Method for producing bicyclic guanidine

Abstract

The present invention relates to a method for producing bicyclic guanidine salts that are useful as catalysts in various polyurethane applications.

Description

[Technical Field]

[0001] The present invention relates to a method for producing bicyclic guanidine salts that are useful as catalysts in various polyurethane applications.

[0002] Background of the Invention Highly basic bicyclic and tricyclic guanidine compounds have been shown to have applications in the fields of organic synthesis and polymer additives. Some methods for synthesizing these compounds either produce toxic byproducts such as hydrogen sulfide or require extremely harsh conditions. Bicyclic guanidines such as 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD) have been prepared by using triamines in combination with reagents such as carbon disulfide, dialkyl carbonates, and guanidine. In the case of carbon disulfide, hydrogen sulfide (H2S), a toxic gas, is released immediately after the reaction, thus requiring special handling and disposal. In the case of dialkyl carbonates, this process requires very high temperatures to cause condensation while removing water. To prevent TBD hydrolysis, water removal is crucial, and high-boiling point desiccants are used to aid in water removal. However, an additional step is required to remove the desiccant during the isolation of the product. When acyclic guanidine is used as a starting material, ammonia is released during the process, and the reaction proceeds under milder conditions. However, batch addition of triamine to guanidine typically produces monocyclic and acyclic guanidine species at significant concentrations that 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 affect the performance of bicyclic guanidine when used in applications including its use as a catalyst to accelerate polymerization reactions such as polyurethane reactions.

[0003] U.S. Patent No. 4,797,487 describes the CS2 pathway. This pathway has the advantages of using inexpensive starting materials and yielding high yields. However, it also produces a large amount of hydrogen sulfide (H2S), a toxic and foul-smelling compound, as a reaction byproduct. The production of H2S necessitates additional safety measures, as well as the use of expensive scrubbers, to prevent its release into the environment.

[0004] More recent approaches are described in U.S. Patent Application Publication 2009 / 0281314 and International Publication 2009 / 137728. In the routes disclosed in these publications, cyclic urea is used as the sole carbon source. This is an improvement over the CS2 route because no H2S is produced, but chemically it requires a multi-step process and harsh reaction conditions necessary to facilitate the dehydration of the urea intermediate.

[0005] U.S. Patent No. 8,642,771 describes a method for contacting a guanidine salt with dipropylenetriamine, but this method does not address the necessary conditions for a procedure that can result in minimizing impurities present in the TBD, such as urea, monocyclic and acyclic guanidine intermediates, and residual dipropylenetriamine, which are highly detrimental to use in polyurethane applications. These compounds are known to cause premature bubble release in the production of polyurethane foams, significantly reducing the tolerance of the process, or even causing the collapse of polyurethane reactive mixtures; therefore, the presence of these impurities during production, and minimizing, removing, or avoiding them, is essential. The described method can be carried out in the presence of a solvent or using a pure mixture of the reagents. The solvent includes mixtures of two or more of any one of the aforementioned hydrocarbons, ethers, esters, nitriles, sulfoxides, amides, chlorinated hydrocarbons, and / or solvents. The present invention is preferably carried out without these added solvents. However, whether these solvents are present or absent, no means are provided to eliminate the formation of urea, monocyclic and acyclic guanidine intermediates, and residual dipropylenetriamines, which are detrimental to performance in various applications. Furthermore, in the absence of solvents, TBD is formed as a high-melting-point solid, thereby making product isolation more difficult.

[0006] Therefore, there is still a need for an economically viable method to produce cyclic guanidines such as TBD or aminoalkyl TBD with sufficient purity to be suitable as appropriate catalysts for the production of urethane polymers.

[0007] Brief summary of the invention In one embodiment, the present invention provides a convenient method for producing high-purity polycyclic guanidine compounds, particularly bicyclic guanidines.

[0008] In another embodiment, the present invention relates to a method for producing bicyclic guanidine and its salts in a reactor system, a) a compound having formula CX2Y [wherein X=NH2 and Y=NH, O or S, preferably X=NH2 and Y=NH] in the presence of an acid of pKa ≤ 2, the compound H(OC n H 2n-x )(OH) x+1 b) The step of reacting at least one reactive glycol represented by [wherein n=2~6 and x=0~10] with a reaction product which is a clear, homogeneous solution, at a temperature in the range of 50°C to 190°C to release ammonia; b) the step of supplying the reaction product from a) to a supply pump; c) the step of supplying the supply pump to dipropylenetriamine of formula H2N-(CH2)3-NH-(CH2)3-NH2 or formula H2N-(CH2) m -NH-(CH2) n -NH-R[wherein m and n are independently 2 to 5, preferably 2 to 3, more preferably 3, and R=C 1~18 The present invention provides a method for producing dialkylentriamine, which is alkyl, alkylcycloalkyl, OH-alkyl(hydroxyalkyl), H2N-alkyl(aminoalkyl), alkenyl, aryl, arylalkyl, or substituted arylalkyl, preferably R is aminopropyl, aminoethyl, hydroxyethyl, and hydroxypropyl, more preferably aminopropyl; and d)a) the reaction product is supplied to a reactor vessel where the internal temperature is in the range of 160-200°C to produce a solution of a bicyclic guanidine salt with high yield (85% or more), high dipropylenetriamine conversion rate (over 99%), and minimal or no undesirable urea impurities.

[0009] In one embodiment, bicyclic guanidine salts can be recovered as the free base by removing the solid salt by filtration using standard procedures, followed by neutralization with a solution of sodium methoxide or potassium methoxide in methanol. The bicyclic guanidine base can be further converted to salts of carboxylic acids including monocarboxylic acids, dicarboxylic acids, and polycarboxylic acids.

[0010] In another aspect, the present invention provides a method for producing bicyclic guanidines in high yield and high conversion with minimal or no presence of undesirable urea and monocyclic and acyclic guanidine impurities.

[0011] In another aspect, the present invention provides a method for controlling the yield and purity of bicyclic guanidines by appropriate selection of reactants.

[0012] The present invention also provides a method for controlling the yield and purity of bicyclic guanidine in either salt and / or free base form by appropriate selection of reactants to minimize the degradation of bicyclic guanidine during purification and isolation procedures.

[0013] In a further aspect, the present invention provides a method for controlling the yield and purity of bicyclic guanidine in either salt and / or free base form by appropriate selection of reactants to minimize the formation of impurities during production.

[0014] The present invention provides high-purity bicyclic guanidines such as TBD that are suitable for use as curing agents in silyl-terminated polyurethane (STPU) applications.

[0015] The present invention provides a method for preparing a silyl-terminated polyurethane (STPU) application comprising a curing agent, wherein the curing agent comprises at least one high-purity bicyclic guanidine.

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

[0017] The bicyclic guanidine produced by this invention is also a useful catalyst for water-curable silyl-modified polymers (SMPs). In this application, the bicyclic guanidine is part of a water-curable one-component (1K) silane-terminated polyurethane (STPU).

[0018] In another aspect, the present invention provides bicyclic guanidines such as high-purity TBD suitable for use as curing agents in silane-modified polymer (SMP) systems. For the purposes of the present invention, SMPs typically refer to polymers functionalized with at least two alkoxysilane groups at the terminal chain ends. Typically, in the presence of water in the form of ambient moisture, alkoxysilanes are hydrolyzed to form silanol-containing species, which then undergo polycondensation reactions to increase the molecular weight and / or crosslink density of the polymer, thereby curing / hardening the system. The hydrolysis / condensation curing process in SMP systems is relatively slow but can be accelerated by catalysts such as organotin compounds. It has been found that TBD produced by the present invention is also a very efficient catalyst for curing such silane-modified polymers, in particular SMPs functionalized with even less reactive ethoxysilyl groups instead of methoxysilyl groups. The present invention provides a method for preparing a silane-modified polymer (SMP) system comprising a curing agent, wherein the curing agent comprises at least one high-purity bicyclic guanidine.

[0019] Silane-terminated polyurethane (STPU) systems are a representative subtype of SMP systems that are rapidly and widely adopted in coatings, adhesives, sealants, and elastomers (CASE) applications because they benefit from both polyurethane performance and isocyanate-free processing. STPU prepolymers are the main components of such SMP formulations, and they are typically prepared from two different approaches: in one method, STPU prepolymers are prepared by the reaction of a polyol, such as a polyester or polyether polyol, with a γ-isocyanatopropyl alkoxysilane. A second preparation method for STPU prepolymers starts with a polyol, such as a polyether or polyester polyol, which is reacted with an excess of diisocyanate or polyisocyanate in the first reaction step. The resulting isocyanate-terminated prepolymer is then reacted with a γ-aminopropyl functionalized alkoxysilane to yield the desired alkoxysilane-terminated prepolymer. In addition to STPU prepolymers, various types of functional additives such as fillers, pigments, catalysts, moisture scavengers, UV absorbers and stabilizers, adhesion promoters, wetting agents, and defoamers can be used in such SMP formulations, depending on the end application.

[0020] A typical measure for evaluating the reactivity of SMP formulations is the tack-free time, or skinning time. Tack-free time refers to the time elapsed after application of the SMP formulation until the polymer surface hardens to the point where the material no longer transfers to the glove when touched with a gloved finger.

[0021] In another embodiment, the present invention provides bicyclic guanidines such as high-purity TBD that are suitable for use as polyurethane foam catalysts. [Brief explanation of the drawing]

[0022] [Figure 1] This is a diagram showing the rise time for Example 16. [Figure 2] These are photographs of a foam produced with Polycat® 8 and a foam produced with TBD. [Figure 3] It is a diagram of rise speed for Example 17. [Figure 4] These are photographs of a foam produced with DABCO® K15 and a foam produced with 33.9% TBD in EG. [Figure 5] It is a rise profile of succinic acid blocked TBD in a high-density spray foam formulation. [Figure 6] It is a photograph of a sample of manually mixed foam. [Figure 7] It is a diagram showing FTIR spectra of guanidine hydrochloride and the product of Example 1. [Figure 8] It is a diagram showing FTIR spectra of guanidine hydrochloride and the product of Example 4.

[0023] Detailed Description of the Invention The present invention provides a method for producing bicyclic guanidine and salts thereof in a reactor system, comprising: a) reacting a compound having the formula CX₂Y, wherein X=NH₂ and Y=NH, O or S, in the presence of an acid having pKa ≦ 2, with the formula H(OC n H 2n-x )(OH) x+1 wherein n=2~6 and x=0~10, with at least one reactive glycol represented by the formula at a temperature ranging from 50°C to 190°C to release ammonia and produce a reaction product which is a clear and homogeneous solution; b) feeding the reaction product from step a) into a feed pump; and c) supplying, via the feed pump, dipropylene triamine of formula H₂N-(CH₂)₃-NH-(CH₂)₃-NH₂ or H₂N-(CH₂) of formula m -NH-(CH₂) n -NH-R, wherein m and n are each independently 2 to 5, and R=C 1~18The present invention relates to a method comprising the steps of connecting a dialkylentriamine [which is alkyl, alkylcycloalkyl, OH-alkyl(hydroxyalkyl), H2N-alkyl(aminoalkyl), alkenyl, aryl, arylalkyl, or substituted arylalkyl] to a reactor vessel into which a dialkylentriamine has been introduced; and supplying the reaction product of d)a) to a reactor vessel with an internal temperature in the range of 160-200°C to produce a solution of a bicyclic guanidine salt in high yield, with a high dipropylenetriamine conversion rate and minimal or no undesirable urea impurities.

[0024] In one preferred embodiment, a compound having the formula CX2Y [wherein X=NH2 and Y=NH, O, or S] is subjected to the reaction of H(OC) in the presence of an acid with pKa ≤ 2. n H 2n-x )(OH) x+1 A glycol represented by [wherein n=2~6 and x=0~10] is reacted with a glycol at a temperature in the range of 50°C to 100°C to release ammonia, and formula: [ka] Carbamidate and formula: [ka] A reaction product containing dioxolane is produced, The amount of carbamidate in the reaction product is greater than the amount of dioxolane in the reaction product.

[0025] In a preferred embodiment, when X=NH2, Y=NH, n=2, and x=0, the carbamidate is 2-hydroxyethylcarbamimidate and the dioxolane is 1,3-dioxolane-2-imine.

[0026] In another preferred embodiment, a compound having the formula CX2Y [wherein X=NH2 and Y=NH, O, or S] is subjected to the reaction H(OC) in the presence of an acid with pKa ≤ 2. n H 2n-x )(OH) x+1A glycol represented by [wherein n=2~6 and x=0~10] is reacted with a glycol at a temperature in the range of 100°C to 190°C to release ammonia, and formula: [ka] Carbamidate and formula: [ka] A reaction product containing dioxolane is produced, The amount of dioxolane in the reaction product is greater than the amount of carbamidate in the reaction product.

[0027] In a preferred embodiment, when X=NH2, Y=NH, n=2, and x=0, the carbamidate is 2-hydroxyethylcarbamimidate and the dioxolane is 1,3-dioxolane-2-imine.

[0028] Preferably, in one embodiment, the reactive glycol is of formula H(OC) n H 2n-x )(OH) x+1 This can be expressed as [where n = 2 to 6 and x = 0 to 10].

[0029] More preferably, in another embodiment, the reactive glycol is of formula H(OC) n H 2n-x )(OH) x+1 This can be expressed as [where n = 2 to 4 and x = 0 to 1].

[0030] Preferably, in another embodiment, equation H(OC) is given by x=0 and n=2~4. n H 2n-x )(OH) x+1 The OH group in the reactive glycol is the OH group on the terminal carbon.

[0031] In another preferred embodiment, 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. 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.

[0032] Preferably, in one embodiment, the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, and phosphoric acid.

[0033] Preferably, in another embodiment, the formula H2N-(CH2) m -NH-(CH2) n In the case of the -NH-R dialkylentriamine, m and n are independently 2 to 3. Preferably, in another embodiment, the formula H2N-(CH2) m -NH-(CH2) n In the case of the -NH-R dialkylentriamine, m and n are independently 3. Preferably, in another embodiment, the formula H2N-(CH2) m -NH-(CH2) n In the case of dialkylentriamines of -NH-R, R is aminopropyl, aminoethyl, hydroxyethyl, and hydroxypropyl.

[0034] Preferably, in another embodiment, the bicyclic guanidine salt as a solution having a high yield is 85% or more. Preferably, in another embodiment, the bicyclic guanidine salt as a solution having a high dipropylenetriamine conversion rate is over 99%.

[0035] Next, after removing the solid salt by filtration using standard procedures, the bicyclic guanidine salt can be recovered as a free base by neutralization with a solution of sodium methoxide or potassium methoxide in methanol. The bicyclic guanidine base can be further converted into salts of carboxylic acids, including monocarboxylic acids, dicarboxylic acids, and polycarboxylic acids.

[0036] In a preferred embodiment, the method further includes the step of removing the solid salt by filtration and then neutralizing it with a solution of sodium methoxide or potassium methoxide in methanol.

[0037] In one preferred embodiment, bicyclic guanidines are prepared by using combinations of guanidine with various acids to produce the corresponding salts. Preferred examples of guanidine salts include guanidine sulfate, guanidine p-toluenesulfonate, guanidine hydrochloride, guanidine phosphate, guanidine triflate, and most preferably guanidine hydrochloride.

[0038] In preferred embodiments, the reactive glycol is a bio-based glycol. Preferably, in this embodiment, the guanidine salt is made from a sustainable glycol such as bio-based glycerol obtained from the hydrolysis of oils and fats.

[0039] In another preferred embodiment, the guanidine salt is prepared using bio-based 1,3-propanediol obtained by biomass fermentation, in which case the resulting solution has a composition that can be measured by ASTM D6866. 14 It is characterized by having a radioactive carbon isotope C.

[0040] In another preferred embodiment, the bicyclic guanidine salt as a solution in bio-based glycol contains a bio-based content of 95-60% by weight. In another preferred embodiment, the bicyclic guanidine salt as a solution in bio-based glycol contains a bio-based content of 80-60% by weight. In yet another preferred embodiment, the bicyclic guanidine salt as a solution in bio-based glycol contains a bio-based content of 70-60% by weight.

[0041] In another preferred embodiment, the bicyclic guanidine salt is of the formula H2N-(CH2) m -NH-(CH2) n -NH-R[wherein m and n are independently 2 to 5, preferably 2 to 3, more preferably 3, and R = hydrogen or C 1~18 The present invention is produced by using a dialkylentriamine which is alkyl or alkylcycloalkyl, OH-alkyl(hydroxyalkyl), H2N-alkyl(aminoalkyl), alkenyl, aryl, arylalkyl or substituted arylalkyl. In preferred embodiments, R is hydrogen, aminopropyl, aminoethyl, hydroxyethyl, and hydroxypropyl. In another preferred embodiment, R is aminopropyl.

[0042] In another preferred embodiment of the present invention, the bicyclic guanidine salt produced by the present invention allows for improved control of ammonia emissions during the reaction. Controlling ammonia emissions is important to reduce the risk of ammonia release into the environment and related consequences. Ammonia released during the reaction of glycol and guanidine can be captured within an emission control device. The rate of ammonia formation in a semi-batch step is related to the supply rate of the reactive glycol product. Ammonia formation can be rapidly reduced by stopping the supply pump. In contrast, in a batch process, the reaction temperature is the only way to control ammonia. Uncontrollable rapid ammonia formation can result in ammonia production rates exceeding the amount that the emission control device can handle. Furthermore, in the event of a failure of the emission control device, it has not been easy to stop ammonia formation.

[0043] In another preferred embodiment of the present invention, the bicyclic guanidine salts and bicyclic guanidines produced by the present invention result in a nearly quantitative conversion of the dialcylenetriamine. Dialkylentriamine is an undesirable component in bicyclic guanidine due to urea formation in the presence of isocyanates and degradation of the hydrofluoroolefin foaming agent. Dipropylenetriamine is a particularly undesirable component in the TBD product mixture due to its hazard classification. Specifically, it is germ cell mutagenic (Category 2) and specific target organ toxicity (repeated exposure), which need to be classified if present in the product mixture at concentrations of 1.0% or more. In particular, it is skin sensitizing, which needs to be classified if present in the product mixture at concentrations of 0.1% or more.

[0044] In another preferred embodiment of the present invention, the bicyclic guanidine salt produced by the present invention improves process safety by preventing unintended solid formation during process shutdown.

[0045] The reaction between the guanidine salt and the glycol ensures that the reaction mixture remains liquid at all times. In contrast, the batch process involves a two-phase reaction mixture until the guanidine salt dissolves at a reaction temperature above 60°C.

[0046] In a preferred embodiment, the present invention provides a bicyclic guanidine useful for producing rigid, flexible, and semi-flexible polyurethane foams having optimal physical properties, a regular cellular structure, low odor, and no discharge. Such polyurethane materials can be prepared using the bicyclic guanidine produced by the method of the present invention, and the concentrations of impurities such as urea, cyclic urea, and guanidine can be minimized because these are detrimental to the cellular structure of the foamed polyurethane.

[0047] In another preferred embodiment, the present invention provides a bicyclic guanidine, such as high-purity TBD, suitable for use as a curing agent in silyl-terminated polyurethane applications (STPUs). The present invention provides a method for preparing a silyl-terminated polyurethane application (STPU) comprising a curing agent, wherein the curing agent comprises at least one high-purity bicyclic guanidine.

[0048] In another preferred embodiment, the present invention provides bicyclic guanidines such as high-purity TBD suitable for use as curing agents in silane-modified polymer (SMP) systems. For the purposes of the present invention, a silane-modified polymer (SMP) refers to a polymer functionalized with at least two alkoxysilane groups. Typically, in the presence of water in the form of ambient moisture, the alkoxysilane is hydrolyzed to form silanol-containing species, which then undergo polycondensation reactions to increase the molecular weight and / or crosslink density of the polymer, and thus curing / hardening the system. The hydrolysis / condensation curing process can be accelerated by a catalyst such as a tin-based salt. The present invention provides a method for preparing a silane-modified polymer (SMP) system comprising a curing agent, wherein the curing agent comprises at least one high-purity bicyclic guanidine.

[0049] In another preferred embodiment, the method of the present invention involves 1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD, triazabicyclodecene), 1,5,7-triazabicyclo[4.3.0]non-6-ene (TBN, triazabicyclononane), 1,6,8-triazabicyclo[5.3.0]deca-7-ene, 1,6,8-triazabicyclo[5.4.0]undeca-7-ene, 7-(3-aminopropyl)-1,5,7-triazabicyclo[4.4.0]deca-7-ene, and 7-(3-aminopropyl)-1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD, triazabicyclodecene), 1,5,7-triazabicyclo[4.3.0]non-6-ene (TBN, triazabicyclononane), 1,6,8-triazabicyclo[5.3 1,6,8-triazabicyclo[5.4.0]undeca-7-ene, and 7-(3-aminopropyl)-1,5,7-triazabicyclo[4.4.0]deca-5-ene (TBD, triazabicyclodecene), 1,5,7-triazabicyclo[4.3.0]non-6-ene (TBN, triazabicyclononane), 1,6,8-triazabicyclo[5.3.0]deca-7-ene, 1,6,8- The present invention provides a bicyclic guanidine comprising bicyclo[4.4.0]deca-5-ene (aminopropyl-TBD, aminopropyl-triazabicyclodecene), 7-(3-aminopropyl)-1,5,7-triazabicyclo[4.3.0]non-6-ene (aminopropyl-TBN, aminopropyltriazabicyclononane), and at least one member selected from the group consisting of the following acids: hydrochloric acid, sulfuric acid, and phosphoric acid, and their corresponding salts.

[0050] In another preferred embodiment, the present invention provides a method for preparing a solution of a bicyclic guanidine salt having at least one organic carbone diacid, triacid or polyacid component, such salts being useful catalysts in spray foam applications using foaming agents such as hydrofluorocarbons, hydrochlorocarbons, hydrochloroolefins, hydrofluoroolefins, hydrofluorochloroolefins, fluoroolefins, chloroolefins, and hydrochlorofluorocarbons.

[0051] In another preferred embodiment, the 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 an organic carbone diacid, triacid, or polyacid made from a bicyclic guanidine.

[0052] In another preferred embodiment, the present invention relates to a method for producing a PIR / PUR rigid foam, comprising contacting at least one bicyclic guanidine with a polyisocyanate having a polyol premix with an isocyanate index of 120 to 800, the polyol premix comprising a polyol or polyol mixture, a surfactant, a flame retardant, an amine catalyst, water, various additives such as fillers, chain extenders, crosslinkers and colorants, as well as other additives and a blowing agent.

[0053] The catalyst composition of the present invention exhibits a substantially constant rise in form height over time, even at high isocyanate indexes, thereby providing advantages in the processing surface during high-speed PIR lamination processes.

[0054] In another preferred embodiment of the present invention, the catalyst prepared according to the present invention can be thermally stable at standard foaming temperatures and can produce PIR / PUR foam that is substantially free of volatile amines and / or amine odors.

[0055] In another preferred embodiment, the bicyclic guanidine produced by the present invention can be used together with other additives, depending on the type of application, including tertiary amines having or not having isocyanate-reactive groups, metal catalysts, trimer catalysts, chain extenders, crosslinking agents, fillers, and various other additives known in the art.

[0056] Preferred examples of tertiary amines that can be used with bicyclic guanidines are conventional tertiary amines, such as triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole, N-methylmorpholine (commercially available as DABCO® NMM), N-ethylmorpholine (commercially available as DABCO® NEM), triethylamine (commercially available as DABCO® TETN), N,N'-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine (commercially available as Polycat® 41), and 2,4,6-tris(dimethylaminomethyl)phenol (DABCO This includes, but is not limited to, TMR(registered trademark) 30, N-methyldicyclohexylamine (commercially available as Polycat(registered trademark) 12), pentamethyldipropylenetriamine (commercially available as Polycat(registered trademark) 77), N-methyl-N'-(2-dimethylamino)-ethylpiperazine, tributylamine, pentamethyldiethylenetriamine (commercially available as Polycat(registered trademark) 5), hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexylamine (commercially available as Polycat(registered trademark) 8), triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl) ether (commercially available as DABCO(registered trademark) BL19), tris(3-dimethylaminopropyl)amine (commercially available as Polycat(registered trademark) 9), 1,8-diazabicyclo[5.4.0]12-ndecane (commercially available as DABCO(registered trademark) DBU), or their acid block derivatives, and any mixture thereof. Polycat® 5, chemically known as pentamethyldiethylenetriamine, is particularly useful as a urethane catalyst for foam applications related to the present invention.

[0057] Preferably, the bicyclic guanidine can also be used with a tertiary amine having at least one isocyanate-reactive group, including a primary hydroxyl group, a secondary hydroxyl group, a primary amine group, a secondary amine group, a urea group, or an amide group.

[0058] Preferred examples of tertiary amine catalysts having isocyanate-reactive groups include N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, N,N-dimethylaminoethyl-N'-methylethanolamine, N,N,N'-trimethylaminopropylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dimethyl-N',N'-(2-hydroxypropyl)-1,3-propylenediamine, dimethylaminopropylamine, (N,N-dimethylaminoethoxy)ethanol, N-methyl-N'-(2-hydroxyethyl)piperazine, bis(N,N-dimethyl-3-aminopropyl)amine, and N,N-dimethylaminopropyl This includes, but is not limited to, urea, N,N-diethylaminopropylurea, N,N'-bis(3-dimethylaminopropyl)urea, bis(dimethylamino)-2-propanol, 6-dimethylamino-1-hexanol, N-(3-aminopropyl)imidazole, N-(2-hydroxypropyl)imidazole, N-(2-hydroxyethyl)imidazole, 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, N,N-dimethylaminoethyl-N'-methyl-N'-ethanol, dimethylaminoethoxyethanol, N,N,N'-trimethyl-N'-3-aminopropyl-bis(aminoethyl) ether, or combinations thereof.

[0059] In a preferred embodiment, the bicyclic guanidine may also be used with a tertiary amine acid-blocked with an acid, including carboxylic acids (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic), sulfonic acids, or other organic or inorganic acids. Preferred examples of carboxylic acids include monoacids, diacids, or polyacids, 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-ethylhexylcarboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, 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.

[0060] In one preferred embodiment, bicyclic guanidine may also be used in combination with a metal catalyst. For example, in one preferred embodiment, the tertiary amine catalyst component is used with an organotin compound, a tin(II) carboxylate, a bismuth(III) carboxylate, or a combination thereof. Preferred examples of organotin compounds or transition metal catalysts such as bismuth carboxylate may include at least one member selected from the group consisting of dibutyltin dilaurate, dimethyltin dilaurate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilauryl mercaptide, dibutyltin dilauryl mercaptide, dimethyltin diisooctyl maleate, dibutyltin diisooctyl maleate, dimethyltinbi(2-ethylhexyl mercaptoacetate), dibutyltinbi(2-ethylhexyl mercaptoacetate), stannous octanoate, other suitable organotin catalysts, or combinations thereof. Other metals such as bismuth (Bi) may also be included. Suitable bismuth carboxylic acid salts include salts of pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexylcarboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, and other suitable carboxylic acids. Other salts of transition metals of lead (Pb), iron (Fe), and zinc (Zn) may also include salts of pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexylcarboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids.

[0061] Preferably, the bicyclic guanidine of the present invention may further contain any amount of other catalytic material, such as a carboxylate. Specific examples of alkali metals, alkaline earth metals, 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 octanoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonanoate, potassium stearate, sodium octanoate, lithium stearate, sodium caprate (sodium n-decanoate), lithium octanoate, 2-hydroxypropyltrimethylammonium octanoate solution, or any combination thereof.

[0062] Preferably, the amounts of other catalyst materials and salts may be in the range of 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.

[0063] Form preparation Any of the various types of foams known in the art can be produced using the method of the present invention, which uses a typical polyurethane formulation with an appropriate amount of bicyclic guanidine added, as illustrated in the following example.

[0064] For example, the excellent properties of flexible polyurethane foam described herein typically include the components shown in Table A below, in the amounts indicated. The components shown in Table A will be discussed in detail later below.

[0065] [Table 1]

[0066] The amount of polyisocyanate used in the polyurethane formulation according to the present invention is not limited, but will typically be within the range known to those skilled in the art. Exemplary ranges are given in Table A and are indicated by reference to the “NCO index” (isocyanate index). As known in the art, the NCO index is defined as the number of isocyanate equivalents divided by the total number of active hydrogen equivalents, multiplied by 100. The NCO index is expressed by the following formula:

[0067] NCO index=[NCO / (OH+NH)] * 100 In flexible foams, copolymer polyols are typically used as part of the total polyol content in the foam composition, along with base polyols having a weight-average molecular weight of about 4000–5000 and a hydroxyl value of about 28–35. Base polyols and copolymer polyols will be described in detail later in this specification.

[0068] Polyols may have a functional value of about 2 to about 8, about 2 to about 6, and in some cases about 2 to about 4. Polyols may also have a hydroxyl value of about 10 to about 900, typically about 15 to about 600, and more typically about 20 to about 200.

[0069] catalyst Preferably, the amount of bicyclic guanidine may be in the range of 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 components may be in the range of 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.

[0070] Preferred examples of foaming co-catalysts containing isocyanate reactive groups that can be used in combination with the catalysts mentioned above 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 foaming co-catalyst may be in the range of 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.

[0071] Preferably, the catalyst composition may also contain other components, such as organotin compounds or transition metal catalysts such as bismuth carboxylate, when the desired polyurethane foam is a flexible slab stock. The metal catalyst may include at least one member selected from the group consisting of dialkyltin carboxylates such as dibutyltin dilaurate, dimethyltin dilaurate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilauryl mercaptide, dibutyltin dilauryl mercaptide, dimethyltin diisooctyl maleate, dibutyltin diisooctyl maleate, dimethyltin bis(2-ethylhexyl mercaptoacetate), dibutyltin bis(2-ethylhexyl mercaptoacetate), dimethyltin neodecanoate, dibutyltin neodecanoate, dimethyltin isononanoate, dibutyltin isononanoate, stannous octanoate, stannous neodecanoate, stannous isononanoate, or other suitable organotin catalysts, or other suitable stannous carboxylates, or combinations thereof. It may also include other metals such as bismuth (Bi) and its salts. Suitable metal salts include carboxylate salts containing salts of acetic acid, propanoic acid, butanoic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexylcarboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, 16-decanoic acid, heptadecanoic acid, octadecanoic acid, and other suitable carboxylic acids. Other salts of transition metals of lead (Pb), iron (Fe), or zinc (Zn) may also contain salts of pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexylcarboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids. Preferably, the amount of the aforementioned metal catalyst may be in the range of about 0 pphp to about 20 pphp, about 0 pphp to about 10 pphp, and in some cases, about 0 pphp to about 0.01 pphp.

[0072] Bicyclic guanidines may be acid-blocked with acids, including carboxylic acids (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic), sulfonic acids, or other organic or inorganic acids. Examples of carboxylic acids include monoacids, diacids, or polyacids, 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-ethylhexylcarboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanoic acid, neoheptanoic acid, nonanoic acid, neononanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, 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.

[0073] The bicyclic guanidine of the present invention can be used with the amines listed above, but typically the total amount of tertiary amine catalyst (i.e., the bicyclic guanidine of the present invention + any co-gelling catalyst) introduced to produce the form according to the present 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 can be used. The term "pphp" means parts per 100 parts of polyol.

[0074] Organic isocyanates Preferred and 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 present invention, polyurethane foam is produced using 2,4-TDI, 2,6-TDI, or any mixture thereof. Other suitable isocyanate compounds are diisocyanate mixtures commercially known as "crude MDI." One example is sold by Dow Chemical Company under the name PAPI, which contains about 60% 4,4'-diphenylmethane diisocyanate along with other isomers and similar higher-grade polyisocyanates. Any suitable isocyanate can be used, but one example of such is an isocyanate having an index range of about 60 to about 200, typically about 90 to about 120. The amount of isocyanate is typically in the range of about 95 to about 105, and in one aspect of the present invention, the isocyanate index is in the range of about 60 to about 65.

[0075] Polyol components Polyurethanes are produced by the reaction of an organic isocyanate with the hydroxyl group of a polyol, typically a mixture of polyols. The polyol component of the reaction mixture includes at least a major or "base" polyol. Suitable base polyols for use in the present invention include, as non-limiting examples, polyether polyols. Polyether polyols include poly(alkylene oxide) polymers such as poly(ethylene oxide) polymers and poly(propylene oxide) polymers, as well as copolymers having terminal hydroxyl groups derived from polyvalent compounds including diols, triols, and higher alcohols. Preferred examples of diols and triols for reaction with 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, trimethylolpropane, and similar low molecular weight polyols. Other examples of base polyols known in the art include polyhydroxy-terminated acetal resins, hydroxyl-terminated amines, and hydroxyl-terminated polyamines. Examples of these and other suitable isocyanate-reactive materials can be found in U.S. Patent No. 4,394,491, incorporated herein by reference. Suitable polyether polyols include those containing tertiary amine groups that can catalyze the gelation and foaming reactions of polyurethanes, including, for example, those described in U.S. Patent No. 8,367,870, International Publication No. 03 / 016373, International Publication No. 01 / 58976, International Publication No. 2004 / 060956, International Publication No. 03 / 016372, and International Publication No. 03 / 055930, the disclosures of the aforementioned U.S. patents and international publications incorporated herein by reference. Other useful polyols may include polyalkylene carbonate-based polyols and polyphosphate-based polyols.

[0076] In one aspect of the present invention, a single high molecular weight polyether polyol can be used as the base polyol. Alternatively, mixtures of high molecular weight polyether polyols, such as difunctional and trifunctional materials and / or mixtures of materials with different molecular weights or different chemical compositions, can be used. Such difunctional and trifunctional 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.

[0077] In addition to, or instead of, the base polyols described above, materials commonly referred to as "copolymer polyols" may be included in the polyol components for use according to the present invention. Copolymer polyols can be used in polyurethane foams to increase resistance to deformation and, for example, improve load-bearing properties. Depending on the load-bearing requirements, copolymer polyols may account for about 0 to about 80 weight percent of the total polyol content.

[0078] Preferred examples of copolymer polyols include, but are not limited to, graft polyols and polyurea-modified polyols, both of which are known and commercially available in the art.

[0079] Grafted polyols are prepared by copolymerizing vinyl monomers, typically styrene and acrylonitrile, in a starting polyol. The starting polyol is typically a glycerol-started triol, typically end-capped with ethylene oxide (about 80–85% primary hydroxyl groups). Part of the copolymer is grafted onto part of the starting polyol. Grafted polyols also contain homopolymers of styrene and acrylonitrile, as well as the unmodified starting polyol. The styrene / acrylonitrile solid content of grafted polyols is typically in the range of 5% to 45% by weight, but any type of grafted polyol known in the art can be used.

[0080] Polyurea-modified polyols are formed by the reaction of a diamine with a diisocyanate in the presence of a starting polyol, and the product contains a polyurea dispersion. A suitable variant of polyurea-modified polyol for use is polyisocyanate polyaddition (PIPA) polyol, which is formed by the in situ reaction of an isocyanate with an alkanolamine in the polyol.

[0081] Other suitable polyols that can be used in this invention include natural oil polyols or polyols obtained from renewable natural resources such as vegetable oils. Polyols useful for preparing polyurethane foams from inexpensive and renewable resources are highly desirable in order to minimize the depletion of fossil fuels and other unsustainable resources. Natural oils consist of triglycerides of saturated and unsaturated fatty acids. One natural oil polyol is castor oil, i.e., the natural triglyceride of ricinoleic acid, which is commonly used to make polyurethane foams, although it has certain limitations such as a low hydroxyl content. Other natural oils need to be chemically modified to introduce a sufficient hydroxyl content to make these natural oils useful for the production of polyurethane polymers. There are two chemically reactive sites that can be considered when attempting to modify natural oils or fats into useful polyols: 1) unsaturated sites (double bonds); and 2) ester functional groups. Unsaturated sites present in oils or fats can be hydroxylated by epoxidation, followed by ring-opening or hydroformylation, followed by hydrogenation. Alternatively, transesterification can be used to introduce OH groups into natural oils and fats. The chemical process for preparing natural polyols using the epoxidation route involves a reaction mixture requiring epoxidized natural oils, a ring-opening acid catalyst, and a ring-opening agent. Epoxidized natural oils include epoxidized vegetable-based oils (epoxidized vegetable oils) and epoxidized animal fats. 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, cottonseed oil, safflower oil, peanut oil, linseed oil, and combinations thereof. Animal fats include fish, animal fat, and lard. These natural oils are C 12 ~C 24These are triglycerides of fatty acids that may be saturated or unsaturated, having various chain lengths. These acids may be: 1) saturated: lauric acid, myristic acid, palmitic acid, stearic acid, arachidonic acid, and lignoceric acid; 2) monounsaturated: palmitoleic acid, oleic acid; 3) polyunsaturated: linoleic acid, linolenic acid, and arachidonic acid. Partially or completely epoxidized natural oils can be prepared by reacting peroxy acids under appropriate reaction conditions. Examples of peroxy acids used for oil epoxidation are described in International Publication No. 2006 / 116456, incorporated herein by reference. Ring-opening of epoxidized oils can be performed with alcohols, water, and other compounds having one or more nucleophiles. Depending on the reaction conditions, oligomerization of epoxidized oils may also occur. Ring-opening produces natural oil polyols that can be used in the production of polyurethane products. In the hydroformylation / hydrogenation process, oils are 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 then hydrogenated in the presence of a cobalt or nickel catalyst to form a polyol. Alternatively, polyols from natural oils and fats can be produced by transesterification with a suitable polyhydroxyl-containing substance using an alkali metal or alkaline earth metal base or salt as a transesterification catalyst. Any natural oil or any partially hydrogenated oil can be used in the transesterification process. Examples of oils include, but are not limited to, soybean oil, corn oil, cottonseed oil, peanut oil, castor oil, sunflower oil, canola oil, rapeseed oil, safflower oil, fish oil, seal oil, palm oil, tung oil, olive oil, or blends thereof. Any polyfunctional hydroxyl compound, such as lactose, maltose, raffinose, sucrose, sorbitol, xylitol, erythritol, mannitol, or any combination thereof, may also be used.

[0082] The amount of polyol is defined in pphp. Three types of polyols are defined first: standard polyols, or polyether polyols, which can be used in the range of approximately 100 pphp (sole polyol) to approximately 10 pphp. Copolymer polyols (CPPs) can be used in the range of approximately 0 to approximately 80 pphp. Finally, NOPs (natural oil polyols) can typically exist in the range of approximately 0 to approximately 40 pphp.

[0083] The polyol may have an OH number of 10 to about 900 and a functional value of about 2 to 8. The OH number and functional value of the polyol are selected to obtain a form having the desired physical properties.

[0084] In open-cell flexible molded foams, primary or "base" polyether polyols are typically used. Polyether polyols include poly(alkylene oxide) polymers such as poly(ethylene oxide) polymers and poly(propylene oxide) polymers, as well as copolymers having terminal hydroxyl groups derived from polyvalent compounds including diols and triols. These polyols may have a functional value of about 2 to about 8, about 2 to about 6, typically about 2 to about 4. Polyols may have a hydroxyl value of about 10 to about 900, typically about 15 to about 600, more typically about 20 to about 50. In flexible molded foams, copolymer polyols are also used as part of the total polyol content in the foam composition, typically having an OH value in the range of 15 to 50, a MW range typically 1200 to 8000, more typically 2000 to 6000, and a % solids content of 10% to 60%. In open-cell low-density spray foams, polyether polyols with an average MW of 1500–6000 and an OH number of 15–50 are typically used. The polyol content is defined in pphp. Four types of polyols are defined: standard polyols, or polyether polyols which can be used in the range of about 100 pphp (sole polyol) to about 10 pphp; copolymer polyols (CPPs) which can be used in the range of about 0 to about 80 pphp; and NOPs (natural oil polyols) which can exist in the range of about 0 to about 40 pphp. Finally, Mannich polyols are used in combination with other polyols in the range of 0 pphp–80 pphp, about 0 pphp–about 50 pphp, and in some cases about 0 pphp–about 20 pphp.

[0085] Other polyols typically used in PIR / PUR foaming processes include polyalkylene ethers and polyester polyols. Polyalkylene ether polyols include poly(alkylene oxide) polymers such as poly(ethylene oxide) polymers and poly(propylene oxide) polymers, as well as copolymers having terminal hydroxyl groups derived from polyvalent compounds including diols and triols. These include, but are not limited to, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylolpropane, cyclohexanediol, and sugars such as sucrose, as well as similar low molecular weight polyols.

[0086] Amine polyether polyols can be used in the present invention. These can be prepared, for example, by reacting amines such as ethylenediamine, diethylenetriamine, tolylenediamine, diphenylmethanediamine, or triethanolamine with ethylene oxide or propylene oxide.

[0087] In another aspect of the present invention, a single high molecular weight polyether polyol, or a mixture of high molecular weight polyether polyols such as a mixture of different polyfunctional materials and / or materials having different molecular weights or different chemical compositions, can be used.

[0088] In yet another aspect of the present invention, polyester polyols, including those produced by reacting a dicarboxylic acid with an excess diol, can be used. 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 diol, for example, by reacting caprolactone with propylene glycol. In further aspects, active hydrogen-containing compounds such as polyester polyols and polyether polyols, as well as combinations thereof, are useful in the present invention.

[0089] Preferably, the polyol may have an OH value of about 5 to about 600, about 100 to about 600, and in some cases about 50 to about 100, and a functional value of about 2 to about 8, about 3 to about 6, and in some cases about 4 to about 6.

[0090] Preferably, the amount of polyol may be in the range of approximately 0 pphp to approximately 100 pphp, approximately 10 pphp to approximately 90 pphp, and in some cases approximately 20 pphp to approximately 80 pphp.

[0091] foaming agent The formation of polyurethane foam can be assisted by creating voids within the polyurethane matrix during polymerization, including the use of a blowing agent (BA). Any suitable blowing agent can be used. Suitable blowing agents include compounds with low boiling points that evaporate during the exothermic polymerization reaction. Such blowing agents are often inert, or they are less reactive and therefore may decompose or not react during the polymerization reaction. Preferred examples of low-reactivity blowing agents include, but are not limited to, carbon dioxide, chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), fluoroolefins (Fos), chlorofluoroolefins (CFOs), hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), acetone, and low-boiling hydrocarbons such as cyclopentane, isopentane, n-pentane, and mixtures thereof. The amount of BA is typically about 0 pphp (e.g., when water is used to foam the polyurethane polymer) to about 80 pphp. Other suitable blowing agents include compounds that react with isocyanate compounds to produce gas, such as water. Water (which reacts with isocyanates to produce CO2) can exist in concentrations ranging from approximately 0 (if BA is present) to approximately 60 pphp (in very low-density forms), typically from approximately 1.0 pphp to approximately 10 pphp, and in some cases from approximately 2.0 pphp to approximately 5 pphp.

[0092] Preferred examples of HFCs include, but are not limited to, HFC-245fa, HFC-134a, and HFC-365, and specific examples of HCFCs include, but are not limited to, HCFC-141b, HCFC-22, and HCFC-123.

[0093] Exemplary hydrocarbons include, but are not limited to, n-pentane, isopentane, cyclopentane, 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.

[0094] Furthermore, in another aspect of the present invention, the foaming agent essentially consists of n-pentane, or a mixture of n-pentane and one or more foaming agents.

[0095] Preferred examples of hydrohaloolefin blowing agents, among other HFOs, include HFO-1234ze (trans-1,3,3,3-tetrafluoropropane), HFO-1234yf (2,3,3,3-tetrafluoropropene), and HFCO-1233zd (1-propene, 1-chloro-3,3,3-trifluoro), and HFO-1336mzz I (trans-1,1,1,4,4,4-hexafluoro-2-butene).

[0096] Other optional components The formulation for producing the foam according to the present invention may contain a variety of other components. Preferred optional components include, but are not limited to, foam stabilizers, crosslinking agents, chain extenders, pigments, fillers, flame retardants, auxiliary urethane gelling catalysts, auxiliary urethane foaming catalysts, transition metal catalysts, alkali and alkaline earth metal carboxylates, and any combination thereof.

[0097] Preferred foam stabilizers may include, for example, silicone surfactants, as well as organic anionic, cationic, amphoteric, 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 sulfate esters, salts of phosphate esters, salts of sulfonic acids, and any combination thereof. Preferred suitable cationic surfactants include, but are not limited to, quaternary ammonium salts (pH-dependent or permanently charged) such as cetyltrimethylammonium chloride, cetylpyridinium chloride, polyethoxylated tallowamines, benzalkonium chloride, and benzethonium chloride. Preferred suitable amphoteric or amphoteric surfactants include, but are not limited to, sultaines, amino acids, imino acids, betaines, and phosphates. Preferred and suitable nonionic 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 alkylphenol ethers, and glycol alkyl esters. Preferably, the foam stabilizer can be used in amounts of about 0.1 to about 20 pphp, typically about 0.1 to about 10 pphp, and in some cases about 0.1 to about 5.0 pphp. Preferably, the flame retarder can be used in amounts of about 0 to about 20 pphp, about 0 to about 10 pphp, and about 0 to about 5 pphp.

[0098] The crosslinking agents include, but are not limited to, low molecular weight compounds comprising at least two moieties selected from hydroxyl groups, primary amino groups, secondary amino groups, and other active hydrogen-containing groups reactive with isocyanate groups. Preferred crosslinking agents include, for example, polyhydric alcohols (particularly trihydric alcohols such as glycerol and trimethylolpropane), polyamines, and combinations thereof. Non-limiting examples of polyamine crosslinking agents include diethyltoluenediamine, chlorodiaminobenzene, diethanolamine, diisopropanolamine, triethanolamine, tripolanolamine, 1,6-hexanediamine, and combinations thereof. Typical diamine crosslinking agents contain 12 or fewer carbon atoms, more generally 7 or fewer. Preferably, the crosslinking agent can be used in amounts of about 0.1 to about 20 pphp, typically about 0.1 to about 10 pphp, and in some cases about 0.1 to about 5.0 pphp.

[0099] Preferred chain extenders include, but are not limited to, compounds having hydroxyl or amino functional groups, such as glycols, amines, diols, and water. Specific non-limiting examples of chain extenders include 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 amounts of about 0.1 to about 100 pphp, typically about 0.1 to about 50 pphp, and in some cases about 0.1 to about 5.0 pphp.

[0100] Pigments can be used to color-code polyurethane foam during manufacturing, for example, to identify the grade of the product or to conceal yellowing. The pigments may include any suitable organic or inorganic pigments known in polyurethane technology. 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 oxide, or chromium oxide. Preferably, the amount of pigment may range from about 0 pphp (no pigment added) to about 40 pphp.

[0101] Fillers can be used to improve the density and load-bearing properties of polyurethane foam. Suitable fillers include, but are not limited to, barium sulfate or calcium carbonate. Preferably, the amount of filler may range from about 0 pphp (no filler added) to about 40 pphp.

[0102] Flame retardants can be used to reduce the flammability of polyurethane foam. Suitable flame retardants include, but are not limited to, chlorinated phosphate esters, chlorinated paraffins, or melamine powder. Preferably, the flame retardant can be used in amounts of about 0 to about 20 pphp, about 0 to about 10 pphp, and about 0 to about 5 pphp.

[0103] In one aspect of the present invention, the bicyclic guanidine of the present invention can be used together with an isocyanate-free amine catalyst, which is typically known as a fugitive catalyst. Preferred examples of volatile amine catalysts in this category include triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole, N-methylmorpholine, N-ethylmorpholine, triethylamine, N,N'-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 2,4,6-tris(dimethylamino-methyl)phenol, N-methyldicyclohexylamine, pentamethyldipropylenetriamine, 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]26-ndecane, or their acid block derivatives, and any mixtures thereof.

[0104] Certain aspects of the present invention are illustrated by the following examples. These examples are for illustrative purposes only and do not limit the scope of the claims attached herein. The forms were evaluated using manual mixed evaluation or machine evaluation, as described below.

[0105] Examples Example 1: The present invention Preparation of reaction products from guanidine and ethylene glycol Guanidine hydrochloride (95.5 g, 1.00 mol) was suspended in 143 g of ethylene glycol in a 250 mL three-necked RB flask. The reactor assembly was purged with nitrogen for at least 5 minutes. A scrubber supplied with glacial acetic acid and deionized water was connected to the reactor via a tube to capture the generated ammonia. The suspension was heated to approximately 50°C, with ammonia generation, and stirred until the mixture became clear. The IR spectra of the reactants and products were recorded. The reaction was monitored by IR. Changes in the IR spectrum occurred particularly at the C=NH stretching frequency, which indicates the disappearance of guanidinium chloride (ν=1625 cm⁻¹). -1 and 1590cm -1 ) and the appearance of new products (ν = 1655 cm⁻¹) -1 This essentially demonstrated the following. The shift to higher frequencies coincides with the formation of 2-hydroxyethylcarbamimidate and its equilibrium product, 1,3-dioxolane-2-imine. The reaction mixture was not purified and was used in the next step as obtained.

[0106] [ka]

[0107] [Table 2]

[0108] The FTIR spectra of guanidine hydrochloride and the product of Example 1 are shown in Figure 7.

[0109] Example 2: The present invention Preparation of reaction products from guanidine and ethylene glycol Guanidine hydrochloride (95.5 g, 1.00 mol) was suspended in 143 g of ethylene glycol in a 250 mL three-necked RB flask. The reactor assembly was purged with nitrogen for at least 5 minutes. A scrubber supplied with glacial acetic acid and deionized water was connected to the reactor via tubing to capture the generated ammonia. The suspension was heated to approximately 170°C, with ammonia generation, and stirred until the mixture became clear. The released ammonia was captured in an acid scrubber. The IR spectra of the reactants and products were recorded, and changes in the IR spectra, particularly the C=NH stretching, indicated product formation, as described in Example 1. The reaction mixture was not purified and was used in the next step as obtained.

[0110] Example 3: The present invention Reaction of product mixture from Example 1 with DPTA The product obtained in Example 1 was loaded into an addition funnel. Dipropylenetriamine (DPTA, 131.2 g, 1.00 mol) and a magnetic stirring rod were loaded into the reaction flask. The reaction apparatus was essentially a three-necked round-bottom flask containing DPTA and connected to an addition funnel with a reflux condenser, a thermocouple, and the reaction product of Example 1. The reactor assembly was purged with nitrogen for at least 5 minutes. A scrubber supplied with glacial acetic acid and deionized water was connected to the reactor via tubing to capture the generated ammonia. The DPTA was heated to 170°C with stirring. The reaction product of Example 1 was then slowly added, at which point the generation of ammonia was detected. Heating was continued for approximately 5.5 hours until the generation of ammonia stopped. The reaction flask was cooled to room temperature. The contents of the flask weighed approximately 320 g, and a GC sample was prepared in MeOH, to which 1 M KOH was added to produce a free base. Unreacted DPTA was not observed in the GC chromatogram. TBD was the largest component in the GC chromatogram, excluding EG. The DPTA conversion rate (quantified) and TBD salt yield (91%) were calculated from the NMR results.

[0111] [ka]

[0112] Example 4: The present invention Preparation of reaction products from guanidine and 1,3-propanediol Guanidine hydrochloride (95.5 g, 1.00 mol) was suspended in 223 g of 1,3-propanediol in a 250 mL three-necked RB flask. The reactor assembly was purged with nitrogen for at least 5 minutes. A scrubber supplied with glacial acetic acid and deionized water was connected to the reactor via tubing to capture the generated ammonia. The suspension was heated to approximately 50°C, with ammonia generation, and stirred until the mixture became clear. The IR spectra of the reactants and products were recorded. Immediately after the reaction, changes in the IR spectrum occurred, particularly at the C=NH stretching frequency, which substantially indicated the disappearance of guanidinium chloride. The reaction mixture was not purified and was used in the next step as obtained. The FTIR spectra of guanidine hydrochloride and the product of Example 4 are shown in Figure 8.

[0113] Example 5: The present invention Reaction of the product mixture in Example 4 with DPTA The product obtained in Example 4 was loaded into an addition funnel. Dipropylenetriamine (DPTA, 131.2 g, 1.00 mol) and a magnetic stirring rod were loaded into a reaction flask (500 mL, three-neck RB). The reaction apparatus was assembled and purged with nitrogen for at least 5 minutes. The reaction apparatus was connected to an acid scrubber via tubing and the entire apparatus was purged with nitrogen for at least 5 minutes. The DPTA was heated to 170°C with stirring, and the product from Example 4 was slowly added at 170°C. Heating was continued for approximately 7 hours until the generation of ammonia stopped. The reaction flask was cooled to room temperature, and a yellow liquid was observed. The contents of the flask weighed approximately 387 g, and a GC sample was prepared in MeOH. Free bases were produced by adding 1 M KOH to the MeOH. Unreacted DPTA was not observed in the GC chromatogram. TBD was the largest component in the GC chromatogram, except for propanediol (PDO). The DPTA conversion rate (quantitative) and TBD salt yield (90%) were calculated from the NMR results.

[0114] Example 6: The present invention TBD in Biobase 1,3-propanediol * Preparation of HCl The procedures 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 bio-based PDO commercially available as SUSTERRA®. The DPTA conversion rate (quantified) and TBD salt yield (89%) were calculated from the NMR results.

[0115] Example 7: The present invention Preparation of TBD sulfate in ethylene glycol (EG) Guanidine sulfate (16.2 g, 0.075 mol) was suspended in 25 g of ethylene glycol in a 100 mL three-necked RB flask. The reactor assembly was purged with nitrogen for at least 5 minutes. A scrubber supplied with glacial acetic acid and deionized water was connected to the reactor via tubing to capture the generated ammonia. The suspension was reacted as described in Example 1. The reaction mixture was cooled and placed in an addition funnel. Dipropylenetriamine (DPTA, 19.7 g, 0.150 mol) and a magnetic stirring rod were added to the reaction flask (100 mL, three-necked RB). EG (19 g) was also added to the reaction flask to obtain a DPTA solution (52 wt%) in EG. The reactor was assembled and purged with nitrogen for at least 5 minutes. The DPTA solution was heated to 170°C with stirring, and the reaction product was slowly added at 170°C. Heating was continued for approximately 5 hours until the generation of ammonia stopped. The reaction flask was cooled to room temperature, and a golden-yellow liquid was observed. The contents of the flask weighed approximately 72 g. The GC sample was prepared in MeOH, and 1 M KOH was added to the MeOH to produce a free base. Unreacted DPTA was not observed in the GC chromatogram. TBD was the largest component in the GC chromatogram, excluding EG. The DPTA conversion rate (quantification) and TBD salt yield (97%) were calculated from the NMR results.

[0116] Example 8: The present invention Preparation of TBD methanesulfonate in ethylene glycol 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 supplied with glacial acetic acid and deionized water was connected to the reactor via a tube to capture the generated ammonia. This suspension was reacted as described above to obtain a methanesulfonate salt mixture as described in Example 1. Dipropylenetriamine (DPTA, 9.84 g, 0.0750 mol) and a magnetic stirring rod were placed in a reaction flask (100 mL, three-neck RB). The reaction apparatus was assembled and purged with nitrogen for at least 5 minutes. DPTA was heated to 170°C with stirring, and the reaction product was slowly added at 170°C. Heating was continued for approximately 5 hours until the generation of ammonia stopped. The reaction flask was cooled to room temperature, and a yellow liquid was observed. The contents of the flask weighed approximately 77 g. The GC sample was prepared in MeOH, and 1 M KOH was added to the MeOH to produce a free base. Unreacted DPTA was not observed by the GC chromatogram. TBD was the largest component in the GC chromatogram, excluding EG. The DPTA conversion rate (quantification) and TBD salt yield (over 99%) were calculated from the NMR results.

[0117] Example 9: The present invention TBN in ethylene glycol * Preparation of HCl 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 stirring rod were placed in a reaction flask (100 mL, three-neck RB). The reaction apparatus was assembled and purged with nitrogen for at least 5 minutes. AEPDA was heated to 170°C with stirring, and the reaction product was slowly added at 170°C. Heating was continued for approximately 4 hours until the generation of ammonia stopped. The reaction flask was cooled to room temperature, and a pale yellow liquid was observed. The contents of the flask weighed approximately 37 g, and a GC sample was prepared in MeOH. 1 M KOH was added to the MeOH to produce a free base. Unreacted AEPDA was not observed in the GC chromatogram. TBN was the largest component in the GC chromatogram, excluding EG. The AEPDA conversion rate (quantified) and TBN salt yield (94%) were calculated from the NMR results.

[0118] Example 10: The present invention AP-TBD in ethylene glycol * Preparation of HCl 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 stirring rod were placed in a reaction flask (100 mL, three-neck RB). The reaction apparatus was assembled and purged with nitrogen for at least 5 minutes. TPTA was heated to 170°C with stirring, and the reaction product was slowly added at 170°C. Heating was continued for approximately 4.5 hours until the generation of ammonia stopped. The reaction flask was cooled to room temperature, and a pale yellow liquid was observed. The contents of the flask weighed approximately 30 g, and a GC sample was prepared in MeOH. 1 M KOH was added to the MeOH to produce a free base. Unreacted TPTA was not observed in the GC chromatogram. AP-TBD was the largest component in the GC chromatogram. The TPTA conversion rate (quantitative) and AP-TBD salt yield (89%) were calculated from the NMR results.

[0119] Example 11: The present invention Preparation of TBD in ethylene glycol using NaOMe solution TBD during EG *HCl (157 g, 0.500 mol) was placed in a 1 L reaction flask that had been dried in an oven. The apparatus was assembled and purged with nitrogen for approximately 10 minutes. A room temperature water bath was used for cooling. The solution was mixed using a mechanical stirrer (150 rpm). Sodium methoxide (NaOMe) solution (28 wt%, 101 g, 0.52 mol) was placed in the addition funnel. The apparatus was purged with nitrogen for approximately 10 minutes before addition. The NaOMe solution was added over 5 minutes, and salt formation was observed immediately after addition. No exothermic reaction was observed immediately after addition. The addition funnel was rinsed with an additional approximately 120 mL of anhydrous IPA. The white slurry was mixed for a further 60 minutes, and the white slurry was transferred to a glass bottle. The mixture was filtered using a 1 L Millipore pressure filter equipped with Whatman Grade I filter paper (150 mm diameter). The filtrate was pale yellow and contained fine solids, and 309 g was collected. Volatile components were removed under reduced pressure using a rotary evaporator. The weight of the concentrated filtrate was 127 g, and nitrogen was sprayed onto the filtrate overnight. A considerable amount of salt precipitated on the flask wall overnight, and the final weight of the concentrated filtrate was 126 g. The concentrated filtrate was filtered using a 1 L Millipore pressure filter with a 0.45 micron Millipore Duropore filter membrane (142 mm). The filtrate (112 g) was a golden yellow liquid. A certain amount was taken for GC analysis in MeOH. GC chromatography showed that TBD was the largest component in the GC chromatogram, excluding EG. The TBD yield was approximately 73%.

[0120] Example 12: The present invention Preparation of TBD in ethylene glycol using KOMe solution TBD during EG *HCl (162.3 g, 0.501 mol) was placed in a 1 L reaction flask that had been dried in an oven. The apparatus was assembled and purged with nitrogen for approximately 10 minutes. A room temperature water bath was used for cooling. The solution was mixed using a mechanical stirrer. Potassium methoxide (KOMe) solution (25.1 wt%, 144 g, 0.52 mol) was placed in the addition funnel. The apparatus was purged with nitrogen for approximately 10 minutes before addition. The KOMe solution was added over 30 minutes, and salt formation was observed immediately after addition. No exothermic reaction was observed immediately after addition. The addition funnel was rinsed with an additional approximately 150 mL of anhydrous IPA. The white slurry was mixed for a further 2 hours, and the white slurry was transferred to a glass bottle. The mixture was filtered using a 1 L Millipore pressure filter equipped with Whatman Grade I filter paper (150 mm diameter). The filtrate was pale yellow, contained trace amounts of solid, and 444 g was collected. 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 a 1 L Millipore pressure filter equipped with a 0.45 micron Millipore Duropore filter membrane (142 mm). The filtrate (134 g) was a golden yellow liquid. To remove residual solvent, nitrogen was sprayed onto the filtrate overnight, yielding 133 g after spraying. A fixed amount was taken for GC analysis in MeOH. GC chromatogram showed that TBD was the largest component in the GC chromatogram, excluding EG. The TBD yield was approximately 88%.

[0121] Example 13: The present invention Preparation of TBD in 1,3-propanediol using NaOMe solution TBD during PDO *HCl (214.6 g, 0.501 mol) was placed in a 1 L reaction flask that had been dried in an oven. The apparatus was assembled and purged with nitrogen for approximately 10 minutes. The solution was mixed using a mechanical stirrer (100 rpm). NaOMe solution (28.1 wt%, 102 g, 0.53 mol) was placed in the addition funnel. The apparatus was purged with nitrogen for approximately 10 minutes before addition. The NaOMe solution was added over 5 minutes, and salt formation was observed immediately after addition. No exothermic reaction was observed immediately after addition. An additional 35 mL of MeOH was added to rinse the addition funnel. The white slurry was mixed for a further 60 minutes, and the white slurry was transferred to a glass bottle. The mixture was filtered using a 1 L Millipore pressure filter equipped with Whatman Grade I filter paper (150 mm diameter). The filtrate was pale yellow and contained fine solid particles. The volatile components were removed under reduced pressure using a rotary evaporator. The weight of the concentrated filtrate was 191 g, and nitrogen was sprayed onto the filtrate overnight. A considerable amount of salt precipitated on the flask wall overnight, and the final weight of the concentrated filtrate was 190 g. The concentrated filtrate was filtered using a 1 L Millipore pressure filter equipped with a 0.45 micron Millipore Duropore filter membrane (142 mm). The filtrate (175 g) was a yellow liquid. A certain amount was taken for GC analysis in MeOH. The GC chromatogram showed that TBD was the largest component in the GC chromatogram, apart from PDO. The TBD yield was approximately 89%.

[0122] Example 14: The present invention Preparation of TBD in bio-based 1,3-propanediol using NaOMe solution TBD in bio-based PDO (Susterra®, 216.4 g, 0.500 mol) *HCl was added to a reaction flask (1 L) that had been dried in an oven. The apparatus was assembled and purged with nitrogen for about 10 minutes. The solution was mixed using a mechanical stirrer (100 rpm). NaOMe solution (29.9 wt%, 96.6 g, 0.53 mol) was added to the addition funnel. The apparatus was purged with nitrogen for about 10 minutes before addition. The NaOMe solution was added over 15 minutes, and salt formation was observed immediately after addition. No exothermic reaction was observed immediately after addition. Additional MeOH (53 g) was added, and the addition funnel was rinsed. The white slurry was mixed for a further 4 hours, and the white slurry was transferred to a glass bottle. The mixture was filtered using a 1 L Millipore pressure filter equipped with Whatman Grade I filter paper (150 mm diameter). The filtrate was pale yellow and contained fine solids. Volatile components were removed under reduced pressure using a rotary evaporator. The weight of the concentrated filtrate was 173 g, and nitrogen was sprayed onto the filtrate overnight. A considerable amount of salt precipitated on the flask wall overnight, and the final weight of the concentrated filtrate was 172 g. The concentrated filtrate was filtered using a 1 L Millipore pressure filter equipped with a 0.45 micron Millipore Duropore filter membrane (142 mm). The filtrate (169 g) was a yellow liquid. A certain amount was taken for GC analysis in MeOH. The GC chromatogram showed that TBD was the largest component in the GC chromatogram, apart from PDO. The TBD yield was approximately 84%.

[0123] Example 15: The present invention Catalyst for water-curing SMP applications: TBD:1K STPU water-curing formulations The one-component (1K) silane-terminated polyurethane (STPU) water-curing formulations used in Examples 1, 2, and 3 were as follows:

[0124] [Table 3]

[0125] The one-component (1K) silane-terminated polyurethane (STPU) water-curing formulations used in Examples 4, 5, and 6 were as follows:

[0126] [Table 4]

[0127] The following abbreviations were used in the following examples: Polymer ST 80 is a high modulus SMP resin based on a polypropylene oxide skeleton functionalized with trimethoxysilane groups at the ends, with a viscosity of 20,000 mPa·s at 25°C. (Evonik Corp.) Dynasylan VTMO is a vinyltrimethoxysilane. (Evonik Corp.) Aerosil R 106 is a hydrophobic fumed silica surface-treated with D4 (octamethylcyclotetrasiloxane). (Evonik Corp.) VESTINOL 9 is a diisononyl phthalate. (Evonik Corp.) Elatur CH is a diisononylcyclohexanoate. (Evonik Corp.) Dynasylan DAMO-T is N-(2-aminoethyl)-3-aminopropyltrimethoxysilane. (Evonik Corp.) DBU is 1,8-diazabicyclo(5.4.0)undeca-7-ene. DBTDL is dibutyltin dilaurate.

[0128] The example formulation was prepared using a centrifugal high-speed mixer and then subjected to the following tests:

[0129] Tack-free time test The tack-free time, also known as the skinning time, was evaluated by touching the surface of the cured mixture with a gloved finger at regular intervals until no more material transferred to the glove. For Examples 1-6, the tests were conducted at 25°C and 50% relative humidity.

[0130] The test results are shown in Tables 1 and 2.

[0131] [Table 5]

[0132] [Table 6]

[0133] Example 16: The present invention TBD as a catalyst for the preparation of rigid foam used in thermal insulation applications. Samples of 36.1% by weight of TBD in EG were prepared by diluting the product of Example 11 or Example 12 with additional ethylene glycol. This solution was used as a catalyst for producing rigid polyurethane foam for use in thermal insulation applications. Typical polyurethane foam formulations for thermal insulation are shown in the table below:

[0134] [Table 7]

[0135] The catalytic reactivity in rigid polyurethane systems was evaluated using a FOMAT sonar rise-to-rate (ROR) device with free-rise cup foam samples. The FOMAT standard software generates both height-versus-time and velocity-versus-time plots. These plots are useful for comparing the relative reactivity of different catalyst formulations. MDI polyurethane foams were prepared using conventional manual mixing methods.

[0136] The table below shows the amount of catalyst required to match the string gel time in the standard rigid formulation when using a TBD solution in ethylene glycol. Clearly, TBD exhibits higher activity than the standard Polycat® 8 catalyst, demonstrating that TBD is an efficient catalyst for the production of rigid polyurethane foams.

[0137] [Table 8]

[0138] In Figure 1, the curve slightly to the left corresponds to Polycat® 8, while the curve slightly to the right corresponds to the TBD solution in EG. Both curves almost overlap and can be considered equivalent within the experimental error of manual mixing evaluation. The foam samples can be seen in Figure 2, with the foam made with Polycat® 8 shown on the left and the foam made with TBD shown on the right.

[0139] Example 17: The present invention TBD as a catalyst for the preparation of PIR rigid foam used in thermal insulation applications. The foam was produced in a 1759 mL beaker by adding the catalyst to a premix of a polyol (a polyester polyol supplied by Stepanpol, having a hydroxyl value of 230-250 and equivalent weight = 234), a flame retardant (TCPP; tris(1-chloro-2-propyl) phosphate), a surfactant (for pentane foam Dabco® DC5598 and formic acid / pentane foam DABCO® SI3201, both of which are silicone surfactants supplied by Evonik Corporation), a blowing agent (typically n-pentane, or a mixture of n-pentane in water with 85% formic acid), and alternatively, a water mixture. The composition was mixed for about 5 seconds (s) at about 5,000 RPM (or 3,000 rpm if specified) using an overhead stirrer fitted with a 6.2 cm diameter stirring paddle. Next, isocyanates were added to achieve the desired isocyanate index, typically in the range of 270–300. The premix was then thoroughly mixed using the same stirrer for about 5 seconds (s) at about 5,000 RPM. A 1759 mL beaker was placed under a FOMAT sonar device. This allowed the foam to expand and move upward within the 1759 mL beaker, as the beaker walls restricted the lateral expansion of the foam mass. At the end of the foaming process, the foam height was about 10 cm higher, exceeding the rim of the 1759 mL beaker. String gel time (defined as the time in seconds that the polymer mass can form a polymer string when touched with a wooden tongue depressor) and tack-free time (TFT; defined as the time in seconds that the surface reaches a sufficiently robust or hardened state that the surface does not become damaged or sticky when touched with a wooden tongue depressor) were measured using a chronometer and manually determined using a tongue depressor. The start time was defined as the time in seconds that the foam mass began to expand.

[0140] [Table 9]

[0141] The table below shows the effectiveness of a 36.9 wt% TBD solution in ethylene glycol when used as a catalyst in a 270-index PIR formulation. Figure 3 also shows the smooth rise profile of TBD (lower curve) compared to two runs with the standard catalyst DABCO® K15, where a typical "PIR step" is formed in approximately 60 seconds. The smooth rise profile offers the advantage of easier processing within a high-speed laminator.

[0142] [Table 10]

[0143] TBD is an effective trimer catalyst, as evidenced by the following data, which shows a % trimer conversion rate of approximately 73%.

[0144] [Table 11]

[0145] The form samples can be seen in Figure 4, with the form made with DABCO(registered trademark) K15 shown on the left and the form made with 33.9% TBD in EG shown on the right.

[0146] Example 18: The present invention Acid block TBD as a catalyst for the preparation of high-density rigid spray foam used in thermal insulation applications with commercially available hydrofluoroolefin blowing agents. Samples of acid-blocked TBD in EG were prepared by mixing the product of Example 11 or 12, succinic acid, and water with or without additional ethylene glycol. This solution, having the composition shown below, was used as a catalyst for producing rigid polyurethane foam used in thermal insulation applications.

[0147] [Table 12]

[0148] Table IV shows a typical formulation of high-density spray foam:

[0149] [Table 13]

[0150] The table below shows the usage levels of EG solution for acid-blocking TBD to provide good quality form:

[0151] [Table 14]

[0152] Figure 5 shows the rise profile of succinate block TBD in a high-density spray foam formulation, and Figure 6 shows a sample of manually mixed foam representing the microbubble structure of the test specimen.

Claims

1. A method for producing bicyclic guanidine and salts thereof in a reactor system, comprising: a) a compound of formula CX ２ Y, wherein X=NH ２ and Y is NH, O or S, reacting said compound in the presence of an acid with pKa≦2 with at least one reactive glycol represented by formula H(OC ｎ H ２ｎ－ｘ )(OH) ｘ＋１ , wherein n is 2 to 6 and x is 0 to 10, at a temperature ranging from 50°C to 190°C to release ammonia and produce a reaction product that is a clear, homogeneous solution; b) feeding said reaction product of a) into a feed pump; c) connecting said feed pump to a reactor vessel into which dipropylene triamine of formula H ２ N-(CH ２ ) ３ -NH-(CH ２ ) ３ -NH ２ or a dialkylene triamine of formula H ２ N-(CH ２ ) ｍ -NH-(CH ２ ) ｎ -NH-R, wherein m and n are each independently 2 to 5, and R is C １～１８ alkyl, alkylcycloalkyl, OH-alkyl (hydroxyalkyl), H ２ N-alkyl (aminoalkyl), alkenyl, aryl, arylalkyl, or substituted arylalkyl group, has been fed; and d) feeding said reaction product of a) into said reactor vessel having an internal temperature in the range of 160 to 200°C to produce a solution of a bicyclic guanidine salt in high yield, with a high conversion of dipropylene triamine, and with minimal or no undesirable urea impurities.

2. Formula CX ２ Y [wherein, X=NH ２ The compound having [and Y = NH, O, or S] is subjected to the reaction of formula H(OC) in the presence of an acid with pKa ≤ 2. ｎ H ２ｎ－ｘ ) (OH) ｘ＋１ A glycol represented by [wherein n = 2 to 6 and x = 0 to 10] is reacted with a glycol at a temperature in the range of 50°C to 100°C to release ammonia, and the formula is: 【Chemistry 1】 The carbamidate and formula: 【Chemistry 2】 A reaction product containing dioxolane is produced, The amount of carbamidate in the reaction product is greater than the amount of dioxolane in the reaction product. The method according to claim 1.

3. Formula CX ２ Y [wherein, X=NH ２ The compound having [and Y = NH, O, or S] is subjected to the reaction of formula H(OC) in the presence of an acid with pKa ≤ 2. ｎ H ２ｎ－ｘ ) (OH) ｘ＋１ A glycol represented by [wherein n = 2 to 6 and x = 0 to 10] is reacted with a glycol at a temperature in the range of 100°C to 190°C to release ammonia, and the formula is: 【Transformation 3】 The carbamidate and formula: 【Chemistry 4】 A reaction product containing dioxolane is produced, The amount of dioxolane in the reaction product is greater than the amount of carbamidate in the reaction product. The method according to claim 1.

4. The reactive glycol is of formula H(OC) ｎ H ２ｎ－ｘ ) (OH) ｘ＋１ The method according to any one of claims 1 to 3, expressed by [wherein n = 2 to 6 and x = 0 to 10].

5. The reactive glycol is of formula H(OC) ｎ H ２ｎ－ｘ ) (OH) ｘ＋１ The method according to any one of claims 1 to 4, expressed by [wherein n = 2 to 4 and x = 0 to 1].

6. The reactive glycol is of formula H(OC) ｎ H ２ｎ－ｘ ) (OH) ｘ＋１ The method according to any one of claims 1 to 5, represented by the formula [wherein n = 2 to 4 and x = 0, and the OH group is on the terminal carbon].

7. X = NH ２ The method according to any one of claims 1 to 6, wherein when Y = NH, n = 2, and x = 0, the carbamidate is 2-hydroxyethylcarbamimidate and the dioxolane is 1,3-dioxolane-2-imine.

8. The method according to any one of claims 1 to 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 method according to claim 8, wherein the reactive glycol is glycerol.

10. The method according to any one of claims 1 to 9, wherein the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, and phosphoric acid.

11. Formula H ２ N-(CH ２ ) ｍ -NH-(CH ２ ) ｎ The method according to any one of claims 1 to 10, wherein, in the case of a NH-R dialkylentriamine, m and n are independently 2 to 3.

12. Formula H ２ N-(CH ２ ) ｍ -NH-(CH ２ ) ｎ The method according to any one of claims 1 to 11, wherein, in the case of the NH-R dialkylentriamine, m and n are independently 3.

13. Formula H ２ N-(CH ２ ) ｍ -NH-(CH ２ ) ｎ The method according to any one of claims 1 to 12, wherein, in the case of a dialkylentriamine of -NH-R, R is aminopropyl, aminoethyl, hydroxyethyl, and hydroxypropyl.

14. Formula H ２ N-(CH ２ ) ｍ -NH-(CH ２ ) ｎ The method according to claim 16, wherein in the case of a dialkylentriamine of -NH-R, R is aminopropyl.

15. The method according to any one of claims 1 to 14, wherein the bicyclic guanidine salt, as a solution having a high yield, is present in an amount of 85% or more.

16. The method according to any one of claims 1 to 15, wherein the bicyclic guanidine salt, as a solution having a high dipropylenetriamine conversion rate, is present in a concentration of more than 99%.

17. The method according to any one of claims 1 to 16, further comprising the step of removing the solid salt by filtration and then neutralizing with a solution of sodium methoxide or potassium methoxide in methanol.

18. The method according to any one of claims 1 to 17, wherein the reactive glycol is a bio-based reactive glycol.

19. The method according to claim 18, wherein the bicyclic guanidine salt as a solution in a bio-based reactive glycol contains a bio-based content of 95 to 60% by weight.

20. The guanidine salt is added to the composition. １４ The method according to any one of claims 1 to 19, wherein the preparation is carried out in a biobase 1,3-propanediol obtained by fermentation of biomass characterized by having a C isotope.

21. Use of a bicyclic guanidine salt according to any one of claims 1 to 20 as a curing agent in silyl-terminated polyurethane (STPU) applications.

22. Use of a bicyclic guanidine salt according to any one of claims 1 to 20 as a curing agent in a silane-modified polymer (SMP) system.

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