JPS6230114A - Epoxy and urethane catalyst - Google Patents

Abstract

PURPOSE:The titled catalyst, a high-boiling, low volatile compound consisting of a specific epsilon-caprolactam derivative, having no influence on water absorption ratio of cured resin although it is water-soluble. CONSTITUTION:The aimed catalyst consisting of an epsilon-caprolactam derivative shown by the formula (R is H, hydroxyetyl, hydroxypropyl or cyanoethyl). The amount of the catalyst used is preferably 0.1-5pts.wt. based on 100pts.wt. epoxy compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides an epoxy curing and urethanization catalyst (hereinafter referred to as
Simply abbreviated as catalyst. ) regarding.

[Conventional technology]

It has been known for a long time that compounds having a dimethylamino group are useful as epoxy and urethane catalysts, and many of them are in practical use. Widely used examples of these include, for example, cyclohexyldimethylamine, benzyldimethylamine, tris(dimethylaminomethy/L/)pheno-/L/I tetramethylhexamethylenediamine, tris(dimethylaminopropyl/L) /) amines, etc. Although these conventional compounds have good catalytic activity, many of them are water-soluble or highly hygroscopic compounds, which adversely affect the physical properties of the resin, such as water absorption. Furthermore, even if they have low water solubility or hygroscopicity, they have problems with volatility, compatibility with resins, etc. Furthermore, the odor caused by the dimethylamino group is strong.
Alternatively, there are problems such as skin irritation, and a better catalyst is desired from the viewpoint of improving the performance required for the physical properties of the resin or from the viewpoint of safety.

[Means for solving problems]

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention discovered that the ε-caprolactam derivative represented by the following general formula is a useful epoxy and urethane catalyst that solves the above-mentioned problems. I was able to complete it.

R In the formula, ■ represents H2 and a droxyethyl, hydroxylpropyl/v, or cyanethyl group. The compound in which R is H is α-dimethylamino-ε-caprolactam (hereinafter DM
-CL), and its manufacturing method is described in Japanese Patent Publication No. 4211926, Japanese Patent Application Laid-Open No. 54-76590, etc. For compounds in which R is a hydroxyethyl, hydroxypropyl, or cyanoethyl group, ethylene oxide is added to α-dimethylamine-ε-caprolactam.

Obtained by adding propylene oxide or acrylonitrile (hereinafter referred to as DM-OL-EO, respectively).

It is abbreviated as DM-CL-PO or DM-CL-ON. )
. These addition reactions can be carried out by known methods.

For example, DM-C! without a catalyst or in the presence of an alkali catalyst such as potassium hydroxide or benzyltrimethylammonium hydroxide at a temperature of 60 to 180°C! What is necessary is to add an equivalent amount to L (in a closed container if necessary) and react. This addition amount does not need to be equivalent. If less than the equivalent amount is added, the target product can be isolated by distillation after the reaction. On the other hand, for example, when adding ethylene oxide, an equivalent amount or more may be added for the purpose of reducing unreacted DM-OL. It can also be reacted. In this case, the by-produced adduct containing 2 moles or more of ethylene oxide can be used without any particular need for isolation as long as its content is less than 40% by weight. This content is 40% by weight
The above is not preferable because it leads to a decrease in catalytic activity. Moreover, it goes without saying that the compounds of the present invention can be used in combination as desired.

The epoxy resin in which the catalyst of the present invention is used is Inters
Encyc by cie-nce Publishers
ropedia of Polymer 5science
and, Technology Volume 6, 209-27
1 page (1967). Epoxy resins include, for example: pinylcyclohexene diepoxide, dicyclopentadiene dieboxide, ethylene glycol pinu(3,4-epoxytetrahydrodicyclopentadiene-8-4/L/)-nyf/Vf! to(
D-cyclic polyepoxy compounds and diethylene glycol bis(3,4-epoxycyclohexanecarboxylate)
, bis-3,4-(epoxycyclohexylmethy)V
)-polyglycidyl ether compounds, dihydric alcohols, polyhydric alcohols, diphenol-/L, obtained by reacting compounds containing two epoxycyclohexyl groups such as succinate, dicarboxylic acids, and epichlorohydrin in the presence of an alkali. / (e.g. bisphenol A, tetrabromobispheno-/L/A, bispheno-/shiF, bispheno-1vS, acetaltechtophenol condensate), polyphenol or phenol novolac resin, novolac resin such as 0-cresol novolac. It is a polyglycidyl ether compound obtained by etherifying epichlorohydrin or dichlorohydrin in the presence of an alkali. Mixtures of two or more of the aforementioned epoxy compounds can also be used.

In the present invention, not only the epoxy resin alone but also a compound that reacts with the epoxy compound, that is, a so-called curing agent, or additives such as a coloring agent, a filler, and a lubricant can be used in combination. Examples of curing agents include the Encyclopedia mentioned above.
of Polymer 5science and T
technology volume 6 pages 209-271 (196
7), Japan Adhesive Association Journal (J, of The Ad
hesion 5ociety of Japan)
Pressure+102, 141 (1979) and Polymer Processing (Polymer Appl 1cation
(in; Japanesc) 25, 383 (1
976), 26, 64°120.184 (197
7)]. For example, chain aliphatic amines such as diethylenetriamine, triethylenetetramine, and diethylaminopropylamine, cyclic aliphatic polyamines such as N-aminoethylpiperazine and isophoronediamine, xylylenediamine, its polymer, phenylenediamine, diaminodiphenyl-methane. - Aromatic ring amines such as sulfone, Polymide L manufactured by Sanyo Chemical
- type polyamides; modified amines such as ethylene oxide, propylene oxide and epoxy resin modified amines, cyanoethylated amines, ketiminated amines, phenol and formalin modified amines;
n 3-800 Polymercaptans such as LC and Thioko/L/LP; phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, methylnadic anhydride, tetra-mada anhydride Acid anhydrides such as hexahydrophthalic acid, methylhexahydrophthalic anhydride, and halides of the above acid anhydrides; 2-ethylhexanoic acid, benzoic acid, salicylic acid, adipic acid, phthalic acid, dodecanedicarboxylic acid,
Substituted and unsubstituted mono- and polycarboxylic acids such as hydroquine stearic acid and trimellitic acid; amino resins such as butylated melamine resins, phthylated urea resins, p-oxybenzoic acid and formalin condensates, phenolic resins, etc. Synthetic resin initial condensates such as poly(p-vinylpheno-)L/) resin; -f such as phenol and resorcinol
ftilc is polyhydric phenol; decyl alcohol.

Alcohols and glycols such as alcohol, ethylene glycol, and trimethylolpropane; Isocyanates such as tolylene diisocyanate, crude diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, and their combination with glycols and active hydrogen compounds such as water. Reactants and polymers of the above isocyanates; hydrazine derivatives such as dicyandiamide and organic acid hydrazides.

The amount of the catalyst of the present invention to be used is usually o, o i to 20 parts by weight, preferably 0 to 100 parts by weight of the epoxy compound.
1 to 5 parts by weight.

The catalyst of the present invention is 2,4,6. -1-Linu(dimethylaminomethy)V) phenol, tris(dimethylaminopropyl)V)amine, tetramethylguanidine, 2-ethyl/L/4-methylimidazo-/L/, secondary products such as DBU and its salts and tertiary amines; they may be used in combination with known catalysts such as Lewis acids such as BF3 or amine salts thereof.

The urethane resin for which the catalyst of the present invention is used includes the reaction of an active hydrogen-containing compound defined by the Tselevitinov method with isocyanates, the trimerization of isocyanate, the production reaction of uretidinedione and isocyanurate by Sankeika, and the decarboxylation of 2 moles of isocyanate. It is produced by a carbodiimide production reaction.

Isocyanate and active hydrogen compound polyol/L/
The materials include all the raw materials commonly used in the production of rigid, semi-rigid, and flexible polyurethane foams, elanuttomer foams, and polyurethane molded articles.

For example, as isocyanates, aromatic polyisonanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.), aliphatic polyisocyanates (
(hexamethylene diisocyanate, etc.), alicyclic polyisocyanates (such as isophorone diisocyanate), modified products thereof (for example, carbodiimide modification), and prepolymers containing free isocyanates obtained by reacting these with polyols.

Polyols include polymeric polyols such as alkylene oxides (ethylene oxide, etc.).

water, polyhydric alcohols (propylene oxide, 1,2- and 1,4-butylene oxide, etc.); glycols such as ethylene glycol, propylene glycol; glycerin, trimethylolpropane, triethanolamine, pentaerythrin) - Le 2 Sorbi)-A/
, L, polyols having 3 or more OH groups such as sucrose)
and polyether polyols having a structure added to amine compounds (ethylenediamine, diethylenetriamine, tolylenediamine, xylylenediamine, piperazine, N-aminoalkylpiperazine, N,N-dimethylaminopropylamine, cyclohexylenediamine, etc.); Polyether polyols and ethylenically unsaturated monomers (acrylonitrile, nutylene.

Polymer polyolefins reacted in the presence of a polymerization catalyst such as methyl methacrylate, butadiene, etc.
/L/ (described in U.S. Pat. No. 3,883,151); polycarboxylic acid (succinic acid, sebacic acid, maleic acid, adipic acid, fumaric acid, phthalic acid, dimer acid, etc.) and the above polyhydric alcohol; Polyether polyol: Examples include polyester polyether polyol and mixtures of two or more of these. In addition, if necessary, active hydrogen compounds can be used as crosslinking agents or chain extenders, such as low molecular polyols [triethanolamine,
Jetanolamine, ethylene glycol, diethylene glycol/v, butanediol, trimethylolpropane, glycerin, p-bis(2-hydroxyethyl/I/
) phenylene ether] and polyamines (tolylene diamine, etc.).

Xylylenediamine, diaminodiphenylmethane.

Methyleppinu〇-chloraniline, etc.) can be used.

Further, when a blowing agent is used, examples thereof include a halogen-substituted aliphatic hydrocarbon blowing agent (furongane, methylene chloride, etc.), water, and the like.

In addition, surfactants (silicone foam stabilizers, etc.), colorants, fillers, stabilizers, etc. can also be used if necessary.

The amount of the catalyst of the present invention used is generally 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, per 100 parts by weight of polyol. If it is less than 0.01 part by weight, the catalyst activity will be low and it will take too long to complete the reaction.

Further, if the amount used is greater than 5 parts by weight, the physical properties of the obtained urethane foam, particularly the compressive strength (ILD), will deteriorate, which is not preferable.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1. ~41. Comparative example 1. ~2°DM-OL was used by distilling and purifying α-dimethylamino-ε-cabrolactam manufactured by Toshi.

DM-OL-EO and DΔ1-CL-PO are produced by adding ethylene oxide and propylene oxide to DM-OL purified by distillation at a temperature of 110 to 150°C using 0.1% by weight of potassium hydroxide as a catalyst. The reaction was carried out under pressure, the catalyst was neutralized, and after removal by filtration, the ethylene oxide adduct was used as it was, and the propylene oxide adduct was purified by distillation.

The content of 1 molar adducts is approximately 70% by weight and 10%, respectively.
It was 0% by weight.

DMCL-ON is produced by adding the equivalent mole of 7crylonitrile to α-dimethylamino-ε-caprolactam at a temperature of 70 to 90°C in the presence of 0.5% by weight of benzyltrimethylammonium hydroxide, and then purifying it by distillation. I used it.

Table 1. The properties, etc. are shown together with the compounds of comparative examples. The compound of the present invention has a high boiling point, low volatility) and low amine odor.

Test Example 1 (Catalytic activity test of epoxy resin) Gel time of acid anhydride curing and phenol novolac curing (test tube method/120°C, respectively) using the following formulations.
, and hot plate method/170°C) to test the catalytic activity. The results are shown in Table 2. Shown below.

Acid anhydride cured vinylphenol/l/A type liquid 100 parts Epo・'
Resin (epoxy equivalent: 186) Methylhexahydrophthalic acid 90 parts Anhydride (acid value: 667) Catalyst: 1 part Pheno-p novolac cured cresol novolak epoxy 100 parts Resin (epoxy equivalent: 199°, softening point: 81°C) 55 parts Phenol novolac resin (softening point 80°C) Catalyst 3 parts Table 2. As can be seen, the catalyst of the present invention has a catalytic activity equivalent to or close to that of Comparative Example 2.0 catalyst, although the theoretical molecular weight per dimethylamino group, which can be said to be an indicator of catalytic activity, is large. Therefore, it can be said that it is a practically useful catalyst.

Table 2゜Test Example 2. Epoxy resin water absorption effect test example 1. In the acid anhydride curing formulation, 1 part of catalyst,
Alternatively, use 2 parts and place 6g of the mixture into a 4-inch thick mold.
It was cured under the conditions of 2 hours at 100°C plus 7 hours at 130°C. The cured product was allowed to cool to room temperature in a desiccator and used as a sample. Table 3. The water absorption rate of the sample was measured under the conditions shown below. In addition, the Tg (TMA) of the cured products is approximately 131°.
It was C.

Table 3 As is clear from Table 2, although the catalyst of the present invention is water-soluble, the water absorption rate of the cured product is low), and there is no effect of the amount added.

Test example 3. (Foaming test of urethane foam with PVC sheet and discoloration test of PVC sheet) Using the foaming recipe below, create a so-called cold cure foam with PVC sheet, put it in an oven at 120°C, and discolor the PVC sheet. Checked raw material temperature =
25°C, 20 x 20 x 1 mouth cast iron mold temperature = 4
0"C9 mold release agent Nibond Wax URT-35T (manufactured by Bond Wax KK), curing conditions: 10 minutes at room temperature Foaming recipe: (parts by weight) Sanix FA-701 (note) 100 triethanolamine 4 water
2.5 catalyst
1.0)) )v -)' MDI
(1051ndex) 58
．． 9 (Note) Sannix FA-701 (manufactured by Sanyo Chemical Industries) Hue (Hazen) 75 or less, OH value 33 ± 5. pH5
, 5-7.5. Moisture 0.1% or less, viscosity (25°C) 8
Ethylene oxide-chipped polyol formulation having an analysis value of 00±50 cps A light brown slush-molded PVC sheet of 10×10 CrIL was previously attached to the inner surface of the mold with double-sided adhesive tape.

A predetermined amount of crude MDI is added to a homogeneous mixture of raw materials other than crude MDI in the foaming formulation and stirred with a high-speed stirrer,
The mixture was poured into the above-mentioned mold to obtain a salt vinyl mold form. The total specific gravity excluding vinyl chloride was 0.12-0.14.

This form was placed in an oven at 110°C, and the discoloration of the PVC sheet was examined. These results are shown in Table 4.

Table 4゜Table 4. As shown in the figure, the catalyst of the present invention has the same catalytic function as the conventional catalyst, and has the excellent feature of not discoloring the PVC sheet. This result is considered to be attributable to the high boiling point of the catalyst of the present invention as well as its excellent compatibility with the foam.

〔Effect of the invention〕

The ε-caprolactam derivative of the present invention is a low-volatility compound with a high boiling point and has a mild amine odor. Furthermore, although it is a water-soluble compound, it does not affect the water absorption rate of the cured resin and has excellent compatibility.
It is useful as an epoxy and urethane catalyst.

Claims (1)

[Claims] 1. An epoxy curing and urethanization catalyst comprising an ε-caprolactam derivative represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R is H, hydroxyethyl, hydroxypropyl, or cyanoethyl group. ]