTA was heated to 170°C with stirring, and the above reaction product was slowly added at 170°C. Heating was continued up to about 5 hours until ammonia evolution ceased. The reaction flask was cooled to room temperature, and a yellow liquid was observed. The flask contents weighed about 77 g, and a GO sample was prepared in MeOH with added 1 M KOH in MeOH to generate the free base. Unreacted DPTA was not observed by GC chromatogram. TBD was the largest component in the GC chromatogram excluding EG. DPTA conversion (quantitative) and TBD salt yield (> 99%) were calculated from the NMR results.

EXAMPLE 9 Inventive

Preparation of TBN*HCI in Ethylene Glycol

[00117] Guanidine hydrochloride (9.5 g, 0.1 mol) was suspended in 22 g of ethylene glycol and reacted as described in example 1 . The product from this reaction was transferred to an addition funnel. N-(2-Aminoethyl)-1,3-propanediamine (AEPDA, 11.7 g, 0.10 mol) and a magnetic stir bar were charged into the reaction flask (100 mL, 3-neck RB). The reaction apparatus was assembled and was purged with nitrogen for at least 5 minutes. AEPDA was heated to 170°C with stirring, and the above reaction product was slowly added at 170°C. Heating was continued up to about 4 hours until ammonia evolution ceased. The reaction flask was cooled to room temperature, and a light-yellow liquid was observed. The flask contents weighed about 37 g, and a GC sample was prepared in MeOH with added 1 M KOH in MeOH to generate the free base. Unreacted AEPDA was not observed in the GC chromatogram. TBN was the largest component in the GC chromatogram excluding EG. AEPDA conversion (quantitative) and TBN salt yield (94%) were calculated from the NMR results.

30

RECTIFIED SHEET (RULE 91 ) ISA/EP EXAMPLE 10 Inventive

Preparation of AP-TBD*HCI in Ethylene Glycol

[00118] Guanidine hydrochloride (7.2 g, 0.075 mol) was suspended in 17 g of ethylene glycol and reacted as described in example 1. N,N’-Bis(3-aminopropyl)-1 ,3- propanediamine (TPTA, 14.1 g, 0.075 mol) and a magnetic stir bar were charged into the reaction flask (100 mL, 3-neck RB). The reaction apparatus was assembled and was purged with nitrogen for at least 5 minutes. TPTA was heated to 170°C with stirring, and the above reaction product was slowly added at 170°C. Heating was continued up to about 4.5 hours until ammonia evolution ceased. The reaction flask was cooled to room temperature, and a light-yellow liquid was observed. The flask contents weighed about 30 g, and a GC sample was prepared in MeOH with added 1 M KOH in MeOH to generate the free base. Unreacted TPTA was not observed in the GC chromatogram. AP-TBD was the largest component in the GC chromatogram. TPTA conversion (quantitative) and AP- TBD salt yield (89%) were calculated from the NMR results.

Example 11 Inventive

Preparation of TBD in Ethylene Glycol Using NaOMe Solution

[00119] TBD*HCI in EG (157 g, 0.500 mol) was charged into an oven dried reaction flask (1 L). The apparatus was assembled and was purged with nitrogen for approximately 10 minutes. A room temperature water bath was used for cooling. The solution was mixed using the mechanical stirrer (150 rpm). The sodium methoxide (NaOMe) solution (28 wt.%, 101 g, 0.52 mol) was charged to the addition funnel. The apparatus was purged with nitrogen for ~10 minutes prior to addition. The NaOMe solution was added over 5 minutes, and a salt formation was observed upon addition. An exotherm was not observed upon addition. Additional anhydrous IPA (-120 mL) was added to rinse the addition funnel. The white slurry was mixed for an additional 60 min, and the white slurry was transferred to a glass bottle. The mixture was filtered using a 1 L Millipore pressure filtration apparatus equipped with Whatman Grade I filter paper (150 mm diameter). The filtrate was light yellow with fine solids, and 309 g was collected. The volatile components were removed under reduced pressure using a rotary evaporator. The weight of the concentrated filtrate was 127 g, and the filtrate was sparged with nitrogen overnight. A noticeable amount of salt had settled overnight on the flask walls, and the final weight of the concentrated filtrate was 126 g. The concentrated filtrate was filtered using the 1 L Millipore pressure filtration

31

RECTIFIED SHEET (RULE 91 ) ISA/EP apparatus equipped with a 0.45-micron Millipore Duropore filter membrane (142mm). The filtrate (112 g) was a golden yellow liquid. An aliquot was taken for GC analysis in MeOH. The GC chromatogram showed that TBD was the largest component in the GC chromatogram excluding EG. TBD yield was about 73 %.

Example 12 Inventive

Preparation of TBD in Ethylene Glycol Using KOMe Solution

[00120] TBD*HCI in EG (162.3 g, 0.501 mol) was charged into an oven dried reaction flask (1 L). The apparatus was assembled and was purged with nitrogen for approximately 10 minutes. A room temperature water bath was used for cooling. The solution was mixed using the mechanical stirrer. The potassium methoxide (KOMe) solution (25.1 wt%, 144 g, 0.52 mol) was charged to the addition funnel. The apparatus was purged with nitrogen for -10 minutes prior to addition. The KOMe solution was added over 30 minutes, and a salt formation was observed upon addition. An exotherm was not observed upon addition. Additional anhydrous IPA (-150 mL) was added to rinse the addition funnel. The white slurry was mixed for an additional 2 h, and the white slurry was transferred to a glass bottle. The mixture was filtered using a 1 L Millipore pressure filtration apparatus equipped with Whatman Grade I filter paper (150 mm diameter). The filtrate was light yellow with trace solid, and 444 g was collected. The volatile components were removed under reduced pressure using a rotary evaporator. The weight of the concentrated filtrate was 145 g. The concentrated filtrate was filtered using the 1 L Millipore pressure filtration apparatus equipped with a 0.45-micron Millipore Duropore filter membrane (142mm). The filtrate (134 g) was a golden yellow liquid. The filtrate was sparged with nitrogen overnight to remove any residual solvent, and 133 g was obtained after sparging. An aliquot was taken for GC analysis in MeOH. The GC chromatogram showed that TBD was the largest component in the GC chromatogram excluding EG. TBD yield was about 88%.

Example 13 Inventive

Preparation of TBD in 1,3-Propanediol Using NaOMe Solution

[00121] TBD*HCI in PDO (214.6 g, 0.501 mol) was charged into an oven dried reaction flask (1 L). The apparatus was assembled and was purged with nitrogen for approximately 10 minutes. The solution was mixed using the mechanical stirrer (100 rpm). The NaOMe solution (28.1 wt%, 102 g, 0.53 mol) was charged to the addition funnel. The apparatus

32

RECTIFIED SHEET (RULE 91 ) ISA/EP was purged with nitrogen for ~10 minutes prior to addition. The NaOMe solution was added over 5 minutes, and a salt formation was observed upon addition. An exotherm was not observed upon addition. Additional MeOH (~35 mL) was added to rinse the addition funnel. The white slurry was mixed for an additional 60 min, and the white slurry was transferred to a glass bottle. The mixture was filtered using a 1 L Millipore pressure filtration apparatus equipped with Whatman Grade I filter paper (150 mm diameter). The filtrate was light yellow with fine solids. The volatile components were removed under reduced pressure using a rotary evaporator. The weight of the concentrated filtrate was 191 g, and the filtrate was sparged with nitrogen overnight. A noticeable amount of salt had settled overnight on the flask walls, and the final weight of the concentrated filtrate was 190 g. The concentrated filtrate was filtered using the 1 L Millipore pressure filtration apparatus equipped with a 0.45-micron Millipore Duropore filter membrane (142mm). The filtrate (175 g) was a yellow liquid. An aliquot was taken for GC analysis in MeOH. The GC chromatogram showed that TBD was the largest component in the GC chromatogram excluding PDO. TBD yield was about 89 %.

Example 14 Inventive

Preparation of TBD in biobased 1 ,3-Propanediol Using NaOMe Solution

[00122] TBD*HCI in biobased PDO (Susterra®, 216.4 g, 0.500 mol) was charged into an oven dried reaction flask (1 L). The apparatus was assembled and was purged with nitrogen for approximately 10 minutes. The solution was mixed using the mechanical stirrer (100 rpm). The NaOMe solution (29.9 wt%, 96.6 g, 0.53 mol) was charged to the addition funnel. The apparatus was purged with nitrogen for ~10 minutes prior to addition. The NaOMe solution was added over 15 minutes, and a salt formation was observed upon addition. An exotherm was not observed upon addition. Additional MeOH (53 g) was added to rinse the addition funnel. The white slurry was mixed for an additional 4 h, and the white slurry was transferred to a glass bottle. The mixture was filtered using a 1 L Millipore pressure filtration apparatus equipped with Whatman Grade I filter paper (150 mm diameter). The filtrate was light yellow with fine solids. The volatile components were removed under reduced pressure using a rotary evaporator. The weight of the concentrated filtrate was 173 g, and the filtrate was sparged with nitrogen overnight. A noticeable amount of salt had settled overnight on the flask walls, and the final weight of the concentrated filtrate was 172 g. The concentrated filtrate was filtered

33

RECTIFIED SHEET (RULE 91 ) ISA/EP using the 1 L Millipore pressure filtration apparatus equipped with a 0.45-micron Millipore Duropore filter membrane (142mm). The filtrate (169 g) was a yellow liquid. An aliquot was taken for GC analysis in MeOH. The GC chromatogram showed that TBD was the largest component in the GC chromatogram excluding PDO. TBD yield was about 84%.

EXAMPLE 15 Inventive

TBD as Catalyst for Moisture-Cure SMP Applications: Catalyst for 1K STPU Moisture- Cure formulations

[00123] The one-component (1 K) silane-terminated polyurethane (STPU) moisture-cure formulation employed in Examples 1, 2 and 3 was as follows:

Table I: One Component Silane Terminated Polyurethane Control Formulation

Polymer ST 80 57.33

Dynasylan VTMO 3.03

Aerosil R 106 9.00

VESTINOL 9 29.33

Dynasylan DAMO-T 1.01

Catalyst (TBD/DBU/DBTDL) 0.30

[00124] The one-component (1 K) silane-terminated polyurethane (STPU) moisture-cure formulation employed in Examples 4, 5 and 6 was as follows:

Table II: One Component Silane Terminated Polyurethane Control Formulation

Polymer ST 80 57.33

Dynasylan VTMO 3.03

Aerosil R 106 9.00

Elatur CH 29.33 [00125] The following abbreviations were

Dynasylan DAMO-T 1.01

Catalyst (TBD/DBU/DBTDL) 0.30 employed in the examples below:

Polymer ST 80 is a high modulus SMP resin based on polypropylene oxide backbone terminally functionalized with trimethoxysilane groups, of a viscosity of 20,000 mPa s at 25 °C. (Evonik Corp.)

Dynasylan VTMO is vinyltrimethoxysilane. (Evonik Corp.)

Aerosil R 106 is a hydrophobic fumed silica surface treated with D4

(octamethylcyclotetrasiloxane). (Evonik Corp.)

VESTINOL 9 is diisononyl phthalate. (Evonik Corp.)

Elatur CH is diisononyl cyclohexanoate. (Evonik Corp.)

34

RECTIFIED SHEET (RULE 91 ) ISA/EP Dynasylan DAMO-T is N-(2-aminoethyl)-3-aminopropyltrimethoxysilane. (Evonik Corp.) DBU is 1 ,8-diazabicyclo(5.4.0)undec-7-ene.

DBTDL is dibutyltin dilaurate.

[00126] The example formulations were prepared with a centrifugal speed mixer, and then subjected to the following test:

[00127] Tack-free Time Test

[00128] The tack-free time, also known as skinning time, was evaluated by touching the surface of the curing mixture with a gloved finger at set intervals until there is no material being transferred onto the glove. For Examples 1-6, the tests were conducted at 25 °C and 50% relative humidity.

[00129] The test results are indicated in Table 1-2.

Table 1

Examples

1 2 3

Catalyst TBD DBU DBTDL

Tack-free Time (min) 6 23 32

Table 2

Examples

4 5 6

Catalyst TBD DBU DBTDL

Tack-free Time (min) 6 23 32

EXAMPLE 16 Inventive

TBD as Catalyst for the Preparation of Rigid Foam Used in Insulation Applications [00130] A 36.1 wt.% sample of TBD in EG was prepared by diluting the product of Example 11 or Example 12 with additional ethylene glycol. This solution was used as catalysts to make rigid polyurethane foam used in insulation applications. A typical polyurethane foam formulation for insulation is described in the following table:

Table II: Rigid Foam Control Formulation

35

RECTIFIED SHEET (RULE 91 ) ISA/EP ¹

: S ucrose-i n itiated ethylene oxide/propylene oxide copolymer with a hydroxyl number of about 350 to 400; ²: Polysiloxane silicone surfactant commercially available from Evonik as Tegostab®8465; ³: Amine catalyst N,N-dimethylaminocyclohexane, commercially available from Evonik as Polycat®8; ⁴: Trimer catalyst is a 70 wt.% solution of potassium 2-ethylhexanoate in diethylene glycol commercially available from Evonik as DABCO®K15; ⁵: Blowing agent is 1 ,1 ,1 ,3,3-pentafluoropropane a liquid hydrofluorocarbon commercially available from Honeywell as Enovate®245fa; ⁶: Rubinate®M is a commercially available MDI from Huntsman.

[00131] The evaluation of the catalyst reactivity in a rigid polyurethane system was conducted using free-rise cup foam sample with a FOMAT sonar Rate-Of-Rise (ROR) device. The FOMAT standard software generates both height versus time plots and velocity versus time plots. These plots are useful for comparing the relative reactivity of different catalyst formulations. MDI polyurethane foam was prepared in a conventional hand mix manner.

[00132] The table below shows the amount of catalyst needed for matching the string gel time in a standard rigid formulation when using a solution of TBD in ethylene glycol. Clearly, TBD shows higher activity than the standard Polycat®8 catalysts showing that it is an efficient catalyst for making rigid polyurethane foam.

[00133] In Fig.1 , the curve on the slight left corresponds to Polycat®8 while the curve on the slight right corresponds to the TBD solution in EG. Both curves are nearly on top of each other and can be considered equivalent within the experimental error of hand mix evaluation. Foam samples can be seen in Fig. 2 where foam made with Polycat®8 is shown on the left and foam made with TBD is shown on the right.

EXAMPLE 17 Inventive

TBD as Catalyst for the Preparation of PI R Rigid Foam Used in Insulation Applications [00134] The foams were produced by adding catalysts into a premix of a polyol (polyester polyol with 230-250 hydroxyl number and equivalent weight = 234 supplied by Stepanpol), flame retardant (TCPP; tris(1-chloro-2-propyl) phosphate), surfactant (for pentane blown Dabco®DC5598 and for formic acid/pentane blown DABCO®SI3201 both of which are silicone surfactants supplied by Evonik Corporation), blowing agent (typically n-pentane or a mixture of n-pentane and 85% formic acid in water) and

36

RECTIFIED SHEET (RULE 91 ) ISA/EP alternatively water mixture in a 1759 mL beaker. This composition was mixed for about 5 seconds (s) at about 5,000 RPM (or 3000 rpm where specified) using an overhead stirrer fitted with a 6.2-cm diameter stirring paddle. Isocyanate was then added to achieve the desired Isocyanate Index which was typically in the 270-300 range. Then the premix was mixed well for about 5 seconds (s) at about 5,000 RPM using the same stirrer. The 1759 mL beaker was placed under a FOMAT sonar device. This allows the foam to expand inside the 1759 ml beaker and move upwards since the walls of the beaker restricts lateral expansion of the foaming mass. At the end of the foaming process, the foam height was about 10 cm higher and above the 1759 ml beaker edge. String gel time (defined as the time in seconds at which the polymerizing mass is able to form polymer strings when touched with a wooden tongue suppressor) and tack free time (TFT; defined as the time in seconds for the surface to attain a sufficient robust state or cure that no damage or stickiness occurs on the surface when touched with a wooden tongue suppressor) were measured using a chronometer and determined manually using a tongue suppressor. Start time was defined as the time in seconds when the foaming mass begins expansion.

Table III: Lamination Control Formulation

Control Formulation of Foams

Formulation Type Control A Experimental NOTES

COMPONENTS Weight (g)

Weight (g) NOTES

Stepanpol®PS2352 100 100 Polyester polyol with 230-250 hydroxyl number and equivalent weight = 234 supplied by Stepanpol

Dabco®DC5598 1.97 1 97 Silicone surfactant supplied by Evonik

Corporation

TCPP 13 55 13 55 tris(1 -chloro-2-propyl) phosphate flame retardant

H₂O 0.51 0 51 Water

Pentane 19.68 19.68 n-pentane blowing agent

Polycat®-5 0.17 0 17 Pentamethyldiethylenetriamine supplied by

Evonik Corporation

DABCO®K15 1 85 1 85 Potassium 2-ethylhexanoate solution in diethylene glycol

TBD Trimer Catalyst — Varied A 36.9 wt. % solution of TBD made according to the invention

Isocyanate 191.4 191.4

37

RECTIFIED SHEET (RULE 91 ) ISA/EP Isocyanate Index 270 270 Commercially available MDI with % NCO =

31.2

[00135] The following table illustrates the efficacy of a 36.9 wt. % solution of TBD in ethylene glycol when used as catalysts in a 270 index PIR formulation. Also, Fig. 3 illustrates the smooth rise profile of TBD (lower curve) when compared with two runs on the standard catalysts DABCOOK15 where the typical “PIR step” is formed at about 60 seconds. A smooth rise profile provides the advantage of easier processing in high speed laminators.

[00136] TBD is an effective trimer catalyst as evidenced by the following data highlighting the % trimer conversion of about 73 %.

Foam samples can be seen in Fig. 4 where foam made with DABCOOK15 is shown on the left and foam made with 33.9% TBD in EG is shown on the right.

EXAMPLE 18 Inventive

Acid Blocked-TBD as Catalyst for the Preparation of High Density Rigid Spray Foam Used in Insulation Applications with Commercially Available Hydrofluoroolefin Blowing Agent

[00137] A sample of acid blocked TBD in EG was prepared by mixing the product of Example 11 or 12, succinic acid and water with or without additional ethylene glycol. This solution with the composition shown below was used as catalysts to make rigid polyurethane foam used in insulation applications:

38

RECTIFIED SHEET (RULE 91 ) ISA/EP

[00138] A typical high density spray foam formulation is shown in Table IV:

Terol ®305 is a polyrester polyol and Jeffol ®R470x is a polyether polyol obtained from Huntsman. Flame retardant: TCPP obtained from ICL-IP. Surfactant : DABCO®DC193 obtained from Evonik Industries. Forane®1233zd is a blowing agent obtained from Arkema (1-chloro-3,3,3-trifluoropropane). HFO solubility enhancer: DABCO®PM301 obtained from Evonik Industries.

[00139] The table below shows the use level of the EG solution of acid blocked TBD to provide a good quality foam:

[00140] Fig. 5 shows the rise profile of succinic acid blocked TBD in high density spray foam formulation and Fig. 6 shows a sample of hand mixed foam highlighting the fine cell structure of the specimen.

39

RECTIFIED SHEET (RULE 91 ) ISA/EP

Claims

1) A process for making bicyclic guanidine and its salts in a reactor system comprising the steps of a) reacting a compound having the formula CX₂Y, wherein X = NH₂ and Y = NH, O, or S in the presence of an acid with a pKa < 2 with at least one reactive glycol represented by the formula H(OC_nH2n-_x)(OH)_x+i where n = 2-6 and x = 0- 10 at a temperature in the range of 50°C and up to 190°C to release ammonia and produce a reaction product that is a clear homogeneous solution; b) loading the reaction product of a) to a feeding pump; c) connecting the feeding pump to a reactor vessel loaded with dipropylene triamine of formula H₂N-(CH2)3-NH-(CH₂)3-NH2 or dialkylene triamines of formula H₂N-(CH2)m-NH-(CH2)_n-NH-R where m and n are independently 2 to 5 and R = CM₈ alkyl, alkyl-cycloalkyl, OH-alkyl (hydroxyalkyl), H₂N-alkyl (amino-alkyl), alkenyl, aryl, arylalkyl or substituted arylalkyl group; and d) feeding the reaction product of a) into the reactor vessel, wherein the temperature in the reactor vessel is in the range of 160-200°C to yield a solution of the bicyclic guanidine salt in high yields, high dipropylene triamine conversion, and minimal or no presence of undesired urea impurities.

2) The process according to claim 1 , wherein the compound having the formula CX₂Y, wherein X = NH₂ and Y = NH, O, or S in the presence of an acid with a pKa < 2 is reacted with glycol represented by the formula H(OC_nH2n-_x)(OH)_x+i where n = 2-6 and x = 0-10 at a temperature in the range of 50°C and up to 100°C to release ammonia and produce a reaction product comprising a carbamimidate of formula:

and a dioxolan of formula:

3) The process according to claim 1 , wherein the compound having the formula CX₂Y, wherein X = NH₂ and Y = NH, O, or S in the presence of an acid with a pKa < 2 is reacted with glycol represented by the formula H(OC_nH_2n-x)(OH)_x+i where n = 2-6 and x = 0-10 at a temperature in the range of 100°C and up to 190°C to release ammonia and produce a reaction product comprising a carbamimidate of formula:

and dioxolan of formula:

4) The process according to any of the previous claims, wherein the reactive glycol is represented by the formula H(OC_nH_2n-x)(OH)_x+i where n = 2-6 and x = 0-10.

5) The process according to any of the previous claims, wherein the reactive glycol is represented by the formula H(OC_nH_2n-x)(OH)_x+i where n = 2-4 and x = 0-1 .

6) The process according to any of the previous claims, wherein the reactive glycol is represented by the formula H(OC_nH_{2n x})(OH)_x+i where n = 2-4 and x = 0 with the OH- groups at the terminal carbons.

7) The process according to any of the previous claims, wherein the carbamimidate is 2-hydroxyethyl carbamimidate and the dioxolan is 1 ,3-dioxolan-2-imine when X = NH₂, Y = NH, n = 2 and x = 0. 8) The process according to any of claims 1-4, wherein the reactive glycol is ethylene glycol, 1 ,3-propanediol, 1 ,4-tetramethylene glycol, glycerol, diglycerol, MP-diol (2-methyl-1 ,3-propanediol) or any combination thereof.

9) The process according to claim 8, wherein the reactive glycol is glycerol.

10) The process according to any of the preceding claims, wherein the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, and phosphoric acid.

1 1) The process according to any of the preceding claims, wherein m and n are independently 2 to 3 for the dialkylene triamines of formula H₂N-(CH2)m-NH-(CH2)_n-NH-R.

12) The process according to any of the preceding claims, wherein m and n are independently 3 for the dialkylene triamines of formula H₂N-(CH2)m-NH-(CH2)_n-NH-R.

13) The process according to any of the preceding claims, wherein R is aminopropyl, aminoethyl, hydroxyethyl and hydroxypropyl for the dialkylene triamines of formula H₂N- (CH₂)_m-NH-(CH₂)n-NH-R.

14) The process of claim 16, wherein R is aminopropyl for the dialkylene triamines of formula H₂N-(CH2)m-NH-(CH₂)n-NH-R.

15) The process according to any of the preceding claims, wherein the bicyclic guanidine salt as a solution with high yields is 85 % or higher.

16) The process according to any of the preceding claims, wherein the bicyclic guanidine salt as a solution with high dipropylene triamine conversion is greater than 99%.

17) The process according to any of the preceding claims, further comprising the step of neutralization with a solution of sodium methoxide or potassium methoxide in methanol after solid salt removal by filtration. 18) The process according to any of the preceding claims, wherein the reactive glycol is a biobased reactive glycol.

19) The process of claim 18, wherein the bicyclic guanidine salt as a solution in biobased reactive glycol contains 95 to 60 wt. % biobased content.

20) The process according to any of the preceding claims, wherein the guanidine salts are made in biobased 1 ,3-propanediol which is obtained by fermentation of biomass characterized in having ¹⁴C isotope in their composition.

21) Use of the bicyclic guanidine salt according to any of the preceding claims as a curing agent in silyl-terminated polyurethane applications (STPU).

22) Use of the bicyclic guanidine salt according to any of the preceding claims as a curing agent in Silane Modified Polymer (SMP) systems.