WO2011125310A1

WO2011125310A1 - Catalyst for production of polyurethane resin and method for producing polyurethane resin

Info

Publication number: WO2011125310A1
Application number: PCT/JP2011/001892
Authority: WO
Inventors: 榊原徳; 田中宣志
Original assignee: サンアプロ株式会社
Priority date: 2010-04-05
Filing date: 2011-03-30
Publication date: 2011-10-13
Also published as: JPWO2011125310A1

Abstract

Disclosed is a catalyst for the production of a polyurethane resin, which is capable of maintaining good fillability into a mold or good applicability to a base by maintaining sufficiently long working life (pot life) of a resin, while enabling rapid curing of the resin after a certain period of time. Specifically disclosed is a catalyst for the production of a polyurethane resin, which is characterized by being a salt (E) that uses a cycloamidine (C) represented by general formula (1) in combination with one or more acids selected from the group consisting of acids (A1) having pKa₁ of 8-11 and one or more acids selected from the group consisting of acids (A2) having pKa₁ of 4-6. The catalyst for the production of a polyurethane resin is also characterized in that the content of the acids (A1) is 0.2-0.8 mole per 1 mole of the cycloamidine (C), the content of the acids (A2) is 0.2-0.8 mole per 1 mole of the cycloamidine (C), and the content of acids (A1 + A2) is 0.8-1.2 moles per 1 mole of the cycloamidine (C). (In general formula (1), m represents an integer of 2-6, and a hydrogen atom in the methylene group may be substituted by an organic group.)

Description

Polyurethane resin production catalyst and polyurethane resin production method

The present invention relates to a catalyst for producing a polyurethane resin and a method for producing a polyurethane resin using the catalyst. More specifically, the present invention relates to a catalyst suitable for producing a polyurethane resin such as a rigid / semi-rigid / soft foam and a production method suitable for a rigid / semi-rigid / soft foam using the catalyst.

Polyurethane resins formed by reacting polyols with organic polyisocyanates or isocyanate prepolymers can be used as hard and flexible foams, paints, adhesives, elastomers, sealants, etc., because they have a variety of physical properties and functions. It is used in a wide range of industrial fields, from materials to building materials, automobiles, electronics / electricity, and industrial materials.
In a two-part curable polyurethane resin that cures by mixing a polyol with an organic polyisocyanate or an isocyanate prepolymer, it can be filled into a mold after two-part mixing or applied to a substrate to cause a curing reaction. The method is generally practiced.
As the catalyst for producing these polyurethane resins, amine catalysts and metal catalysts are usually used. However, when the catalyst is used, the curing reaction is accelerated, but the pot life of the two-component liquid mixture is shortened. Problems such as insufficient filling in the mold and curing start before application of the base material are likely to occur. In addition, metal catalysts tend to be used from the viewpoint of safety because of their strong toxicity, and the need for alternative catalysts is increasing year by year.
In order to solve the problem of shortening the pot life of this two-component liquid mixture, by suppressing the initial reactivity after two-component mixing, the filling property in the mold and the application to the base material are good. And a method using a cycloamidine (salt) that can bring about rapid curing after a certain time as a catalyst is employed (see, for example, Patent Document 1 and Patent Document 2).

Japanese Patent Laid-Open No. 9-34215 Japanese Patent Laid-Open No. 60-240415

Conventionally, chlorofluorocarbon foaming agents have been mainly used for rigid foam applications such as panels and boards. However, due to the problem of ozone layer destruction, switching from chlorofluorocarbon foaming agents to water is proceeding.
However, when water is used as a foaming agent, the viscosity-reducing effect of the fluorocarbon foaming agent is lost, so the filling property in the mold is lowered, and even if cycloamidine (salt) is used, insufficient filling occurs. There is a problem that it becomes easy.
The object of the present invention is to increase the viscosity of a mixed solution by suppressing the initial reactivity after two-component mixing of a polyol and an organic polyisocyanate, even in the case of rigid foams such as panels and boards using water as a foaming agent. It is an object of the present invention to provide a catalyst for producing a polyurethane resin, which can moderately maintain the filling property in a mold and can cause rapid curing after a certain time.

The catalyst for producing the polyurethane resin of the present invention is characterized by one or more selected from the group consisting of cycloamidine (C) represented by the general formula (1) and acid (A1) of pKa ₁ = 8 to 11, and pKa ₁ = Salt (E) used in combination with one or more selected from the group consisting of 4 to 6 acids (A2), and the content of (A1) is 0.2 with respect to 1 mol of (C). -0.8 mol, the content of (A2) is 0.2-0.8 mol per mol of (C), and the content of (A1 + A2) is 0.8-1 per mol of (C) The point is that it is 2 mol.

{M represents an integer of 2 to 6, and the hydrogen atom of the methylene group may be substituted with an organic group. }

A feature of the method for producing a polyurethane resin of the present invention is that it includes a step of obtaining a polyurethane resin by reacting the above-mentioned catalyst for producing a polyurethane resin, a polyol and an organic polyisocyanate or an isocyanate prepolymer.

Using the polyurethane resin production catalyst of the present invention, even in the case of rigid foams such as panels and boards using water as a foaming agent, the initial reaction after two-component mixing of polyol and organic polyisocyanate or isocyanate prepolymer, etc. By suppressing the property, the thickening is moderated and the filling property in the mold can be kept good, and then it can be cured quickly.

When the salt of cycloamidine (C) represented by general formula (1) and an acid is used, the initial reaction after mixing the two liquids is suppressed as compared with the case of using only cycloamidine. The pot life can be maintained for a long time.
In this case, as the acid forming the salt with cycloamidine (C) becomes stronger, the initial reactivity can be suppressed, but rapid curing cannot be brought about after a certain period of time, resulting in deterioration of productivity and produced polyurethane. The physical properties of the resin are reduced.
Conversely, the weaker the acid that forms a salt with cycloamidine (C), the more rapid curing can occur after a certain period of time, but the initial reaction becomes faster, filling properties in the mold and application to the substrate. Can not keep good.
Using salts (E) comprising cycloamidine represented by the general formula (1) of the present invention and _{(C) pKa 1 = 8 ~} 11 acid (A1) and an acid of _{pKa 1 = 4 ~ 6 (A2} ) In this case, immediately after the two-component mixing of the polyol and the organic polyisocyanate or the isocyanate prepolymer, the initial reaction is suppressed by the acid (A2) of pKa ₁ = 4 to 6 in the salt (E). It is thought that the thickening of the resin becomes moderate. Further, after a certain time after the polyol and the organic polyisocyanate or the isocyanate prepolymer are reacted, the acid (A1) of pKa ₁ = 8 to 11 in the salt (E) accelerates the curing, so that the productivity of the polyurethane resin is increased. It is considered that deterioration and deterioration of physical properties can be prevented.

According to the production method of the present invention, since the polyurethane resin production catalyst is used, even in the case of rigid foams such as panels and boards using water as a foaming agent, by suppressing the initial reactivity immediately after mixing the two liquids The thickening is moderated and the filling property in the mold is improved. Then, it can be quickly cured.

<Salt (E) containing cycloamidine (C), pKa ₁ = 8 to 11 acid (A1) and pKa ₁ = 4 to 6 acid (A2)>
In the general formula (1), m represents an integer of 2 to 6, and preferably an integer of 3 to 5.
Examples of the organic group that may be substituted for the hydrogen atom of the methylene group include an alkyl group having 1 to 6 carbon atoms (such as methyl, ethyl, isopropyl, n-butyl, t-butyl, and n-hexyl), and 1 to 6 carbon atoms. Hydroxyalkyl groups (such as hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxyisopropyl, 3-hydroxy-t-butyl and 6-hydroxyhexyl) and dialkylamino groups having 2 to 12 carbon atoms (dimethylamino) Methylethylamino, diethylamino, diisopropylamino, t-butylmethylamino, di-n-hexylamino and the like.

Examples of the cycloamidine represented by the general formula (1) include 1,5-diazabicyclo [4,3,0] -nonene-5 (DBN), 1,5-diazabicyclo [4,4,0] -decene-5. 1,8-diazabicyclo [5,4,0] -undecene-7 (DBU; “DBU” is a registered trademark of Sun Apro Corporation), 5-hydroxypropyl-1,8-diazabicyclo [5,4, 0] -undecene-7 and 5-dibutylamino-1,8-diazabicyclo [5,4,0] -undecene-7. Of these, DBN and DBU are preferred.

The acid (A1) having a pKa ₁ = 8 to 11 includes an organic acid and an inorganic acid.
Organic acids include aromatic hydroxy compounds {phenol, alkyl-substituted phenols (o-cresol, m-cresol, p-cresol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, xylenols, trimethylphenols Tetramethylphenols, pentamethylphenols, etc.), alkoxy-substituted phenols (2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, etc.), Halogen-substituted phenols (fluorophenol, chlorophenol, bromophenol, iodophenol, etc.), naphthols, aminophenols, polyphenols (catechol, resorcinol, hydroquinone, biff) Nord, bisphenols, pyrogallol, phloroglucinol, benzenehexol etc.)}, and the like.

Examples of the inorganic acid include boric acid and perhydrohalic acid (perbromic acid, periodic acid, etc.).

Of these acids (A1) with pKa ₁ = 8 to 11, a phenol compound represented by the general formula (2) is preferable.

(Wherein R ₁ to R ₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or an alkoxy group)
Examples of the linear or branched alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, a t-butyl group, and an n-pentyl group.
Examples of the linear or branched alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, isopropoxy group and n-butoxy group.

Of the phenolic compounds represented by the general formula (2), phenol, o-cresol, 2,4,6-trimethylphenol, 2-methoxyphenol and 2-ethoxyphenol are particularly preferable.

As the acid (A2) of pKa ₁ = 4 to 6, carboxylic acid {saturated aliphatic carboxylic acid (acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, methylethylacetic acid, trimethylacetic acid, caproic acid, isocaproic acid, Diethylacetic acid, 2,2-dimethylbutyric acid, enanthic acid, caprylic acid, pelargonic acid, 2-ethylhexanoic acid, n-undecylenic acid, lauric acid, n-tridecylenic acid, myristic acid, n-pentadecylenic acid, palmitic acid, margarine Acid, stearic acid, n-nonadecylene acid, arachidic acid, n-heneicoic acid, etc.), unsaturated aliphatic carboxylic acids (acrylic acid, crotonic acid, isocrotonic acid, vinylacetic acid, methacrylic acid, 2-pentenoic acid, 3-pentene Acid, allyl acetic acid, angelic acid, tiglic acid, 3-methylcrotonic acid, 2-hexenoic acid, -Hexenoic acid, 4-hexenoic acid, 5-hexenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, 4-methyl-2-pentenoic acid, 4-methyl-2-pentenoic acid, 4-methyl-3-pentenoic acid, 2-ethylcrotonic acid, 2-heptenoic acid, 2-octenoic acid, palmitoleic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, elestearic acid, arachidonic acid, etc.) Saturated aliphatic dicarboxylic acids (succinic acid, glutaric acid, methyl succinic acid, adipic acid, ethyl succinic acid, pimelic acid, propyl succinic acid, suberic acid, azelaic acid, sebacic acid, etc.), alicyclic carboxylic acids (cyclopropanecarboxylic acid, Cyclobutanecarboxylic acid, cyclobutenecarboxylic acid, cyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexane Carboxylic acid, cyclohexenecarboxylic acid, cycloheptanecarboxylic acid, cycloheptenecarboxylic acid, etc.), aromatic carboxylic acids (benzoic acid, alkyl-substituted benzoic acids (3-methylbenzoic acid, 4-methylbenzoic acid, 3-ethylbenzoic acid) 4-hydroxybenzoic acid, 4-hydroxybenzoic acid, alkoxy-substituted benzoic acids (2-methoxybenzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, etc.), mercaptobenzoic acids, amino-substituted benzoic acids, 2 -Naphthoic acid, etc.), hydroxycarboxylic acids (ascorbic acid, etc.), ketocarboxylic acids (levulinic acid, etc.)}, monoalkyl carbonates (methyl carbonate, ethyl carbonate, etc.) and the like.
Of course, the above (A2) may be used alone or in combination of two or more.

Of these acids (A2) having a pKa ₁ = 4 to 6, 2-ethylhexanoic acid and oleic acid are preferred.

The content of (A1) is 0.2 to 0.8 mol, preferably 0.4 to 0.6 mol, and the content of (A2) is 1 mol of (C). 0.2 to 0.8 mol, preferably 0.4 to 0.6 mol, and the content of (A1 + A2) is 0.8 to 1.2 mol, preferably 0.9 to 0.1 mol with respect to 1 mol of (C). 1.1 mol, particularly preferably 0.95 to 1.05 mol.

As the salt (E), a salt of DBU, phenol and 2-ethylhexanoic acid {mixing ratio (C: A1: A2) is a molar ratio of 1: 0.5: 0.5}, DBU, phenol and 2-ethyl Hexanoic acid salt {mixing ratio (C: A1: A2) is molar ratio 1: 0.4: 0.4}, DBU, o-cresol and oleic acid salt {mixing ratio (C: A1: A2) is The molar ratio is 1: 0.6: 0.4}, the salt of DBU, 2,4,6-trimethylphenol and 2-ethylhexanoic acid {mixing ratio (C: A1: A2) is 1: 0. 3: 0.7}, DBU, 2-methoxyphenol and 2-ethylhexanoic acid salt {mixing ratio (C: A1: A2) is 1: 0.5: 0.5} in molar ratio, DBU and 2- Methoxyphenol and 2-ethylhexanoic acid salt {mixing ratio (C: A1: A2) is molar ratio 1: 0.5: 0.7}, salt of DBN, phenol and 2-ethylhexanoic acid {mixing ratio (C: A1: A2) is 1: 0.5: 0.5} in molar ratio, DBN and 2 A preferred example is a salt of methoxyphenol and 2-ethylhexanoic acid {mixing ratio (C: A1: A2) is 1: 0.5: 0.5} in molar ratio.

The catalyst of the present invention may contain a known solvent.
Examples of the solvent include water and alcohol (such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and butanediol).
When a solvent is contained, the content can be determined as appropriate, and is, for example, 5 to 1900% by weight based on the weight of the salt (E).

The catalyst of the present invention may contain other catalysts (such as an organometallic catalyst and an amine catalyst) without departing from the spirit of the present invention.
Examples of the organometallic catalyst include known organometallic catalysts, such as potassium carboxylates (such as potassium 2-ethylhexanoate and potassium acetate), organotin catalysts (stannous diacetate, stannous dioctoate, stannous dilaurate, stana Sudiolate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate and dioctyltin dilaurate), organic bismuth catalysts (such as bismuth octylate and bismuth naphthenate), and organic cobalt catalysts (such as cobalt naphthenate) .

Examples of the amine catalyst include known amine catalysts and the like, and amines (triethylenediamine, 2-methyltriethylenediamine, N-methylmorpholine, N-ethylmorpholine, dimorpholinodiethylaminoether, dimethylethanolamine, N, N, N ′ , N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, dimethylcyclohexylamine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine, bis (2-dimethylaminoethyl) ether and dimethylisopropanolamine, 1,2-dimethylimidazole, 1-methylimidazole, 1,4-dimethylimidazole, 1,2,4,5-tetramethylimidazole, 1-methyl-2- Isopropyl imidazole, 1-methyl-2-phenylimidazole, 1- (n-butyl) -2-methylimidazole, 1-isobutyl-2-methylimidazole, 1-benzyl-2-methylimidazole, imidazole and 2-methylimidazole, Quaternary ammonium salts (tetramethylammonium hydroxide salt, hydroxypropyltrimethyl quaternary ammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate and tetramethylammonium 2-ethylhexanoate ), And the like.

In the case of containing other catalyst, the amount (% by weight) of the other catalyst used is preferably 5 to 1900% by weight, more preferably 20 to 900% by weight, based on the weight of the salt (E).

The salt (E) can be obtained by mixing the cycloamidine (C) represented by the general formula (1), the acid (A1) of pKa ₁ = 8 to 11 and the acid (A2) of pKa ₁ = 4 to 6 It is done. The mixing ratio is as described above. When mixing, you may melt | dissolve and mix in a solvent. The solvent and its use amount are as described above.

The catalyst of the present invention is suitable for the production of polyurethane resins such as rigid, semi-rigid and flexible foams.

The method for producing a polyurethane resin of the present invention includes a step of reacting the polyurethane resin production catalyst of the present invention with a polyol and an organic polyisocyanate or an isocyanate prepolymer to obtain a polyurethane resin.

The amount of use (wt%) of the catalyst of the present invention {in the case of use in combination with other catalyst (wt)} is preferably 0.001 to 20 wt%, more preferably based on the weight of the polyol. Is an amount of 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight.

The polyol is not particularly limited, and known polyols can be used, and examples include polyoxyalkylene ether polyols, polyester polyols, amine polyols, polymer polyols, polybutadiene polyols, castor oil-based polyols, acrylic polyols, and mixtures thereof.

As the isocyanate, a known isocyanate or the like can be used. An aromatic polyisocyanate having 6 to 20 carbon atoms (excluding carbon atoms in the isocyanate group, the same shall apply hereinafter), an aliphatic polyisocyanate having 2 to 18 carbon atoms, a carbon number of 4 -15 cycloaliphatic polyisocyanate, C8-15 araliphatic polyisocyanate, modified products thereof (urethane modification, carbodiimide modification, allophanate modification, urea modification, burette modification, uretdione modification, uretoimine modification, isocyanurate) Modified and oxazolidone modified) and mixtures thereof.

Examples of the isocyanate prepolymer include those obtained by reacting the aforementioned polyol and organic polyisocyanate.

The isocyanate index is not particularly limited, but is preferably 50 to 800, more preferably 70 to 400. Within this range, the resin strength is good, and the possibility that unreacted isocyanato groups remain is also reduced.

In the polyurethane resin production method of the present invention, when the polyurethane resin is a polyurethane foam, the polyurethane foam is obtained by reacting the polyurethane resin production catalyst with a polyol and an organic polyisocyanate or an isocyanate prepolymer in the presence of a foaming agent. Obtaining a body.
As the foaming agent, water and a volatile foaming agent can be used.
As the volatile foaming agent, a known volatile foaming agent or the like can be used, such as chlorofluorocarbon (hydrogen atom-containing halogenated hydrocarbon) {for example, 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,3,3,3- Heptafluoropropane (HFC-227ea)}, hydrofluoroether {eg, HFE-254pc}, halogenated hydrocarbon {eg, methylene chloride}, low boiling point hydrocarbon {eg, propane, butane, pentane, cyclopentane}, carbonic acid Examples thereof include gases and mixtures thereof.
The catalyst of the present invention exhibits an effect that cannot be obtained with other catalysts, particularly water, among these blowing agents.

The amount of the foaming agent used is appropriately determined according to the density of the polyurethane foam to be produced and the physical properties of the foam. For example, the density (kg / m ³ ) of the obtained polyurethane foam is determined to be 5 to 200 (preferably 10 to 100).

In the production method of the present invention, when producing paints, adhesives, elastomers, sealants, etc. that do not use a foaming agent, if moisture is present in the system, foaming may occur during the reaction, so moisture is removed. It is desirable to do. When removing the water, it is desirable to subject the raw materials such as polyols and prepolymers to heat vacuum dehydration, or to add molecular sieves, zeolites and the like to the system.

In the production of polyurethane resins, if necessary, various known additives {crosslinking agents, chain extenders, foam stabilizers, flame retardants, viscosity reducers, solvents, antioxidants, ultraviolet absorbers, anti-aging agents, colorants ( Dyes, pigments), reaction retarders, fillers, and the like} and the like. When these various additives are used, these addition amounts are normal addition amounts as long as the respective functions are exhibited without departing from the gist of the present invention.

Hereinafter, although explained based on an example and a comparative example, the present invention is not limited only to these examples.

The example which adjusted the catalyst of this invention and the conventional catalyst is shown below.

<Example 1>
While stirring a predetermined amount of DBU and diethylene glycol as a solvent in a glass round bottom flask, a predetermined amount of phenol (pKa ₁ = 10.0) as acid (A1) of pKa ₁ = 8 to 11 is gradually added dropwise thereto. Then, the mixture was stirred and mixed. Subsequently, a predetermined amount of 2-ethylhexanoic acid (pKa ₁ = 4.8) is added little by little as an acid (A2) of pKa ₁ = 4 to 6, and the mixture is stirred and mixed until completely dissolved. A salt (1) of DBU, phenol and 2-ethylhexanoic acid was obtained.

<Example 2>
The catalyst DBU of the present invention, a salt of phenol and 2-ethylhexanoic acid (2) were obtained in the same manner as in Example 1 except that the ratio of phenol to be reacted with DBU and 2-ethylhexanoic acid was changed.

<Example 3>
The acid (A1) of pKa ₁ = 8 to 11 to be reacted with DBU is o-cresol (pKa ₁ = 10.2), and the acid (A2) of pKa ₁ = 4 to 6 is oleic acid (pKa ₁ = 4.8). The catalyst DBU of the present invention, o-cresol and oleic acid salt (3) were obtained in the same manner as in Example 1 except that

<Example 4>
The catalyst DBU of the present invention was prepared in the same manner as in Example 1 except that the acid (A1) having a pKa ₁ = 8 to 11 to be reacted with DBU was changed to 2,4,6-trimethylphenol (pKa ₁ = 10.8). And 2,4,6-trimethylphenol and 2-ethylhexanoic acid salt (4) were obtained.

<Example 5>
The catalyst DBU of the present invention and 2-methoxy were changed in the same manner as in Example 1 except that the acid (A1) of pKa ₁ = 8 to 11 to be reacted with DBU was changed to 2-methoxyphenol (pKa ₁ = 10.0). A salt of phenol and 2-ethylhexanoic acid (5) was obtained.

<Example 6>
The catalyst DBU of the present invention and the salt of 2-methoxyphenol and 2-ethylhexanoic acid (6) except that the ratio of 2-methoxyphenol and 2-ethylhexanoic acid to be reacted with DBU was changed as in Example 5. Got.

<Example 7>
Examples except that the acid (A1) of pKa ₁ = 8 to 11 reacted with DBU was changed to 2-ethoxyphenol (pKa ₁ = 9.9) and the acid (A2) of pKa ₁ = 4 to 6 was changed to oleic acid In the same manner as in Example 1, the catalyst DBU of the present invention, 2-ethoxyphenol and oleic acid salt (7) were obtained.

<Example 8>
While stirring a predetermined amount of DBN and diethylene glycol as a solvent in a glass round bottom flask, a predetermined amount of phenol as an acid (A1) of pKa ₁ = 8 to 11 was gradually added dropwise thereto, followed by stirring and mixing. Subsequently, a predetermined amount of 2-ethylhexanoic acid as pKa ₁ = 4 to 6 acid (A2) was added little by little, and stirred and mixed until completely dissolved. The catalyst DBN of the present invention, phenol and 2-ethylhexane were mixed. The acid salt (8) was obtained.

<Example 9>
The catalyst DBN of the present invention was mixed with 2-methoxyphenol and 2-ethylhexanoic acid in the same manner as in Example 8 except that the acid (A1) of pKa ₁ = 8 to 11 to be reacted with DBN was changed to 2-methoxyphenol. Salt (9) was obtained.

<Comparative Example 1>
While stirring a predetermined amount of DBU and diethylene glycol as a solvent in a glass round bottom flask, add a predetermined amount of phenol as an acid (A1) of pKa ₁ = 8 to 11 to this, stirring and mixing until completely dissolved The catalyst DBU and phenol salt (H1) of the present invention were obtained.

<Comparative Example 2>
The catalyst DBU of the present invention and a salt of 2-methoxyphenol (H2) were obtained in the same manner as in Comparative Example 1 except that the acid (A1) of pKa ₁ = 8 to 11 to be reacted with DBU was changed to 2-methoxyphenol. It was.

<Comparative Example 3>
While stirring a predetermined amount of DBU and diethylene glycol as a solvent in a glass round bottom flask, add a predetermined amount of 2-ethylhexanoic acid as pKa ₁ = 4-6 acid (A2) little by little to completely dissolve it. The mixture was stirred and mixed until the catalyst DBU of the present invention and 2-ethylhexanoic acid salt (H3) were obtained.

<Comparative Example 4>
The catalyst DBU of the present invention and an oleic acid salt (H4) were obtained in the same manner as in Comparative Example 3 except that the acid (A2) of pKa ₁ = 4 to 6 to be reacted with DBU was changed to oleic acid.

<Comparative Example 5>
While stirring a predetermined amount of DBN and diethylene glycol as a solvent in a glass round bottom flask, add a predetermined amount of 2-ethylhexanoic acid as pKa ₁ = 4-6 acid (A2) little by little to completely dissolve it. The mixture was stirred and mixed until the catalyst DBN of the present invention and 2-ethylhexanoic acid salt (H5) were obtained.

Using the catalysts obtained in Examples 1 to 9 and Comparative Examples 1 to 5, polyurethane foams were prepared in the following manner according to the formulations shown in Table 1, and the filling properties and curability were evaluated. The results are shown in Table 2 (DBU salt) and Table 3 (DBN salt).

<Preparation of polyurethane foam>
Using the raw materials shown in Table 1, at 25 ° C., polyol, water, foam stabilizer, flame retardant, evaluation sample (catalyst) and other catalyst were mixed in this order, and then isocyanate (25 ° C.) was added. (Primix Co., Ltd.) was stirred and mixed at 5000 rpm for 5 seconds to obtain a mixture. Immediately 100 g of this mixture is 10 cm in diameter from the upper opening of the mold (temperature 45 ° C., inner dimension; width 10 cm × depth 100 cm × height 2.5 cm, upper 10 cm × 100 cm opening). A polyurethane foam was obtained by filling along the side wall and foaming.
A blank polyurethane foam was obtained in the same manner as above except that the evaluation sample (catalyst) was not used.

note)
Polyol: Polyol foam stabilizer having a hydroxyl value of 338 obtained by addition reaction of propylene oxide to sucrose: SH
193 (polyether siloxane polymer, Toray Dow Corning Co., Ltd.)
Flame retardant: TMCPP (Tris (β-chloropropyl) phosphate, Daihachi Chemical Industry Co., Ltd.)
Evaluation sample (catalyst): DBU or DBN was added in an amount of 0.3 part.
Other catalysts: U-CAT 420A (Amine-based catalyst, San Apro Corporation)
Isocyanate: Millionate MR-200 (crude MDI, NCO index 110, Nippon Polyurethane Industry Co., Ltd.)

<Fillability>
After injecting 100 g of the mixture into the mold, the minimum distance that flowed from the side wall with an inner size of 10 cm was measured, and this was designated as filling property. The larger this value, the better the filling property.

<Curing property>
After 180 seconds from the start of injecting the mixture into the mold, the foam hardness at a position 20 cm from the side wall having an inner dimension of 10 cm was measured with an E-type hardness meter to make it curable. A larger value means higher curability.

As is apparent from the results of Tables 2 and 3, the catalyst of the present invention is hardened while maintaining good filling properties in the mold even when water is used as a foaming agent, compared to the conventional cycloamidine (salt). I was able to promote it.

The polyurethane resin production catalyst of the present invention is suitably used for production of polyurethane resins such as rigid, semi-rigid and flexible foams.

Claims

From cycloamidine (C) represented by the general formula (1), one or more selected from the group consisting of acids (A1) with pKa 1 = 8 to 11, and acids (A2) with pKa 1 = 4 to 6 A salt (E) used in combination with at least one selected from the group consisting of: (A1) content of 0.2 to 0.8 mol per mol of (C), and content of (A2) The polyurethane is characterized in that the amount is 0.2 to 0.8 mol per 1 mol of (C), and the content of (A1 + A2) is 0.8 to 1.2 mol per 1 mol of (C) Catalyst for resin production.

(M represents an integer of 2 to 6, and the hydrogen atom of the methylene group may be substituted with an organic group.)
2. The polyurethane resin production according to claim 1, wherein the cycloamidine (C) is 1,8-diazabicyclo [5,4,0] undecene-7 or 1,5-diazabicyclo [4,3,0] nonene-5. catalyst.
3. The polyurethane resin production catalyst according to claim 1, wherein the acid (A1) having a pKa 1 = 8 to 11 is a phenol compound represented by the general formula (2).

(Wherein R 1 to R 5 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or an alkoxy group)
The catalyst for producing a polyurethane resin according to claim 3, wherein the phenol compound is phenol, o-cresol, 2,4,6-trimethylphenol, 2-methoxyphenol or 2-ethoxyphenol.
The catalyst for producing a polyurethane resin according to any one of claims 1 to 4, wherein the acid (A2) having a pKa 1 = 4 to 6 is an aliphatic monocarboxylic acid.
The catalyst for producing a polyurethane resin according to claim 5, wherein the aliphatic monocarboxylic acid is 2-ethylhexanoic acid or oleic acid.
A process for producing a polyurethane resin, comprising a step of reacting the catalyst for producing a polyurethane resin according to any one of claims 1 to 6, a polyol and an organic polyisocyanate or an isocyanate prepolymer to obtain a polyurethane resin.
The process according to claim 7, wherein the reaction is carried out in the presence of a foaming agent, and the polyurethane resin is a polyurethane foam.