Process for manufacture of bicyclic guanidines

Abstract

The present invention relates to a process for making bicyclic guanidine salts useful as catalysts in various polyurethane applications.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a bicyclic guanidine salt that can be used as a catalyst in various polyurethane applications. Background Technology

[0002] Highly basic bicyclic and tricyclic guanidine compounds have been used in organic synthesis and polymer additives. Some methods for synthesizing these compounds produce harmful byproducts, such as hydrogen sulfide, or require very harsh conditions. Bicyclic guanidines such as 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) have been prepared by combining them with triamines in combination with reagents such as carbon disulfide, dialkyl carbonates, and guanidines. In the case of carbon disulfide, hydrogen sulfide (H2S), a toxic gas, is released during the reaction, requiring special handling and disposal. In the case of dialkyl carbonates, the method requires very high temperatures to achieve condensation and remove water. Dehydration is important to prevent hydrolysis of TBD, and high-boiling-point desiccants are used to aid in dehydration. However, additional steps are required to remove the desiccants during product separation. In the case of using acyclic guanidines as raw materials, ammonia is released during the process, and the reaction is carried out under milder conditions, but the addition of triamines in batches to guanidines often produces significant concentrations of monocyclic and acyclic guanidines, which are very difficult to separate from the mixture. The presence of monocyclic and acyclic guanidines in the final product is highly undesirable because they can negatively impact the performance of bicyclic guanidines when used in applications, including as catalysts to promote polymerization reactions such as polyurethane reactions.

[0003] The CS2 route is described in U.S. Patent No. 4,797,487. This route has the advantage of using inexpensive starting materials and providing high yields. However, it also produces a large amount of the toxic and foul-smelling compound hydrogen sulfide (H2S) as a reaction byproduct. The generation of H2S requires additional safety precautions and the use of expensive scrubbers to prevent its release into the environment.

[0004] A more recent approach is described in U.S. Patent Publication 2009 / 0281314 and PCT Publication WO2009 / 137728. The routes disclosed therein use cyclic urea as a carbon source. This is an improvement over the CS2 route because no H2S is generated; however, this chemistry requires a multi-step process and harsh reaction conditions to facilitate the dehydration of the urea intermediate.

[0005] US 8642771 describes a method for contacting guanidine salts with dipropylenetriamine, but this method does not address the necessary procedures for minimizing impurities present in TBD that are highly detrimental to its use in polyurethane applications, such as ureas, monocyclic and acyclic guanidine intermediates, and residual dipropylenetriamine. The presence of these impurities and their minimization, removal, or avoidance during the manufacturing process are important because these compounds are known to cause premature cell opening in polyurethane foam manufacturing, thereby significantly reducing processing tolerance or even causing collapse of the polyurethane reactive mixture. The method can be carried out in the presence of a solvent or with a pure mixture of reagents. Solvents include hydrocarbons, ethers, esters, nitriles, sulfoxides, amides, chlorinated hydrocarbons, and / or mixtures of two or more of the above solvents. The invention is preferably carried out without these added solvents. However, the presence or absence of these solvents does not provide a means to eliminate the formation of ureas, monocyclic and acyclic guanidine intermediates, and residual dipropylenetriamine, which are detrimental to performance in various applications. Furthermore, the absence of solvents results in TBD being produced as a high-melting-point solid, making product separation more challenging.

[0006] Therefore, there is still a need for economically viable methods to produce cyclic guanidines, such as TBD or amino-alkyl-TBD, with sufficiently high purity to qualify them as suitable catalysts for the production of urethane polymers. Summary of the Invention Invention Overview

[0008] In one aspect, the present invention provides a convenient method for manufacturing high-purity polycyclic guanidine compounds, particularly bicyclic guanidines.

[0009] In another aspect, the present invention provides a method for manufacturing bicyclic guanidine and its salts in a reactor system, comprising the following steps:

[0010] a) Compounds of formula CX2Y, in which X = NH2 and Y = NH, O, or S, preferably X = NH2 and Y = NH, have a pKa of 0. In the presence of an acid of 2, with at least one of the following formulas: H(OC) where n = 2-6 and x = 0-10 n H 2n-x (OH) x+1 The reactive diols, when reacted at temperatures ranging from 50°C to 190°C, release ammonia and produce reaction products as clear, homogeneous solutions.

[0011] b) Load the reaction product from a) into the feed pump;

[0012] c) Connect the feed pump to a dipropylenetriamine of the formula H2N-(CH2)3-NH-(CH2)3-NH2 or the formula H2N-(CH2)m -NH-(CH2) n The reactor vessel for -NH-R dialkyltriamine, wherein m and n are independently 2 to 5, preferably 2 to 3, more preferably 3, and R = C 1-18 Alkyl, alkyl-cycloalkyl, OH-alkyl (hydroxyalkyl), H2N-alkyl (amino-alkyl), alkenyl, aryl, aralkyl, or substituted aralkyl, preferably R is aminopropyl, aminoethyl, hydroxyethyl, and hydroxypropyl, more preferably aminopropyl; and

[0013] d) Feed the reaction product of a) into the reactor vessel, wherein the temperature in the reactor vessel is in the range of 160-200°C, thereby producing a solution of bicyclic guanidine salt in high yield (85% or higher), high dipropylenetriamine conversion (greater than 99%) and with minimal or no unwanted urea impurities.

[0014] In one embodiment, the bicyclic guanidine salt can then be recovered as a free base by neutralization with a methanol solution of sodium methoxide or potassium methoxide after removing the solid salt by filtration using a standard procedure. The bicyclic guanidine base can be further converted into salts of carboxylic acids, including monocarboxylic acids, dicarboxylic acids, and polycarboxylic acids.

[0015] In another aspect, the present invention provides a method for manufacturing bicyclic guanidine with high yield and high conversion, wherein unwanted urea and monocyclic and acyclic guanidine impurities are minimized or absent.

[0016] In another aspect, the present invention provides a method for controlling the yield and purity of bicyclic guanidine by appropriately selecting reactants.

[0017] The present invention also provides a method for controlling the yield and purity of bicyclic guanidine in the salt and / or free base forms by appropriately selecting reactants to minimize the decomposition of bicyclic guanidine during the purification and separation process.

[0018] In a further aspect, the present invention provides a method for controlling the yield and purity of bicyclic guanidine in the form of salt and / or free base by appropriately selecting reactants to minimize the formation of impurities during the manufacturing process.

[0019] This invention provides high-purity bicyclic guanidine, such as TBD, suitable for use as a curing agent in silyl-terminated polyurethane (STPU) applications.

[0020] The present invention provides a method for preparing a silyl-terminated polyurethane application (STPU) containing a curing agent, wherein the curing agent contains at least one high-purity bicyclic guanidine.

[0021] Furthermore, the present invention provides high-purity bicyclic guanidines, such as TBD, suitable for use as catalysts or co-catalysts in polyurethane applications, including flexible, semi-flexible, rigid, semi-rigid, and CASE polyurethane applications.

[0022] The bicyclic guanidine produced according to the present invention is also a catalyst that can be used in moisture-cured silane-modified polymers (SMPs). In this application, the bicyclic guanidine is part of a moisture-cured one-component (1K) silane-terminated polyurethane (STPU).

[0023] In another aspect, the present invention provides high-purity bicyclic guanidine, such as TBD, suitable for use as a curing agent in silane-modified polymer (SMP) systems. For the purposes of this invention, SMP refers to polymers typically functionalized at the terminal chain ends with at least two alkoxysilyl groups. In the presence of water, typically in the form of ambient moisture, alkoxysilanes hydrolyze to form silanol-containing compounds, which subsequently undergo condensation polymerization to construct the molecular weight and / or crosslinking density of the polymer, thereby curing / hardening the system. The hydrolysis / condensation curing process in SMP systems is relatively slow but can be accelerated with catalysts such as organotin compounds. TBD produced according to the present invention has been found to be a highly efficient catalyst in the curing of such silane-modified polymers, particularly for 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.

[0024] Silane-terminated polyurethane (STPU) systems are a representative subtype of SMP systems, gaining rapid and widespread adoption in coatings, adhesives, sealants, and elastomers (CASE) applications due to their combination of polyurethane performance and isocyanate-free processing. STPU prepolymers are a key component in such SMP formulations, and they are typically manufactured using two different methods: In one method, STPU prepolymers are prepared by reacting polyols such as polyester or polyether polyols with γ-isocyanate-propylalkoxysilanes. A second method for preparing STPU prepolymers starts with a polyol, such as a polyether or polyester polyol, which is reacted with an excess of diisocyanate or polyisocyanate in a first reaction step. The resulting isocyanate-terminated prepolymer is then reacted with a γ-aminopropyl-functionalized alkoxysilane to obtain the desired alkoxysilane-terminated prepolymer. In addition to STPU prepolymers, various types of functional additives, such as fillers, pigments, catalysts, dehumidifiers, UV absorbers & stabilizers, adhesion promoters, wetting agents, defoamers, etc., can be used in such SMP formulations depending on the end application.

[0025] A typical measure for assessing the reactivity of SMP formulations is surface drying time or skinning time. Surface drying time refers to the time elapsed after the application of an SMP formulation until the polymer surface has cured to the point where touching the surface of the curing mixture with a gloved finger no longer causes material to transfer onto the glove.

[0026] In another aspect, the present invention provides high-purity bicyclic guanidines, such as TBD, suitable for use as catalysts for polyurethane foams. Attached Figure Description

[0027] Figure 1 This is the lifting rate diagram for Example 16.

[0028] Figure 2 These are photos of foam made with Polycat®8 and foam made with TBD.

[0029] Figure 3 This is the lifting rate diagram for Example 17.

[0030] Figure 4 These are photos of foam made with DABCO® K15 and foam made with 33.9% TBD in EG.

[0031] Figure 5 This is the rise and distribution curve of succinic acid-blocked TBD in high-density spray foam formulation.

[0032] Figure 6 This is a photo of a sample of manually mixed foam. Invention Details

[0034] This invention relates to a method for producing bicyclic guanidine and its salts in a reactor system, comprising the following steps:

[0035] a) Compounds of formula CX2Y in which X = NH2 and Y = NH, O, or S have a pKa of In the presence of an acid of 2, with at least one of the following formulas: H(OC) where n = 2-6 and x = 0-10 n H 2n-x (OH) x+1 The reactive diols, when reacted at temperatures ranging from 50°C to 190°C, release ammonia and produce reaction products as clear, homogeneous solutions.

[0036] b) Load the reaction product from a) into the feed pump;

[0037] c) Connect the feed pump to a dipropylenetriamine of the formula H2N-(CH2)3-NH-(CH2)3-NH2 or the formula H2N-(CH2) m -NH-(CH2)n A reactor vessel for -NH-R dialkyltriamines, wherein m and n are independently 2 to 5, and R = C 1-18 Alkyl, alkyl-cycloalkyl, OH-alkyl (hydroxyalkyl), H2N-alkyl (amino-alkyl), alkenyl, aryl, aralkyl or substituted aralkyl; and

[0038] d) The reaction product of a) is fed into the reactor vessel, wherein the temperature in the reactor vessel is in the range of 160-200°C, thereby producing a solution of bicyclic guanidine salt in high yield, high dipropylenetriamine conversion and with minimal or no unwanted urea impurities.

[0039] In a preferred embodiment, the compound of formula CX2Y, wherein X = NH2 and Y = NH, O, or S, is in pKa In the presence of acid 2, and with the formula H(OC) where n = 2-6 and x = 0-10. n H 2n-x (OH) x+1 The diol, represented by [insert name here], reacts at temperatures ranging from 50°C to 100°C, releasing ammonia and producing reaction products comprising aminoimine esters of the following formula:

[0040]

[0041] And the following formula for dioxolane:

[0042]

[0043] The amount of aminoimine ester in the reaction product is higher than the amount of dioxolane in the reaction product.

[0044] In a preferred embodiment, when X = NH2, Y = NH, n = 2 and x = 0, the aminoimide ester is 2-hydroxyethyl aminoimide, and the dioxolane is 1,3-dioxolane-2-imine.

[0045] In another preferred embodiment, the compound of formula CX2Y, wherein X = NH2 and Y = NH, O, or S, has a pKa [value missing]. In the presence of an acid of 2, and with the formula H(OC) where n = 2-6 and x = 0-10. n H 2n-x (OH) x+1 The diol, represented by [insert name here], reacts at temperatures ranging from 100°C to 190°C, releasing ammonia and producing reaction products comprising aminoimine esters of the following formula:

[0046]

[0047] And the following formula for dioxolane:

[0048]

[0049] The amount of dioxolane in the reaction product is higher than the amount of aminoimide ester in the reaction product.

[0050] In a preferred embodiment, when X = NH2, Y = NH, n = 2 and x = 0, the aminoimide ester is 2-hydroxyethyl aminoimide, and the dioxolane is 1,3-dioxolane-2-imine.

[0051] Preferably, in one embodiment, the reactive diol is composed of H(OC) of formula where n = 2-6 and x = 0-10. n H 2n-x (OH) x+1 express.

[0052] More preferably, in another embodiment, the reactive diol is H(OC) of formula where n = 2-4 and x = 0-1. n H 2n-x (OH) x+1 express.

[0053] Preferably, in another embodiment, the formula H(OC) where x = 0 and n = 2-4 n H 2n-x (OH) x+1 The OH group of a reactive diol is an OH group at the terminal carbon.

[0054] In another preferred embodiment, the reactive diol is ethylene glycol, 1,3-propanediol, 1,4-tetramethylenediol, glycerol, diglycerol, MP-diol (2-methyl-1,3-propanediol), or any combination thereof. In another preferred embodiment, the reactive diol is diglycerol and / or MP-diol (2-methyl-1,3-propanediol). In another most preferred embodiment, the reactive diol is glycerol.

[0055] Preferably, in one embodiment, the acid is selected from hydrochloric acid, sulfuric acid, and phosphoric acid.

[0056] Preferably, in another embodiment, for the formula H2N-(CH2) m -NH-(CH2) n -NH-R dialkyltriamine, where m and n are independently 2 to 3. Preferably, in another embodiment, for the formula H2N-(CH2) m -NH-(CH2) n-NH-R dialkyltriamine, where m and n are independently 3. Preferably, in another embodiment, for the formula H2N-(CH2) m -NH-(CH2) n -NH-R dialkyltriamine, where R is aminopropyl, aminoethyl, hydroxyethyl, or hydroxypropyl.

[0057] Preferably, in another embodiment, the bicyclic guanidine salt is produced in solution form at a high yield of 85% or higher. Preferably, in another embodiment, the bicyclic guanidine salt is produced in solution form at a high dipropylene triamine conversion rate of over 99%.

[0058] Then, 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 methanol solution of sodium methoxide or potassium methoxide. The bicyclic guanidine base can be further converted into salts of carboxylic acids (including monocarboxylic acids, dicarboxylic acids, and polycarboxylic acids).

[0059] In a preferred embodiment, the method further includes the step of neutralizing with a methanol solution of sodium methoxide or potassium methoxide after removing solid salt by filtration.

[0060] In a preferred embodiment, bicyclic guanidine is manufactured using a combination 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, and guanidine trifluoromethanesulfonate, with guanidine hydrochloride being the most preferred.

[0061] In a preferred embodiment, the reactive diol is a bio-based diol. Preferably, in this embodiment, the guanidine salt is produced in a sustainable diol, such as bio-based glycerol derived from the hydrolysis of oils and fats.

[0062] In another preferred embodiment, the guanidine salt is manufactured using bio-based 1,3-propanediol obtained through the fermentation of biomass. In this case, the resulting solution is characterized by having, as determined by the ASTM D6866 method, […]. 14 C radioactive carbon isotope.

[0063] In another preferred embodiment, the bicyclic guanidine salt, in solution form in a bio-based glycol, contains 95 to 60% by weight of bio-based content. In another preferred embodiment, the bicyclic guanidine salt, in solution form in a bio-based glycol, contains 80 to 60% by weight of bio-based content. In yet another preferred embodiment, the bicyclic guanidine salt, in solution form in a bio-based glycol, contains 70 to 60% by weight of bio-based content.

[0064] In another preferred embodiment, the method according to the invention uses the formula H2N-(CH2). m -NH-(CH2)n The dialkyltriamine of -NH-R is used to produce a bicyclic guanidine salt, wherein m and n are independently 2 to 5, preferably 2 to 3, more preferably 3, and R = hydrogen or C. 1-18 Alkyl or alkyl-cycloalkyl, OH-alkyl (hydroxyalkyl), H2N-alkyl (amino-alkyl), alkenyl, aryl, aralkyl, or substituted aralkyl. In one preferred embodiment, R is hydrogen, aminopropyl, aminoethyl, hydroxyethyl, and hydroxypropyl. In another preferred embodiment, R is aminopropyl.

[0065] In another preferred aspect of the invention, the bicyclic guanidine salt prepared according to the invention allows for improved control of ammonia emissions during the reaction process. Control of ammonia emissions is important for reducing the risk and associated consequences of ammonia release into the environment. Ammonia released during the reaction of the diol with guanidine can be captured in an emission control device. The ammonia formation rate in the semi-batch step is related to the feed rate of the reactive diol product. Ammonia formation can be rapidly reduced by stopping the feed pump. Conversely, for the batch process, reaction temperature is the only way to control ammonia. Rapid and uncontrolled ammonia formation can lead to an ammonia generation rate exceeding the rate that the emission control device can handle. Furthermore, ammonia formation cannot be easily stopped in the event of emission control device failure.

[0066] In another preferred aspect of the invention, the bicyclic guanidine salt and bicyclic guanidine prepared according to the invention provide near-quantitative conversion of dialkyltriamines. Dialkyltriamines are undesirable components in bicyclic guanidines due to the degradation of urea and hydrofluoroolefin foaming agents in the presence of isocyanates. Dipropylenetriamines are particularly undesirable components in TBD product mixtures due to their hazard classification. Specifically, when present in product mixtures at 1.0% or more, they need to be classified as germ cell mutagenic (Category 2) and specific target organ toxicity (repeated exposure). In particular, when present in product mixtures at 0.1% or more, they need to be classified as skin sensitizing.

[0067] In another preferred aspect of the invention, the bicyclic guanidine salt prepared according to the invention improves process safety by preventing unintentional solid formation during process shutdowns.

[0068] This reaction of guanidine salts with diols ensures that the reaction mixture remains liquid throughout. In contrast, the batch reaction involves a two-phase reaction mixture until the guanidine salt dissolves at a reaction temperature above 60°C.

[0069] In a preferred aspect, the present invention provides bicyclic guanidine for use in the production of polyurethane foams, including rigid, flexible, and semi-flexible polyurethane foams, exhibiting optimal physical properties, regular cell structure, low odor, and zero emissions. Such polyurethane materials can be prepared using bicyclic guanidine produced according to the method of the present invention, wherein the concentrations of impurities such as urea, cyclic urea, and guanidine can be minimized, as they are detrimental to the cell structure of the foamed polyurethane.

[0070] In another preferred embodiment, the present invention provides high-purity bicyclic guanidine, such as TBD, suitable for use as a curing agent in silyl-terminated type polyurethane applications (STPUs). The present invention provides a method for preparing a silyl-terminated type polyurethane application (STPU) comprising a curing agent, wherein the curing agent comprises at least one high-purity bicyclic guanidine.

[0071] In another preferred embodiment, the present invention provides high-purity bicyclic guanidine, such as TBD, suitable for use as a curing agent in silane-modified polymer (SMP) systems. For the purposes of this invention, a silane-modified polymer (SMP) refers to a polymer functionalized with at least two alkoxysilyl groups. In the presence of water, typically in the form of ambient moisture, alkoxysilanes hydrolyze to form silanol-containing compounds, which subsequently undergo condensation polymerization to construct the molecular weight and / or crosslinking density of the polymer, thereby curing / hardening the system. This hydrolysis / condensation curing process can be accelerated using catalysts such as tin-based salts. 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.

[0072] In another preferred embodiment, the method of the present invention provides a bicyclic guanidine comprising at least one member selected from the group consisting of: 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD, triazabicyclodecene), 1,5,7-triazabicyclo[4.3.0]non-6-ene (TBN, triazabicyclononane), 1,6,8-triazabicyclo[5.3.0]dec-7-ene, 1,6,8-triazabicyclo[ [5.4.0] Undec-7-ene, 7-(3-aminopropyl)-1,5,7-triazabicyclo[4.4.0]dec-5-ene (aminopropyl-TBD, aminopropyl-triazabicyclodecene), 7-(3-aminopropyl)-1,5,7-triazabicyclo[4.3.0]non-6-ene (aminopropyl-TBN, aminopropyl-triazabicyclononane) and their corresponding salts of the following acids: hydrochloric acid, sulfuric acid and phosphoric acid.

[0073] In another preferred embodiment, the method of the present invention provides a method for preparing a solution of a bicyclic guanidine salt having at least one organic dicarboxylic acid, tricarboxylic acid, or polycarboxylic acid component, wherein these salts are useful catalysts in spray foaming applications using foaming agents such as hydrofluorocarbons, hydrochlorocarbons, hydrochloroolefins, hydrofluoroolefins, hydrochlorofluoroolefins, fluoroolefins, chloroolefins, and hydrochlorofluorocarbons.

[0074] 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 dicarboxylic acid, tricarboxylic acid, or polycarboxylic acid made from a bicyclic guanidine.

[0075] In another preferred embodiment, the present invention relates to a method for manufacturing PIR / PUR rigid foam, comprising contacting at least one bicyclic guanidine with a polyisocyanate (which comprises at least one of toluene diisocyanate and diphenylmethane diisocyanate and their isomers) and a polyol premix at an isocyanate index of 120-800, wherein the polyol premix comprises a polyol or a mixture of polyols, a surfactant, a flame retardant, an amine catalyst, water, various additives such as fillers, chain extenders, crosslinking agents and colorants, as well as other additives and blowing agents.

[0076] Even at high isocyanate indices, the catalyst compositions of the present invention provide substantially consistent foam height increases relative to time, which offers processing advantages in high-speed PIR lamination processes.

[0077] In another preferred aspect of the invention, the catalyst prepared according to the invention can be thermally stable at standard foam processing temperatures, producing PIR / PUR foam that is substantially free of volatile amines and / or amine odors.

[0078] In another preferred aspect, the bicyclic guanidine prepared according to the invention can be used with other additives, depending on the application type, including tertiary amines with or without isocyanate reactive groups, metal catalysts, trimer catalysts, chain extenders, crosslinking agents, fillers, and various other additives known in the art.

[0079] Preferred examples of tertiary amines that can be used with bicyclic guanidine include conventional tertiary amines such as triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole, and N-methylmorpholine (which can be used as DABCO). ® Purchased from NMM), N-ethylmorpholine (can be used as DABCO) ® Purchased from NEM), triethylamine (can be used as DABCO) ® (purchased from TETN), N,N'-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine (can be used as Polycat) ®41 (purchased), 2,4,6-tris(dimethylaminomethyl)phenol (can be used as DABCO TMR) ® Purchased for 30), N-methyldicyclohexylamine (can be used as Polycat) ® Purchased at 12), pentamethyldipropylenetriamine (can be used as Polycat) ® Purchased at 77), N-methyl-N'-(2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyl-diethylenetriamine (can be used as Polycat) ® 5 purchased), hexamethyl-triethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexylamine (can be used as Polycat) ® Purchased from 8), triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl) ether (can be used as DABCO) ® BL19 was purchased), tris(3-dimethylaminopropyl)amine (which can be used as Polycat) ® 9 (purchased), 1,8-diazabicyclo[5.4.0]undecane (12ndecane) (can be used as DABCO) ® DBU (obtained from DBU) or its acid-blocked derivatives, and any mixtures thereof. Polycat is particularly useful as a urethane catalyst for foam applications related to this invention. ® 5, which is chemically known as pentamethyldiethylenetriamine.

[0080] Preferably, bicyclic guanidine can also be used with a tertiary amine having at least one isocyanate reactive group, said isocyanate reactive group comprising a primary hydroxyl group, a secondary hydroxyl group, a primary amino group, a secondary amino group, a urea group, or an amide group.

[0081] Preferred examples of tertiary amine catalysts having isocyanate reactive groups include, but are not limited to, N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, N,N-dimethylaminoethyl-N'-methylethanolamine, N,N,N'-trimethylaminopropylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dimethyl-N',N'-(2-hydroxypropyl)-1,3-propanediamine, dimethylaminopropylamine, (N,N-dimethylaminoethoxy)ethanol, N-methyl-N'-(2-hydroxyethyl)-piperazine, bis(N,N-dimethyl-3-aminopropyl)amine, N,N-dimethylaminopropylurea, N,N-diethylaminopropylurea, N,N'-bis(3-dimethylaminopropyl)urea, bis(dimethylamino)-2-propanol, 6-dimethylamino-1-hexanol, N-(3-aminopropyl)imidazol, N-(2-hydroxypropyl)imidazol, N-(2-hydroxyethyl)imidazol, 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.

[0082] In a preferred embodiment, bicyclic guanidine can also be used with a tertiary amine that is acid-blocked with an acid, including a carboxylic acid (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic), a sulfonic acid, or any other organic or inorganic acid. Preferred examples of carboxylic acids include mono-, dia-, or poly-acids with or without isocyanate reactive groups. Preferred examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, neovaleric 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, heptadecanic acid, octadecanoic acid, benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, salicylic acid, etc.

[0083] In a preferred embodiment, the bicyclic guanidine can also be used in combination with a metal catalyst. For example, in a 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 transition metal catalysts, such as organotin compounds or bismuth carboxylates, may contain at least one member selected from the group consisting of: dibutyltin dilaurate, dimethyltin dilaurate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilauryl mercaptan, dibutyltin dilauryl mercaptan, dimethyltin diisooctyl maleate, dibutyltin diisooctyl maleate, bis(2-ethylhexyl mercaptoacetic acid) dimethyltin, bis(2-ethylhexyl mercaptoacetic acid) dibutyltin, stannous octoate, other suitable organotin catalysts, or combinations thereof. Other metals, such as bismuth (Bi), may also be included. Suitable bismuth carboxylates include salts of the following acids: valeric acid, neovaleric 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 transition metal salts of lead (Pb), iron (Fe), zinc (Zn), valeric acid, neovaleric acid, hexanoic acid, 2-ethylhexylcarboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids may also be included.

[0084] Preferably, the bicyclic guanidine of the present invention may further comprise any amount of other catalytic materials, such as carboxylates. Exemplary examples of alkali metals, alkaline earth metals, and quaternary ammonium carboxylates include, but are not limited to, potassium formate, potassium acetate, potassium propionate, potassium butyrate, potassium valerate, potassium hexanoate, potassium heptanoate, potassium octanoate, potassium 2-ethylhexanoate, potassium decanoate, potassium butyrate, potassium isobutyrate, potassium nonanoate, potassium stearate, sodium octanoate, lithium stearate, sodium decanoate (sodium n-decanoate), lithium octanoate, 2-hydroxypropyltrimethylammonium octanoate solution, etc., or any combination thereof.

[0085] Preferably, the amounts of other catalysts and salts may be from about 0 pphp to about 20 pphp, from about 0.1 pphp to about 15 pphp, and in some cases from about 0.5 pphp to about 10 pphp.

[0086] Preparation of the foam

[0087] The method of the present invention can be used to manufacture any of the various types of foams known in the art using a typical polyurethane formulation in which appropriate amounts of bicyclic guanidine, as illustrated in the following examples, have been added.

[0088] For example, flexible polyurethane foams possessing the excellent properties described herein will typically contain the components shown in Table A below in the indicated amounts. The components shown in Table A will be discussed in detail later below.

[0089] Table A: Polyurethane Components

[0090]

[0091] There is no limitation on the amount of polyisocyanate used in the polyurethane formulations according to the present invention, but it will generally be within those ranges known to those skilled in the art. Exemplary ranges are given in Table A, indicated by reference to the “NCO Index” (isocyanate index). As is known in the art, the NCO index is defined as the equivalent number of isocyanates divided by the total equivalent number of active hydrogens, multiplied by 100. The NCO index is expressed by the following formula.

[0092] NCO index = [NCO / (OH+NH)] 100

[0093] In addition to base polyols with a weight-average molecular weight of approximately 4000-5000 and a hydroxyl value of approximately 28-35, flexible foams typically use copolymer polyols as part of the total polyol content in the foam composition. Base polyols and copolymer polyols will be described in detail later in this document.

[0094] Polyols may have a functionality 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.

[0095] Catalyst

[0096] Preferably, the amount of bicyclic guanidine may be from about 0.01 pphp to about 20 pphp, from about 0.05 pphp to about 10 pphp, and in some cases from about 0.1 pphp to about 5 pphp. Preferably, the amount of other catalytically active ingredients may be from about 0 pphp to about 19 pphp, from about 0 pphp to about 15 ppm, and in some cases from about 0 pphp to about 10 pphp.

[0097] Preferred examples of foaming cocatalysts containing isocyanate reactive groups that can be used in combination with the above-described catalysts include N,N,N'-trimethyl-N'-3-aminopropyl-bis(aminoethyl) ether, 2-[N-(dimethylaminoethoxyethyl)-N-methylamino]ethanol, and N,N,N'-trimethyl-N'-(2-hydroxyethyl)-bis(aminoethyl) ether. Preferably, the amount of foaming cocatalyst can be from about 0 pphp to about 5 pphp, from about 0.01 pphp to about 2 pphp, and in some cases from about 0.05 to about 1 pphp.

[0098] Preferably, the catalyst composition may further include other components, such as transition metal catalysts, like organotin compounds or bismuth carboxylate, for example when the desired polyurethane foam is a flexible slab material. The metal catalyst may also contain at least one member selected from the group consisting of: dialkyltin carboxylates, such as dibutyltin dilaurate, dimethyltin dilaurate, dimethyltin diacetate, dibutyltin diacetate, dimethyltin dilauryl mercaptoacetate, dibutyltin dilauryl mercaptoacetate, dimethyltin diisooctyl maleate, dibutyltin diisooctyl maleate, bis(2-ethylhexylmercaptoacetic acid) dimethyltin, bis(2-ethylhexylmercaptoacetic acid) dibutyltin, dimethyltin neodecanoate, dibutyltin neodecanoate, dimethyltin isononanoate, dibutyltin isononanoate, stannous octoate, stannous neodecanoate, stannous isononanoate, or other suitable organotin catalysts or other suitable stannous carboxylates or combinations thereof. Other metals and their salts may also be included, such as bismuth (Bi). Suitable metal salts include carboxylates, including salts of the following acids: acetic acid, propionic acid, butyric acid, valeric acid, neovaleric 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, heptadecanic acid, octadecanoic acid, and other suitable carboxylic acids. Other transition metal salts of lead (Pb), iron (Fe), or zinc (Zn) with valeric acid, neovaleric acid, hexanoic acid, 2-ethylhexylcarboxylic acid, octanoic acid, neooctanoic acid, neoheptanoic acid, neodecanoic acid, neoundecanoic acid, neododecanoic acid, and other suitable carboxylic acids may also be included. Preferably, the amount of the aforementioned metal catalyst can be from about 0 pphp to about 20 pphp, from about 0 pphp to about 10 pphp, and in some cases from about 0 pphp to about 0.01 pphp.

[0099] Bicyclic guanidines can also be acid-blocked with acids, including carboxylic acids (alkyl, substituted alkyl, alkylene, aromatic, substituted aromatic), sulfonic acids, or any other organic or inorganic acids. Examples of carboxylic acids include mono-, di-, or poly-acids with or without isocyanate reactive groups. Preferred examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, neovaleric 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, octanoic acid, azelaic acid, sebacic acid, glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, salicylic acid, etc.

[0100] Although the bicyclic guanidine of the present invention can be used with the amines listed above, and the total loading of one or more tertiary amine catalysts used to produce foams according to the present invention (i.e., the bicyclic guanidine of the present invention plus any co-gelling catalyst) will generally be in the range of about 0.1 to about 20 pphp, more typically about 0.1 to about 10 pphp, and most typically about 0.1 to about 5 pphp. However, any effective amount may be used. The term "pphp" refers to parts per hundred parts of polyol.

[0101] Organic isocyanate

[0102] Preferred suitable organic isocyanate compounds include, but are not limited to, hexamethylene diisocyanate (HDI), phenyl diisocyanate (PDI), toluene diisocyanate (TDI), and 4,4'-diphenylmethane diisocyanate (MDI). In one aspect of the invention, 2,4-TDI, 2,6-TDI, or any mixture thereof are used in the production of polyurethane foam. Other suitable isocyanate compounds are diisocyanate mixtures commercially known as "crude MDI." One example is sold by Dow Chemical Company under the trade name PAPI and contains approximately 60% 4,4'-diphenylmethane diisocyanate, as well as other isomers and similar higher polyisocyanates. Although any suitable isocyanate can be used, one example includes isocyanates having an index range of approximately 60 to approximately 200, typically approximately 90 to approximately 120. The amount of isocyanate is typically approximately 95 to approximately 105, and in one aspect of the invention, the isocyanate index is approximately 60 to approximately 65.

[0103] Polyol component

[0104] Polyurethanes are produced by reacting organic isocyanates with the hydroxyl groups of polyols, typically mixtures of polyols. The polyol component of the reaction mixture comprises at least a major or “base” polyol. Base polyols suitable for use in this invention include, as a non-limiting example, polyether polyols. Polyether polyols include poly(epoxide) polymers, such as poly(ethylene oxide) and poly(propylene oxide) polymers and copolymers, having terminal hydroxyl groups derived from polyhydroxy compounds, including diols, triols, and higher alcohols. Preferred examples of diols and triols that react 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 hydroxyl-terminated acetals, 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, which is incorporated herein by reference. Suitable polyether polyols also include those containing tertiary amine groups capable of catalyzing the gelation and foaming reactions of polyurethanes, such as those described in US 8,367,870; WO 03 / 016373A1, WO 01 / 58976 A1; WO2004 / 060956 A1; WO003 / 016372 A1; and WO03 / 055930 A1; the disclosures of the aforementioned US and WO publications are incorporated herein by reference. Other usable polyols may include polyalkylene carbonate-based polyols and polyphosphate-based polyols.

[0105] In one aspect of the invention, a single high molecular weight polyether polyol can be used as the base polyol. Alternatively, a mixture of high molecular weight polyether polyols can be used, such as a mixture of difunctional and trifunctional materials and / or materials of different molecular weights or different chemical compositions. Such difunctional and trifunctional materials include, but are not limited to, polyethylene glycol, polypropylene glycol, glycerol-based polyether triol, trimethylolpropane polyether triol, and other similar compounds or mixtures.

[0106] In addition to, or in place of, the base polyols described above, materials commonly referred to as "copolymer polyols" may be included in the polyol components used according to the present invention. Copolymer polyols can be used in polyurethane foams to improve resistance to deformation, for example, to improve load-bearing properties. Depending on load requirements, copolymer polyols may constitute approximately 0 to approximately 80% by weight of the total polyol content.

[0107] Preferred examples of copolymer polyols include, but are not limited to, grafted polyols and polyurea-modified polyols, both of which are known in the art and are commercially available.

[0108] Grafted polyols are prepared by copolymerizing vinyl monomers, typically styrene and acrylonitrile, into a starting polyol. The starting polyol is typically a glycerol-initiated triol and is usually end-capped with ethylene oxide (approximately 80-85% primary hydroxyl groups). Some of the copolymer is grafted onto some of the starting polyol. The grafted polyol also contains a homopolymer of styrene and acrylonitrile and the unmodified starting polyol. The styrene / acrylonitrile solids content of the grafted polyol is typically from 5% to 45% by weight, but any type of grafted polyol known in the art can be used.

[0109] Polyurea-modified polyols are formed by the reaction of diamines and diisocyanates in the presence of a starting polyol, and the product contains a polyurea dispersion. A variant of the polyurea-modified polyol also suitable is a polyisocyanate polyaddition (PIPA) polyol, formed by the in-situ reaction of isocyanates and alkanolamines in a polyol.

[0110] Other suitable polyols that can be used according to the invention include natural oil polyols or polyols obtained from renewable natural resources such as vegetable oils. Polyols derived from inexpensive and renewable resources that can be used to prepare polyurethane foams are highly desirable 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—a natural triglyceride of ricinoleic acid commonly used in the manufacture of polyurethane foams, although it has certain limitations, such as low hydroxyl content. Other natural oils require chemical modification to introduce sufficient hydroxyl content to make them usable for the production of polyurethane polymers. When attempting to modify natural oils or fats into usable polyols, two chemically reactive sites can be considered: 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 by hydroformylation followed by hydrogenation. Alternatively, transesterification can be used to introduce OH groups into natural oils and fats. Chemical methods for preparing natural polyols using the epoxidation pathway involve a reaction mixture requiring epoxidized natural oils, a ring-opening acid catalyst, and a ring-opening agent. Epoxidized natural oils include epoxidized vegetable oils (epoxidized vegetable oils) and epoxidized animal fats. Epoxidized natural oils can be fully or partially epoxidized, and these oils include soybean oil, corn oil, sunflower oil, olive oil, low-erucic acid rapeseed oil, sesame oil, palm oil, rapeseed oil, tung oil, cottonseed oil, safflower oil, peanut oil, flaxseed oil, and combinations thereof. Animal fats include fish oil, beef tallow, and lard. These natural oils are C 12 To C 24The peroxy acids are triglycerides of fatty acids of various chain lengths, which can be saturated or unsaturated. These acids can be: 1) saturated: lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and tetracosanoic acid; 2) monounsaturated: palmitoleic acid and oleic acid; 3) polyunsaturated: linoleic acid, linolenic acid, and arachidonic acid. Partially or fully epoxidized natural oils can be prepared by reacting peroxy acids under suitable reaction conditions. Examples of peroxy acids used in the epoxidation of oils have been described in WO 2006 / 116456 A1, which is incorporated herein by reference. Epoxidized oils can be ring-opened using alcohols, water, and other compounds having one or more nucleophilic groups. Oligopolymerization of epoxidized oils can also occur depending on the reaction conditions. Ring-opening produces natural oil polyols that can be used to manufacture polyurethane products. In the hydroformylation / hydrogenation process, oil is hydroformylated in a reactor filled with a hydrogen / carbon monoxide mixture in the presence of a suitable catalyst (usually 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 derived 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, low-erucic acid rapeseed oil, rapeseed oil, safflower oil, fish oil, seal oil, palm oil, tung oil, olive oil, or any blend. Any polyfunctional hydroxyl compound, such as lactose, maltose, raffinose, sucrose, sorbitol, xylitol, erythritol, mannitol, or any combination thereof, can also be used.

[0111] The amount of polyol is limited by pphp. There are three types of polyols as defined above: standard polyols or polyether polyols, which can be used in the range of approximately 100 pphp (single polyol) to approximately 10 pphp. Copolymer polyols (CPP) can be used in the range of approximately 0 to approximately 80 pphp. Finally, NOP (natural oil polyol) can typically be present in the range of approximately 0 to approximately 40 pphp.

[0112] Polyols can have OH values ​​from 10 to about 900 and functionality from about 2 to 8. The OH value and functionality of the polyol are selected to obtain foams with the desired physical properties.

[0113] Open-cell flexible molding foams typically use a primary or “base” polyether polyol. Polyether polyols include poly(epoxide) polymers, such as poly(ethylene oxide) and poly(propylene oxide) polymers and copolymers, which have terminal hydroxyl groups derived from polyhydroxy compounds, including diols and triols. These polyols may have a functionality of about 2 to about 8, about 2 to about 6, or typically about 2 to about 4. The polyol 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 50. Flexible molding foams also use copolymer polyols as part of the total polyol content in the foam composition, which typically have an OH value in the range of 15 to 50, a MW range of typically 1200 to 8000, and more typically 2000 to 6000, and a % solids content of 10% to 60%. Open-cell, low-density spray foams typically use polyether polyols with an average MW of 1500 to 6000 and an OH value of 15 to 50. The amount of polyol is defined in pphp. There are four types of polyols as defined above: standard polyols or polyether polyols that can be used in the range of about 100 pphp (sole polyol) to about 10 pphp. Copolymer polyols (CPP) that can be used in the range of about 0 to about 80 pphp. NOP (natural oil polyol) that can be present in the range of about 0 to about 40 pphp. Finally, Mannich polyols are used in combination with other polyols and in the range of 0 to 80 pphp, about 0 to about 50 pphp, and in some cases about 0 to about 20 pphp.

[0114] Other polyols commonly used in PIR / PUR foam forming methods include polyalkylene ethers and polyester polyols. Polyalkylene ether polyols include poly(epoxide) polymers, such as poly(ethylene oxide) and poly(propylene oxide) polymers and copolymers, which have terminal hydroxyl groups derived from polyhydroxy compounds, including glycols 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, and similar low molecular weight polyols.

[0115] Amine polyether polyols can be used in this invention. These can be prepared by reacting amines, such as ethylenediamine, diethylenetriamine, toluenediamine, diphenylmethanediamine, or triethanolamine, with ethylene oxide or propylene oxide.

[0116] In another aspect of the invention, a single high molecular weight polyether polyol, or a mixture of high molecular weight polyether polyols, such as different multifunctional materials and / or mixtures of materials with different molecular weights or different chemical compositions, may be used.

[0117] In another aspect of the invention, polyester polyols, including those produced when dicarboxylic acids react with excess diols, can be used. Non-limiting examples include the reaction of adipic acid, phthalic acid, or phthalic anhydride with ethylene glycol or butanediol. Polyols usable in the invention can be prepared by reacting lactones with excess diols, such as caprolactone with propylene glycol. In a further aspect, compounds containing active hydrogen, such as polyester polyols and polyether polyols, and combinations thereof, can be used in the invention.

[0118] 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 functionality of about 2 to about 8, about 3 to about 6 and in some cases about 4 to about 6.

[0119] Preferably, the amount of polyol can be from about 0 pphp to about 100 pphp, from about 10 pphp to about 90 pphp, and in some cases from about 20 pphp to about 80 pphp.

[0120] Blowing agent

[0121] Polyurethane foam production can be aided by incorporating blowing agents (BA) to create voids in the polyurethane matrix during polymerization. Any suitable blowing agent can be used. Suitable blowing agents include low-boiling-point compounds that vaporize during exothermic polymerization. Most such blowing agents are inert or have low reactivity, so they are unlikely to decompose or react during polymerization. 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-point hydrocarbons such as cyclopentane, isopentane, n-pentane, and mixtures thereof. The amount of BA is typically from about 0 (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 be present in the range of about 0 (if BA is included) to about 60 pphp (very low density foam), typically about 1.0 pphp to about 10 pphp and in some cases about 2.0 pphp to about 5 pphp.

[0122] Preferred examples of HFC include, but are not limited to, HFC-245fa, HFC-134a, and HFC-365; exemplary examples of HCFC include, but are not limited to, HCFC-141b, HCFC-22, and HCFC-123.

[0123] Exemplary hydrocarbons include, but are not limited to, n-pentane, isopentane, cyclopentane, and any combination thereof. In one aspect of the invention, the blowing agent or mixture of blowing agents comprises at least one hydrocarbon. In another aspect, the blowing agent comprises n-pentane.

[0124] In another aspect of the invention, the foaming agent is essentially composed of n-pentane or a mixture of n-pentane and one or more foaming agents.

[0125] Preferred examples of hydrohalogenated olefin blowing agents are HFO-1234ze (trans-1,3,3,3-tetrafluoroprop-1-ene), HFO-1234yf (2,3,3,3-tetrafluoropropene), HFCO-1233zd (1-propene,1-chloro-3,3,3-trifluoro), HFO-1336mzz I (trans-1,1,1,4,4,4-hexafluoro-2-butene), etc.

[0126] Other optional components

[0127] Various other components may be included in the formulation for manufacturing foam according to the invention. Preferred examples of optional components include, but are not limited to, cell stabilizers, crosslinking agents, chain extenders, pigments, fillers, flame retardants, auxiliary urethane gelling catalysts, auxiliary urethane foaming catalysts, transition metal catalysts, alkali metal and alkaline earth metal carboxylates, and any combination thereof.

[0128] Preferred cell stabilizers may include, for example, silicone surfactants and organic anionic, cationic, amphoteric, or nonionic surfactants. Preferred examples of suitable silicone surfactants include, but are not limited to, polyalkylsiloxanes, polyoxyethylene 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 sulfates, salts of phosphates, 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 hexadecyltrimethylammonium chloride and hexadecylpyridine chloride. Suitable surfactants include, but are not limited to, ethoxylated tallow amine, benzalkonium chloride, and benzyl chloride. Preferred suitable amphoteric or amphoteric surfactants include, but are not limited to, sulfobetaine, amino acids, imino acids, betaine, and phosphates. Preferred suitable nonionic surfactants include, but are not limited to, fatty alcohols, polyoxyethylene glycol alkyl ethers, polyoxypropylene glycol alkyl ethers, glucosides (such as decyl, dodecyl, and octyl glucosides), polyoxyethylene glycol alkylphenol ethers, and glycol alkyl esters. Preferably, the cell stabilizer can be used in amounts from about 0.1 to about 20 pphp, typically from about 0.1 to about 10 pphp, and in some cases from about 0.1 to about 5.0 pphp. Preferably, the flame retardant can be used in amounts from about 0 to about 20 pphp, from about 0 to about 10 pphp, and from about 0 to about 5 pphp.

[0129] Crosslinking agents include, but are not limited to, low molecular weight compounds containing at least two structural moieties selected from hydroxyl, primary amino, secondary amino, and other groups containing active hydrogen that can react with isocyanate groups. Preferred crosslinking agents include, for example, polyols (especially triols such as glycerol and trimethylolpropane), polyamines, and combinations thereof. Non-limiting examples of polyamine crosslinking agents include diethyltoluenediamine, chlorodiaminobenzene, diethanolamine, diisopropanolamine, triethanolamine, tripropanolamine, 1,6-hexanediamine, and combinations thereof. Typical diamine crosslinking agents contain 12 carbon atoms or less, more typically 7 or less. Preferably, the crosslinking agent can be used in amounts from about 0.1 to about 20 pphp, typically from about 0.1 to about 10 pphp, and in some cases from about 0.1 to about 5.0 pphp.

[0130] Preferred examples of chain extenders include, but are not limited to, compounds having hydroxyl or amino functional groups, such as glycols, amines, diols, and water. Specific, non-limiting examples of chain extenders include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentanediol, 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 from about 0.1 to about 100 pphp, typically from about 0.1 to about 50 pphp, and in some cases from about 0.1 to about 5.0 pphp.

[0131] Pigments can be used to color-code polyurethane foam during manufacturing, for example, to identify product grades or to mask yellowing. Pigments can include any suitable organic or inorganic pigments known in the polyurethane industry. For example, organic pigments or colorants include, but are not limited to, azo / diazo dyes, phthalocyanines, and diazonium chlorides. Azides and carbon black. Examples of inorganic pigments include, but are not limited to, titanium dioxide, iron oxides, or chromium oxide. Preferably, the amount of pigment can be from about 0 pphp (unpigmented) to about 40 pphp.

[0132] 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 can be from about 0 pphp (unfilled) to about 40 pphp.

[0133] Flame retardants can be used to reduce the flammability of polyurethane foam. Suitable flame retardants include, but are not limited to, chlorinated phosphates, 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.

[0134] In one aspect of the invention, the bicyclic guanidine of the invention can be used with an isocyanate-free amine catalyst, commonly referred to as a fugitive catalyst. Preferred examples of short-acting amine catalysts in this category include triethylenediamine (TEDA), N-methylimidazolium, 1,2-dimethylimidazolium, N-methylmorpholine, N-ethylmorpholine, triethylamine, N,N'-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl)hexahydrotriazine, 2,4,6-tris(dimethylaminomethyl)phenol, N-methyldicyclohexylamine, pentamethyldipropylenetriamine, N-methyl-N'-(2-dimethylamino)ethylpiperazine, tributylamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexylamine, bis(dimethylaminoethyl) ether, tris(3-dimethylamino)propylamine, 1,8-diazabicyclo[5.4.0]undecane (26ndecane), or acid-blocked derivatives thereof, and any mixtures thereof.

[0135] Certain aspects of the invention are illustrated by the following examples. These examples are merely illustrative and should not be limited to the scope of any of the appended claims. Foam is evaluated using manual mixing or machine evaluation as described below. Detailed Implementation

[0136] Example

[0137] Example 1: The present invention

[0138] Preparation of reaction product from guanidine and ethylene glycol

[0139] Guanidine hydrochloride (95.5 g, 1.00 mol) was suspended in 143 g ethylene glycol in a 250 mL three-necked RB flask. The reactor assembly was purged with nitrogen for at least 5 minutes. A scrubber containing glacial acetic acid and DI water was connected to the reactor via tubing to capture the precipitated ammonia. The suspension was heated to approximately 50 °C while ammonia precipitated and stirred until the mixture became clear. The infrared spectra of the reactants and products were recorded. The reaction was monitored by IR. Changes in the infrared spectrum particularly occurred, substantially indicating the disappearance of guanidine hydrochloride (…). = 1625 cm -1 and 1590 cm -1 ) and the emergence of new products ( = 1655 cm -1 The C=NH stretching frequency of the compound is present. The shift to higher frequencies coincides with the formation of 2-hydroxyethyl aminoimine and its equilibrium product, 1,3-dioxolane-2-imine. The reacted mixture is not purified and is used as is in the next step.

[0140]

[0141]

[0142] The FTIR spectra of guanidine hydrochloride and the product of Example 1 are shown in Figure 7 middle.

[0143] Example 2 The present invention

[0144] Preparation of reaction product from guanidine and ethylene glycol

[0145] Guanidine hydrochloride (95.5 g, 1.00 mol) was suspended in 143 g ethylene glycol in a 250 mL three-necked RB flask. The reactor assembly was purged with nitrogen for at least 5 minutes. A scrubber containing glacial acetic acid and DI water was connected to the reactor via tubing to capture the precipitated ammonia. The suspension was heated to approximately 170°C while ammonia was precipitating and stirred until the mixture became clear. The released ammonia was collected in an acid scrubber. The infrared spectra of the reactants and products were recorded, wherein changes in the infrared spectra, particularly in the C=NH stretching, as described in Example 1, indicated product formation. The reacted mixture was not purified and was used as is in the next step.

[0146] Example 3 The present invention

[0147] Reaction between product mixture from Example 1 and DPTA

[0148] The product obtained in Example 1 was loaded into a feeding funnel. Dipropylenetriamine (DPTA, 131.2 g, 1.00 mol) and a magnetic stir bar were loaded into a reaction flask. The reaction apparatus was essentially a three-necked round-bottom flask containing DPTA and connected to a reflux condenser, a thermocouple, and a feeding funnel containing the reaction product of Example 1. The reactor assembly was purged with nitrogen for at least 5 minutes. A scrubber containing glacial acetic acid and DI water was connected to the reactor via tubing to capture the precipitated ammonia. The DPTA was heated to 170°C with stirring. The reaction product of Example 1 was then slowly added, at which point ammonia precipitation was detected. Heating continued for approximately 5.5 hours until ammonia precipitation ceased. The reaction flask was cooled to room temperature. The contents of the flask were weighed to approximately 320 g, and a GC sample was prepared in MeOH to generate a free base using 1M KOH added to MeOH. No unreacted DPTA was observed in the GC chromatogram. TBD was the largest component in the GC chromatogram except for EG. The DPTA conversion rate (quantitative) and TBD salt yield (91%) were calculated from the NMR results.

[0149]

[0150] Example 4 The present invention

[0151] Preparation of reaction product from guanidine and 1,3-propanediol

[0152] 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 containing glacial acetic acid and DI water was connected to the reactor via tubing to capture the precipitated ammonia. The suspension was heated to approximately 50°C while ammonia was precipitating and stirred until the mixture became clear. The infrared spectra of the reactants and products were recorded. Once the reaction was complete, changes in the infrared spectra occurred particularly at the C=NH stretching frequency, which substantially indicates the disappearance of guanidine hydrochloride. The reacted mixture was not purified and was used as is in the next step. The FTIR spectra of guanidine hydrochloride and the product of Example 4 are shown in... Figure 8 middle.

[0153] Example 5: The present invention

[0154] Reaction between product mixture of Example 4 and DPTA

[0155] The product obtained in Example 4 was loaded into a feeding funnel. Dipropylenetriamine (DPTA, 131.2 g, 1.00 mol) and a magnetic stir bar were loaded into a reaction flask (500 mL, three-necked 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 of Example 4 was slowly added at 170°C. Heating was continued for approximately 7 hours until ammonia precipitation ceased. 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 using 1M KOH added to MeOH to generate a free base. No unreacted DPTA was observed in the GC chromatogram. TBD was the largest component in the GC chromatogram except for propylene glycol (PDO). The DPTA conversion (quantitative) and TBD salt yield (90%) were calculated from the NMR results.

[0156] Example 6 The present invention

[0157] Preparation of TBD in bio-based 1,3-propanediol HCl

[0158] Repeat the procedures outlined in Examples 4 and 5, but instead of using 1,3-propanediol derived from fossil-based materials, use SUSTERRA. ® The purchased bio-based PDO was used for the reaction. The DPTA conversion rate (quantitative) and TBD salt yield (89%) were calculated from the NMR results.

[0159] Example 7 The present invention

[0160] Preparation of TBD sulfate in ethylene glycol (EG)

[0161] 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 containing glacial acetic acid and DI water was connected to the reactor via tubing to capture the precipitated ammonia. The suspension was reacted as described in Example 1. The reaction mixture was cooled and placed in a feeding funnel. Dipropylenetriamine (DPTA, 19.7 g, 0.150 mol) and a magnetic stir bar were loaded into the reaction flask (100 mL, three-necked RB). EG (19 g) was also loaded into the reaction flask to obtain a solution of DPTA in EG (52 wt%). The reaction apparatus was assembled and purged with nitrogen for at least 5 minutes. The DPTA solution was heated to 170 °C with stirring, and the above reaction product was slowly added at 170 °C. Heating was continued for approximately 5 hours until ammonia precipitation ceased. The reaction flask was cooled to room temperature, and a golden liquid was observed. The contents of the flask weighed approximately 72 g, and a GC sample was prepared in MeOH using 1M KOH added to MeOH to generate free base. No unreacted DPTA was observed in the GC chromatogram. TBD was the largest component in the GC chromatogram besides EG. DPTA conversion (quantitative) and TBD salt yield (97%) were calculated from the NMR results.

[0162] Example 8 The present invention

[0163] Preparation of TBD mesylate in ethylene glycol

[0164] 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 containing glacial acetic acid and DI water was connected to the reactor via tubing to capture the precipitated ammonia. The suspension was reacted as described in Example 1 to obtain a methanesulfonate mixture, as previously stated. Dipropylenetriamine (DPTA, 9.84 g, 0.0750 mol) and a magnetic stir bar were loaded into a reaction flask (100 mL, three-necked 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 above reaction product was slowly added at 170°C. Heating continued for approximately 5 hours until ammonia precipitation ceased. The reaction flask was cooled to room temperature, and a yellow liquid was observed. The contents of the flask weighed approximately 77 g, and a GC sample was prepared in MeOH using 1M KOH added to MeOH to generate free base. No unreacted DPTA was observed in the GC chromatogram. TBD was the largest component in the GC chromatogram except for EG. The DPTA conversion (quantitative) and TBD salt yield (>99%) were calculated from the NMR results.

[0165] Example 9 The present invention

[0166] Preparation of TBN in ethylene glycol HCl

[0167] 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 a feeding funnel. N-(2-aminoethyl)-1,3-propanediamine (AEPDA, 11.7 g, 0.10 mol) and a magnetic stir bar were loaded into a reaction flask (100 mL, three-necked 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 above reaction product was slowly added at 170 °C. Heating was continued for approximately 4 hours until ammonia precipitation ceased. 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 using 1M KOH added to MeOH to generate a free base. No unreacted AEPDA was observed in the GC chromatogram. TBN was the largest component in the GC chromatogram except for EG. The AEPDA conversion rate (quantitative) and TBN salt yield (94%) were calculated from the NMR results.

[0168] Example 10 The present invention

[0169] Preparation of AP-TBD in ethylene glycol HCl

[0170] Guanidine hydrochloride (7.2 g, 0.075 mol) was suspended in 17 g of ethylene glycol and reacted as described in Example 1. N,N'-bis(3-aminopropyl)-1,3-propanediamine (TPTA, 14.1 g, 0.075 mol) and a magnetic stir bar were loaded into a reaction flask (100 mL, three-necked 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 above reaction product was slowly added at 170 °C. Heating continued for approximately 4.5 hours until ammonia precipitation ceased. 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 using 1M KOH added to MeOH to generate a free base. No unreacted TPTA was 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.

[0171] Example 11 The present invention

[0172] Preparation of TBD using NaOMe solution in ethylene glycol

[0173] TBD in EG HCl (157 g, 0.500 mol) was loaded into a dried reaction flask (1 L). The apparatus was assembled and purged with nitrogen for approximately 10 minutes. The mixture was cooled using a water bath at room temperature. The solution was mixed using a mechanical stirrer (150 rpm). Sodium methoxide (NaOMe) solution (28 wt%, 101 g, 0.52 mol) was loaded into a feeding funnel. The apparatus was purged with nitrogen for ~10 minutes before addition. The NaOMe solution was added after 5 minutes, and salt formation was observed upon addition. No exothermic reaction was observed upon addition. An additional 120 mL of anhydrous IPA was added to rinse the feeding funnel. The white slurry was mixed for an additional 60 minutes and 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 fine solids, and 309 g was collected. Volatile components were removed under reduced pressure using a rotary evaporator. The concentrated filtrate weighed 127 g and was bubbled overnight with nitrogen. After overnight precipitation, a significant amount of salt had settled onto the flask walls, and the final weight of the concentrated filtrate was 126 g. This concentrated filtrate was filtered using a 1 L Millipore pressure filter equipped with a 0.45 μm Millipore Duropore filter membrane (142 mm). The filtrate (112 g) was a golden-yellow liquid. Aliquots were taken for GC analysis in MeOH. The GC chromatogram showed that TBD was the largest component in the GC chromatogram besides EG. The TBD yield was approximately 73%.

[0174] Example 12 The present invention

[0175] Preparation of TBD using KOMe solution in ethylene glycol

[0176] TBD in EG HCl (162.3 g, 0.501 mol) was loaded into a dried reaction flask (1 L). The apparatus was assembled and purged with nitrogen for approximately 10 minutes. The mixture was cooled using a water bath at room temperature. The solution was mixed using a mechanical stirrer. A potassium methoxide (KOMe) solution (25.1 wt%, 144 g, 0.52 mol) was loaded into a feeding funnel. The apparatus was purged with nitrogen for ~10 minutes before addition. The KOMe solution was added after 30 minutes, and salt formation was observed upon addition. No exothermic reaction was observed upon addition. An additional 150 mL of anhydrous IPA was added to rinse the feeding funnel. The white slurry was mixed for another 2 hours and then 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 solids, and 444 g was collected. Volatile components were removed under reduced pressure using a rotary evaporator. The concentrated filtrate weighed 145 g. This concentrated filtrate was filtered using a 1 L Millipore pressure filter equipped with a 0.45 μm Millipore Duropore filter membrane (142 mm). The filtrate (134 g) was a golden-yellow liquid. The filtrate was bubbled overnight with nitrogen to remove any residual solvent, yielding 133 g after bubbling. Aliquots were taken for GC analysis in MeOH. The GC chromatogram showed that TBD was the largest component in the GC chromatogram besides EG. The TBD yield was approximately 88%.

[0177] Example 13 The present invention

[0178] Preparation of TBD using NaOMe solution in 1,3-propanediol

[0179] TBD in PDO HCl (214.6 g, 0.501 mol) was loaded into a dried reaction flask (1 L). 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 loaded into a feeding funnel. The apparatus was purged with nitrogen for ~10 minutes before addition. The NaOMe solution was added after 5 minutes, and salt formation was observed upon addition. No exothermic reaction was observed upon addition. Additional MeOH (~35 mL) was added to rinse the feeding funnel. The white slurry was mixed for another 60 minutes and 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 concentrated filtrate weighed 191 g and was bubbled overnight with nitrogen. After overnight precipitation, a significant amount of salt had settled onto the flask walls, and the final weight of the concentrated filtrate was 190 g. This concentrated filtrate was filtered using a 1 L Millipore pressure filter equipped with a 0.45 μm Millipore-Duropore membrane (142 mm). The filtrate (175 g) was a yellow liquid. Aliquots were taken for GC analysis in MeOH. The GC chromatogram showed that TBD was the largest component besides PDO. The TBD yield was approximately 89%.

[0180] Example 14 The present invention

[0181] Preparation of TBD using NaOMe solution in bio-based 1,3-propanediol

[0182] TBD in bio-based PDO HCl (Susterra) ®216.4 g (0.500 mol) was loaded into a dried reaction flask (1 L). The apparatus was assembled and purged with nitrogen for approximately 10 minutes. The solution was mixed using a mechanical stirrer (100 rpm). A NaOMe solution (29.9 wt%, 96.6 g, 0.53 mol) was loaded into a feeding funnel. The apparatus was purged with nitrogen for approximately 10 minutes before addition. The NaOMe solution was added after 15 minutes, and salt formation was observed upon addition. No exothermic reaction was observed upon addition. An additional 53 g of MeOH was added to rinse the feeding funnel. The white slurry was mixed for another 4 hours and then 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 concentrated filtrate weighed 173 g and was bubbled overnight with nitrogen. After overnight precipitation, a significant amount of salt had settled onto the flask walls, and the final weight of the concentrated filtrate was 172 g. This concentrated filtrate was filtered using a 1 L Millipore pressure filter equipped with a 0.45 μm Millipore Duropore filter membrane (142 mm). The filtrate (169 g) was a yellow liquid. Aliquots were taken for GC analysis in MeOH. The GC chromatogram showed that TBD was the largest component besides PDO. The TBD yield was approximately 84%.

[0183] Example 15 The present invention

[0184] TBD as a catalyst for use in moisture-cured SMP applications: Catalyst for 1K STPU moisture-curing formulation

[0185] The one-component (1K) silane-terminated polyurethane (STPU) moisture-curing formulations used in Examples 1, 2, and 3 are as follows:

[0186] Table I: Control Formulations of Single-Component Silane-Ended Polyurethanes

[0187]

[0188] The one-component (1K) silane-terminated polyurethane (STPU) moisture-curing formulations used in Examples 4, 5, and 6 are as follows:

[0189] Table II: Control Formulations of Single-Component Silane-Ended Polyurethanes

[0190]

[0191] The following abbreviations are used in the following embodiments:

[0192] Polymer ST 80 is a high-modulus SMP resin based on a polypropylene oxide backbone functionalized with trimethoxysilyl groups at the ends, with a viscosity of 20,000 mPa·s at 25°C (Evonik Corp.).

[0193] Dynasylan VTMO is a vinyltrimethoxysilane (Evonik Corp.)

[0194] Aerosil R 106 is a hydrophobic fumed silica (Evonik Corp.) surface-treated with D4 (octamethylcyclotetrasiloxane).

[0195] VESTINOL 9 is diisononyl phthalate (Evonik Corp.)

[0196] Elatur CH stands for diisononyl cyclohexanecarboxylate (Evonik Corp.)

[0197] Dynasylan DAMO-T is N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Evonik Corp.)

[0198] DBU is 1,8-diazabicyclo(5.4.0)undec-7-ene.

[0199] DBTDL stands for dibutyltin dilaurate.

[0200] The formulations used in the examples were prepared using a high-speed centrifugal mixer, and then subjected to the following tests:

[0201] Surface drying time test

[0202] Surface drying time, also known as skinning time, is assessed by touching the surface of the curing mixture with gloved fingers at set time intervals until no material transfers to the gloves. For Examples 1-6, tests were conducted at 25°C and 50% relative humidity.

[0203] The test results are shown in Table 1-2.

[0204] Table 1

[0205]

[0206] Table 2

[0207]

[0208] Example 16 The present invention

[0209] TBD as a catalyst for use in the preparation of rigid foams for use in thermal insulation applications

[0210] A 36.1 wt% TBD sample in EG was prepared by diluting the product of Example 11 or Example 12 with additional ethylene glycol. This solution was used as a catalyst to manufacture rigid polyurethane foam for thermal insulation applications. Typical polyurethane foam formulations for thermal insulation are described in the table below:

[0211] Table II: Rigid Foam Control Formulation

[0212]

[0213] 1 : A sucrose-initiated ethylene oxide / propylene oxide copolymer with a hydroxyl value of approximately 350 to 400;

[0214] 2 It can be used as a polysiloxane silicone surfactant, Tegostab® 8465, purchased from Evonik.

[0215] 3 It can be used as an amine catalyst for Polycat®8, N,N-dimethylaminocyclohexane, purchased from Evonik.

[0216] 4 The trimer catalyst is a 70% by weight solution of potassium 2-ethylhexanoate, purchased from Evonik, in diethylene glycol;

[0217] 5 The blowing agent is 1,1,1,3,3-pentafluoropropane, available as Enovate® 245fa, a liquid hydrofluorocarbon from Honeywell.

[0218] 6 Rubinate® M is a commercially available MDI from Huntsman.

[0219] Catalyst reactivity in rigid polyurethane systems was evaluated using a FOMAT sonar rate of rise (ROR) apparatus and free-rising cup foam samples. FOMAT standard software generated height versus time and velocity versus time graphs. These graphs can be used to compare the relative reactivity of different catalyst formulations. MDI polyurethane foam was prepared using conventional manual mixing methods.

[0220] The table below shows the amount of catalyst required to match the string gel time in standard rigid formulations when using a solution of TBD in ethylene glycol. Clearly, TBD exhibits higher activity than the standard Polycat®8 catalyst, indicating that it is an effective catalyst for the manufacture of rigid polyurethane foams.

[0221]

[0222] exist Figure 1 In the diagram, the curve slightly to the left corresponds to Polycat® 8, while the curve slightly to the right corresponds to the TBD solution in EG. The two curves almost superimpose and can be considered equivalent within the experimental error range of manual mixing assessment. Foam samples are visible in... Figure 2 The foam made with Polycat®8 is shown on the left, and the foam made with TBD is shown on the right.

[0223] Example 17 The present invention

[0224] TBD as a catalyst for use in the preparation of PIR rigid foams for use in thermal insulation applications

[0225] Foam is produced by adding a catalyst to a premix consisting of the following substances in a 1759 mL beaker: a polyol (a polyester polyol supplied by Stepanpol with a hydroxyl value of 230-250 and an equivalent of 234), a flame retardant (TCPP; tris(1-chloro-2-propyl) phosphate), a surfactant (Dabco® DC5598 in the case of pentane foaming, and DABCO® SI3201 in the case of formic acid / pentane foaming, both of which are silicone surfactants supplied by Evonik Corporation), a blowing agent (typically n-pentane or a mixture of n-pentane and 85% formic acid aqueous solution), and, optionally, a water mixture. Using a top-mounted stirrer equipped with a 6.2 cm diameter impeller, this composition is mixed at approximately 5,000 RPM (or 3,000 rpm in specified cases) for approximately 5 seconds (s). Isocyanate is then added to achieve the desired isocyanate index, which is typically in the range of 270-300. The premix was then thoroughly mixed at approximately 5,000 RPM for approximately 5 seconds using the same stirrer. A 1759 mL beaker was placed below the 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 foamed material. At the end of the foaming process, the foam height was approximately 10 cm above the rim of the 1759 mL beaker. The string gel time (defined in seconds as the time in seconds when the material in the polymer is in contact with a wooden tongue depressor) and the surface drying time (TFT; defined in seconds as the time in seconds when the surface reaches a sufficiently firm or cured state such that no damage or adhesion occurs on the surface when in contact with a wooden tongue depressor) were measured using a timer and manually determined using a tongue depressor. The onset time was defined in seconds as the time in seconds when the foamed material began to expand.

[0226] Table III: Lamination Control Formulations

[0227]

[0228] The table below illustrates the potency of TBD in a 36.9% by weight solution in ethylene glycol when used as a catalyst in a 270 index PIR formulation. Additionally, Figure 3 The smooth rise curve (lower curve) of TBD is shown compared to two runs using the standard catalyst DABCO® K15 (where a typical “PIR step” is formed at approximately 60 seconds). The smooth rise curve provides the advantage of easier processing in high-speed laminators.

[0229]

[0230] As demonstrated by the following data highlighting a trimer conversion rate of approximately 73%, TBD is an effective trimer catalyst.

[0231]

[0232] Foam samples can be seen in Figure 4 The foam made with DABCO® K15 is shown on the left, and the foam made with 33.9% TBD in EG is shown on the right.

[0233] Example 18 The present invention

[0234] Acid-blocked TBD as a catalyst for use in the preparation of high-density rigid Spray foams for use in thermal insulation applications using commercially available hydrofluoroolefin blowing agents

[0235] A sample of acid-blocked TBD in EG was prepared by mixing the product of Example 11 or 12, succinic acid, and water with or without additional ethylene glycol. This solution, having the following composition, was used as a catalyst to manufacture rigid polyurethane foam for thermal insulation applications:

[0236]

[0237] Typical high-density spray foam formulations are shown in Table IV:

[0238]

[0239] Terol ®305 is a polyester polyol, Jeffol ®R470x is a polyether polyol, obtained from Huntsman. Flame retardant: TCPP obtained from ICL-IP. Surfactant: DABCO®DC193 obtained from Evonik Industries. Forane® 1233zd is a blowing agent (1-chloro-3,3,3-trifluoropropene) obtained from Arkema. HFO solubility enhancer: DABCO®PM301 obtained from Evonik Industries. Figure 5

[0240] The table below shows the amount of EG solution used in acid-blocked TBD to provide high-quality foam:

[0241]

[0242] Figure 6 The rise distribution curve of succinic acid-blocked TBD in high-density spray foam formulation is shown. ​The sample shows a manually mixed foam, highlighting the fine pore structure of the sample.

Claims

1. A method for producing bicyclic guanidine and its salts in a reactor system, comprising the following steps: a) Compounds of formula CX2Y in which X = NH2 and Y = NH, O, or S have a pKa of In the presence of an acid of 2, with at least one of the following formulas: H(OC) where n = 2-6 and x = 0-10 n H 2n-x (OH) x+1 The reactive diols, when reacted at temperatures ranging from 50°C to 190°C, release ammonia and produce reaction products as clear, homogeneous solutions. b) Load the reaction product from a) into the feed pump; c) Connect the feed pump to a dipropylenetriamine of the formula H2N-(CH2)3-NH-(CH2)3-NH2 or the formula H2N-(CH2) m -NH-(CH2) n A reactor vessel for -NH-R dialkyltriamines, wherein m and n are independently 2 to 5, and R = C 1-18 Alkyl, alkyl-cycloalkyl, OH-alkyl (hydroxyalkyl), H2N-alkyl (amino-alkyl), alkenyl, aryl, aralkyl or substituted aralkyl; and d) The reaction product of a) is fed into the reactor vessel, wherein the temperature in the reactor vessel is in the range of 160-200°C, thereby producing a solution of bicyclic guanidine salt in high yield, high dipropylenetriamine conversion and with minimal or no unwanted urea impurities.

2. The method according to claim 1, wherein the compound of formula CX2Y, in which X = NH2 and Y = NH, O or S, has a pKa of In the presence of an acid of 2, and with the formula H(OC) where n = 2-6 and x = 0-10. n H 2n-x (OH) x+1 The diol, represented by [insert name here], reacts at temperatures ranging from 50°C to 100°C, releasing ammonia and producing reaction products comprising aminoimine esters of the following formula: And the following formula for dioxolane: The amount of aminoimine ester in the reaction product is higher than the amount of dioxolane in the reaction product.

3. The method according to claim 1, wherein the compound of formula CX2Y, in which X = NH2 and Y = NH, O or S, has a pKa of In the presence of an acid of 2, and with the formula H(OC) where n = 2-6 and x = 0-10. n H 2n-x (OH) x+1 The diol, represented by [insert name here], reacts at temperatures ranging from 100°C to 190°C, releasing ammonia and producing reaction products comprising aminoimine esters of the following formula: And the following formula for dioxolane: The amount of dioxolane in the reaction product is higher than the amount of aminoimide ester in the reaction product.

4. The method according to any one of the preceding claims, wherein the reactive diol is composed of H(OC) wherein n = 2-6 and x = 0-10. n H 2n-x (OH) x+1 express.

5. The method according to any one of the preceding claims, wherein the reactive diol is composed of H(OC) of formula where n = 2-4 and x = 0-1. n H 2n-x (OH) x+1 express.

6. The method according to any one of the preceding claims, wherein the reactive diol is composed of H(OC) wherein n = 2-4 and x = 0. n H 2n-x (OH) x+1 This indicates that the OH group is located at the terminal carbon.

7. The method according to any one of the preceding claims, wherein when X = NH2, Y = NH, n = 2 and x = 0, the aminoimine ester is 2-hydroxyethyl aminoimine, and the dioxolane is 1,3-dioxolane-2-imine.

8. The method according to any one of claims 1-4, wherein the reactive diol is ethylene glycol, 1,3-propanediol, 1,4-tetramethylenediol, glycerol, diglycerol, MP-diol (2-methyl-1,3-propanediol), or any combination thereof.

9. The method according to claim 8, wherein the reactive diol is glycerol.

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

11. The method according to any one of the preceding claims, wherein for the formula H2N-(CH2) m -NH-(CH2) n -NH-R dialkyltriamine, where m and n are independently 2 to 3.

12. The method according to any one of the preceding claims, wherein for the formula H2N-(CH2) m -NH-(CH2) n -NH-R dialkyltriamine, where m and n are independently 3.

13. The method according to any one of the preceding claims, wherein for the formula H2N-(CH2) m -NH-(CH2) n -NH-R dialkyltriamine, where R is aminopropyl, aminoethyl, hydroxyethyl, or hydroxypropyl.

14. The method according to claim 16, wherein for the formula H2N-(CH2) m -NH-(CH2) n -NH-R dialkyltriamine, where R is aminopropyl.

15. The method according to any one of the preceding claims, wherein the bicyclic guanidine salt is produced in solution form at a high yield of 85% or higher.

16. The method according to any one of the preceding claims, wherein a bicyclic guanidine salt is produced in solution form with a conversion rate of more than 99% of dipropylenetriamine.

17. The method according to any one of the preceding claims, wherein the method further comprises the step of neutralizing with a methanol solution of sodium methoxide or potassium methoxide after removing solid salt by filtration.

18. The method according to any one of the preceding claims, wherein the reactive diol is a bio-based reactive diol.

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

20. The method according to any one of the preceding claims, wherein the guanidine salt is produced in bio-based 1,3-propanediol obtained by fermentation of biomass, characterized in that... Its composition contains 14 C isotopes.

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

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

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