JPH0455419A - Catalyst composition for production of polyurethane and production of polyurethane foam - Google Patents

Abstract

PURPOSE:To obtain a catalyst composition consisting of an imidazole compound and specific amine compound, having a catalytic constant ratio being in a specific range, having excellent adhesion, capable of reducing fluorocarbon amount used as a foaming agent and having excellent curing properties and adhesion. CONSTITUTION:The objective catalyst composition consisting of at least one or more kinds of amine compounds selected from (A) an imidazole compound (preferably 1-methylimidazole, 1,2-dimethylimidazole, 1-(3-dimethylaminopropyl) imidazole, 1-n-butyl-2-methylimidazole or 1-isobutyl-2-methylimidazole) and (B) amine compound in which KB/KP (KB is catalyst constant of foaming reaction per wt.; KP is catalyst constant of resin-forming reaction per wt.) is >=0.1 and having KB/KP of the composition being in the range of 0.10-0.60.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a method for combining a polyol and a polyisocyanate with a catalyst,
This invention relates to a catalyst for the production of polyurethane foam, which is reacted in the presence of a blowing agent, a foam stabilizer, and optionally other auxiliaries. More specifically, the present invention relates to a catalyst composition for producing polyurethane foam that has good fluidity and excellent curability and adhesive properties during production of polyurethane foam, and a production method using the same.

[Prior Art] In recent years, catalysts for producing polyurethane are required to have advanced catalytic functions. For example, hard foams used as heat insulating materials for electric refrigerators and soft foams used as seat cushions for automobiles are becoming larger and more complex in shape. For this reason, there is a need for catalysts that improve the foam fluidity of polyurethane foams, catalysts that have high curability that shorten demolding time to improve foam productivity, and the like. Furthermore, the amount of fluorocarbon-based blowing agents (trichloromonofluoromethane, dichlorodifluoromethane, etc.) that have traditionally been used in large quantities in foam production has been reduced due to the recent problems with fluorocarbons, and the amount of water used as a blowing agent has been reduced. Studies are being carried out on systems that use a large amount of . However, if a large amount of water is used as a foaming agent, the foam surface will become more brittle, and in the case of hard foam insulation materials, the adhesive strength with the facing material will deteriorate. Therefore, in addition to the above-mentioned catalytic function, there is a need for an even more advanced catalytic function that can reduce the amount of fluorocarbons and overcome the problems that occur in systems with increased amounts of water.

Conventionally, organic metal compounds such as organotin and amine compounds have been used as catalysts for producing polyurethane. However, these conventional catalysts cannot be said to be sufficient in the advanced functions required of the catalysts described above, namely, fluidity and curability during the production of polyurethane foam, and adhesive strength in the formulation before water addition. In particular, the improvement of adhesive strength in formulations that reduce the amount of fluorocarbon and increase the amount of water is the biggest problem and urgent improvement is desired. The present inventors have discovered that when an imidazole compound is used as a catalyst in a formulation in which the amount of fluorocarbon is reduced and the amount of water is increased, the adhesive strength is significantly improved (Japanese Patent Application No. 1-142133). However, the fluidity and curability of the resulting polyurethane foam were not necessarily sufficient, and further improvements were desired.

[Problem to be solved by the invention] In view of these circumstances, the present invention provides a formulation in which the amount of fluorocarbons is reduced and the amount of water is increased during the production of polyurethane foam,
The present invention provides a catalyst composition for producing polyurethane foam with excellent fluidity, curability, and adhesive strength, and a production method using the same.

[Means for Solving the Problems] The present inventors have focused on catalysts in the production of polyurethane foam and have conducted extensive studies.

As a result, it is composed of a combination of an imidazole compound and a specific amine compound, and the catalytic constant (KE) of the foaming reaction and the catalytic constant (Kp) of the resinizing reaction per weight of the catalyst composition.
When a catalyst composition having a ratio of K ii / K p in a specific range is used in a formulation with a reduced amount of fluorocarbons and an increased amount of water, a polyurethane foam with excellent flowability, curability and adhesive strength is obtained, and extremely We have discovered a new fact that can be used as a useful catalyst, and have completed the present invention.

That is, the present invention provides a catalyst composition in which the catalyst is composed of an imidazole compound and a specific amine compound, and the catalyst composition has a catalytic constant (K6) for the foaming reaction and a catalytic constant (K6) for the resin-forming reaction per weight of the catalyst composition. Kp ) ratio KI]/Kp
The present invention provides a catalyst composition for producing polyurethane foam, characterized in that the polyurethane foam is in the range of 0.10 to 0.60, and a production method using the same.

[Effect] Next, the present invention will be explained in detail.

The catalyst of the present invention is a catalyst composition comprising an imidazole compound and a specific amine compound. Even if an imidazole compound or a specific amine compound was used alone in a polyurethane foam formulation that reduced the amount of fluorocarbons and increased the amount of water, it was impossible to overcome the above-mentioned problems, but the catalyst of the present invention By using the composition, the aforementioned problems can be solved.

As the imidazole compound of the present invention, a compound represented by the following symbol is used.

(In the formula, RI represents an alkyl group having 1 to 4 carbon atoms, a Hensyl group, a dimethylaminopropyl group, or a hydroxyalkyl group having 1 to 3 carbon atoms, and R2 is hydrogen, an alkyl group having 1 to 4 carbon atoms, or an allyl group. , or represents a benzyl group, R
(3 and R4 represent hydrogen, methyl group or hydroxymethyl group) These imidazole compounds include 1-methylimidazole, 1,2-dimethylimidazole, 1-
(3-dimethylaminopropyl)imidazole, 1-butyl-2-methylimidazole, 1-inbutyl-2
-methylimidazole, 1-benzyl-2-methylimidazole, 1-vinylimidazole, and the like. Among these, 1-methylimidazole, 1,2-dimethylimidazole, 1-(3-dimethylaminopropyl)
imidacil,]-]butyl-2-methylimidazole 1
Isobutyl-2-methylimidazole is more preferably used.

As the amine compound of the present invention, among known amine compounds, those having a K B/K p of 0.10 or more are used. These specific amine compounds include:
For example, triethylamine, triethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, hexamethyltriethylnontetramine, dimethylcyclohexylamine, dimethylpiperazine, N-methyl -N--(2-dimethylaminoethyl)piperazine, dimethylethanolamine, and bis-(dimethylaminoethyl)ether. More preferably triethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, dimethylcyclohexylamine, N-methyl-N(2-dimethylaminoethyl)piperazine , bis-(dimethylaminoethyl)ether.

If an amine compound having a ratio of KB/to of 0.10 or less is used, the fluidity will be extremely deteriorated and it cannot be used. here,
The catalytic constant (KB) of the foaming reaction and the catalytic constant (Kp) of the resin-forming reaction are the catalytic constants per unit weight of catalyst for promoting the polyurethane forming reaction, and the foaming reaction is the reaction between polyisocyanate and water. , resin formation reaction means the reaction of polyisocyanate and polyol, respectively. The catalytic constants of the imidazole compound of the present invention, specific amine compounds, and their ratios are disclosed in Toyo Soda Research Report, Vol. 28, No. 1 (19
84), and compounds not listed were determined by the exact same measurement method as in the same report.

The catalyst composition comprising the imidazole compound of the present invention and a specific amine compound has a K B/K p of 0.10 to 0.
It is blended and combined so that it is in the range of 60.

If this ratio is less than 0.10, the fluidity will deteriorate;
If it is 0 or more, the curability and adhesiveness deteriorate, so it cannot be used. Here, the ratio KB/ of the catalyst composition consisting of the imidazole compound and the specific amine compound is calculated by the following formula.

Kp a X Kpm+ b X Kpb+
The abbreviations in the CX KPc・++・++ formula are as follows.

a, bSc,...; Composition (wt%) of each of the imidazole compound and specific amine compound in the catalyst composition KBl, KBb, K Bcs...; Composition of each of the imidazole compound and specific amine compound in the catalyst composition Catalytic constant of foaming reaction (Ω27g・mol・h) K□, K Pbs K Pus...: Catalytic constant of resinization reaction of each imidazole compound and specific amine compound in the catalyst composition (fJ2/g 11m01 ) Water and an organic solvent can be used in the catalyst composition of the present invention, if necessary, for the purpose of preventing crystallization and liquid separation. As an organic solvent, a polyol having 2 to 4 hydroxyl groups,
For example, ethylene glycol, diethylene glycol,
Examples include propylene glycol, dipropylene glycol, butanediols, 1,6-hexanediol, glycerin, etc., and preferably ethylene glycol, dipropylene glycol, and 1,4-butanediol.

The amount of the catalyst composition of the present invention used is usually 1% of the polyol.
0.00 parts by weight is 0.02 to 10 parts by weight. In addition, known metal catalysts such as organotin compounds and organolead compounds and organic carboxylic acids for the purpose of imparting retardation properties to the catalyst composition of the present invention can be added as appropriate to the extent that the catalytic function of the present invention is not lost. .

In the polyurethane produced using the catalyst composition of the present invention, conventionally known polyols, polyisocyanates, and, if necessary, blowing agents, foam stabilizers, and other auxiliary agents can be used.

Examples of polyols include polyether polyols, polymer polyols, polyester polyols, and phenol polyols having two or more reactive hydroxyl groups. Examples of polyether polyols include polyether polyols obtained by adding ethylene oxide or propylene oxide to ordinary polyhydric alcohols, ammonia, aliphatic amine compounds such as ethylene amine, aromatic amine compounds, and/or mixtures thereof. can be given.

Examples of the polymer polyol include those obtained by reacting the polyether polyol with an ethylenically unsaturated monomer such as butadiene, acrylonitrile, styrene, etc. in the presence of a radical polymerization catalyst. Examples of polyester polyols include those produced from dibasic acids and polyhydric alcohols, such as polyethylene adipate and polyethylene terephthalate, and these may also be recycled from waste. Examples of the phenol polyol include a novolac type obtained by a condensation reaction of phenols and aldehydes, a resol type, and a benzylic type which is a special resol.

The polyisocyanate may be any conventionally known organic polyisocyanate, such as toluene diisocyanate, diphenylmethane-4,4-diisocyanate,
Aromatic polyisocyanates such as their polymerized isocyanates; aliphatic polyisocyanates such as hexamethylene diisocyanate; cycloaliphatic polyisocyanates such as isophorone diisocyanate; and toluene diisocyanate prepolymers made by reacting them with polyols.
Isocyanate-terminated prepolymers such as diphenylmethane-4,4'-di-isocyanate prepolymers; modified isocyanates such as carposiimide modification;
Examples of blowing agents for these mixed polyisocyanates include low-boiling halogenated hydrocarbons and/or water. As the halogenated hydrocarbon, known halogenated methane and halogenated ethane can be used, among which trichloromonofluoromethane (R-11),
Trichlorotrifluoroethane (R-113), and dichlorotrifluoroethane (R-123), which has a low ozone depletion coefficient and is considered a promising alternative CFC compound.
Freon compounds such as dichloromonofluoroethane (R-141b) are preferred. The amounts and ratios of water and fluorocarbon compounds to be used cannot be determined unconditionally, but are determined depending on the desired density and physical properties. However, efforts are being made to reduce the amount of fluorocarbon compounds in response to the fluorocarbon problem, and attempts are being made to develop fluorocarbon reduction systems that use a large amount of water. The catalyst composition of the present invention is suitably used in this fluorocarbon reduction system. As an example, there is a system in which 2.0 parts by weight or more of water and 35 parts by weight or less of a fluorocarbon compound are used as blowing agents in rigid foam based on 100 parts by weight of polyol.

Examples of the foam stabilizer include nonionic surfactants such as organopolysiloxane-polyoxyalkylene copolymers and silicone glycol copolymers, or mixtures thereof, and the amount thereof is not particularly limited. but,
Usually, 0.00 parts per 100 parts by weight of the phenolic resin composition.
It is 1 to 5.0 parts by weight.

In the present invention, other auxiliary agents may be added as necessary, such as conventionally known flame retardants, colorants, extenders,
Examples include antioxidants and ultraviolet inhibitors.

The method for producing polyurethane foam that can be used with the catalyst composition of the present invention is a conventionally known one-shot method, prepolymer method, etc. to produce soft foam, HR foam, semi-rigid foam, hard foam, microcellular foam, etc. be able to.

In particular, due to the demand for reduction in fluorocarbons, it is suitably used in fluorocarbon reduction systems that use a large amount of water and reduce the amount of fluorocarbons used as a foaming agent.

[Effects of the Invention] By using the catalyst composition of the present invention, it is possible to obtain a polyurethane foam that has excellent fluidity during polyurethane production and has excellent curability and adhesive properties. Therefore, in a molded product, the polyurethane resin is spread throughout, improving moldability. Moreover, since it has excellent curability, productivity is improved. Furthermore, since the catalyst composition of the present invention has excellent adhesive properties, it is possible to reduce the amount of fluorocarbons as a blowing agent and overcome the problems of fluorocarbon reduction systems that use a large amount of water.

[Examples] The present invention will be explained in more detail based on Examples below.
The present invention is not limited to these.

Examples 1-6. Comparative Examples 1 to 5 The mixing ratios (formulations) of raw materials for producing polyurethane were as shown below, and foaming was carried out under predetermined foaming conditions according to the usual procedure using the catalyst composition of the present invention and the catalyst of the comparative example. The test was conducted.

Table 1 shows the foaming reaction activity (KB), resin forming reaction activity (K, ), and activity ratio of each catalyst used.

The properties of the produced foam were measured by the following method. The results are shown in Table-2.

a. Formulation polyol Foam stabilizer water R-113) Catalyst 4) Isocyanate 5) (parts by weight) 1.5 4.0 change NGOloR-1, 10 ■) Sucrose/aromatic amine polyol.

OH value 423 KOH/g (manufactured by Mitsui Toatsu Chemical ■, 5U-464/NT-2) Silicone surfactant (L-5340 manufactured by Nippon Unicar ■) 3) Trichlorofluoromethane (manufactured by Mikata Fluorochemical ■) 4) Explanation of catalyst used and catalyst abbreviations in the table NMI2.1-
Methylimidazole DMIZ, 1,2-dimethylimidazole IBI2.1
-Inbutyl-2-methylimidazole DMAP IZ; 1-(3-dimethylaminopropyl)imidazole TEDA; Triethylenediamine (manufactured by Tosoh Corporation, TE
DA) TMEDA, tetramethylethylenediamine (manufactured by Tosoh Kan, TOYOCAT-TE) TMHMDA, tetramethylhexamethylenediamine (manufactured by Tosoh ■, TOYOCAT-MR) TMNAEP, N-methyl-N--(2-dimethylaminoethyl) Piperazine (manufactured by Tosoh, TOYO CAT-NP) D~ICIA/dimethylcyclohexylamine PMDE
TA/pentamethyldiethylenetriamine (TOY OCAT-DT manufactured by Tosoh Corporation) BDMEE, bis=(2-dimethylaminoethyl)ether (TOYOCAT-ETS manufactured by Tosoh Corporation) 5) Crude MDI NC○ concentration -31.0% (Japan Polyurethane Industry Co., Ltd.) ■, MR-200) b1 Foaming conditions Raw material liquid temperature 20±1℃ Stirring speed 6000 rpm (5 seconds) Mold temperature 40℃ C9 measurement item box Foamed aluminum box (dimensions + 25X25X25c)
m) Foaming. Measure the following items.

・Reactive cream time, foam rise time (seconds) Gel time: Resin (stringing) time (seconds) Tack-free time, time when the foam surface is no longer sticky (seconds) Rice time: Foam rise stop time (seconds) ) ・Curing speed The upper part of the foamed foam was measured at Shore C using a hardness meter at each elapsed time. The time (minutes) during which the hardness showed 55 was defined as the curing rate.

・Adhesive strength 5x5 in 4 directions at the center of the side of the aluminum box
cm thick paper was set and foamed. After 10 minutes of foaming, the 90' peel strength of the set cardboard is taken as the adhesive strength, and the adhesive strength (g
/c)-ii11 Separation strength 15 x 5 - Form density Cut the center of the foam into a size of 20 x 20 x 2.5 and determine lOj.

・The foam whose thermal conductivity foam density was measured was
Measured with model 88.

Panel foaming/flowability 100 (length) x 25 (width) x 3. Oc thickness) c71
Pour a certain amount of the mixed liquid into the aluminum mold marked +.
The length (cs) of the generated form is J constant.

As is clear from Table 2, the activity ratio (KB/KP) is 0.
When using a catalyst composition consisting of the imidazole compound of the present invention and an amine compound, which is in the range of 10 to 0.60,
Excellent curing speed, adhesion, and fluidity.

On the other hand, when the imidazole compound of the comparative example was used alone,
Fluidity deteriorates, and when an amine compound is used alone, curing speed and adhesiveness deteriorate.

Furthermore, even when a catalyst composition consisting of an imidazole compound and an amine compound is used, if the activity ratio thereof is out of the range of the present invention, the curing speed and adhesiveness will deteriorate.

Claims (4)

[Claims] (1) (a) an imidazole compound and (b) an amine compound whose K_B/K_P (K_B: catalytic constant of foaming reaction per weight, K_P: catalytic constant of resin-forming reaction per weight) is 0.10 or more A catalyst composition comprising at least one selected amine compound, wherein K_B/
A catalyst composition for producing polyurethane foam, characterized in that K_P is in the range of 0.10 to 0.60. (2) The imidazole compound is selected from 1-methylimidazole, 1,2-dimethylimidazole, 1-(3-dimethylaminopropyl)imidazole, 1-n-butyl-2-methylimidazole, and 1-isobutyl-2-methylimidazole. The catalyst composition according to claim 1, characterized in that it contains at least one selected type. (3) A method for producing polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst, a blowing agent, a foam stabilizer, and other auxiliary agents, as claimed in claim 1 (
A method for producing polyurethane foam, characterized by using the catalyst described in item 1) or item (2). (4) A patent claim characterized in that the polyurethane foam is a rigid polyurethane foam, and the blowing agent is 2.0 parts by weight or more of water and 35 parts by weight or less of halogenated hydrocarbon per 100 parts by weight of polyol. The range of (3rd)
).