JP2664936B2 - Catalyst composition for polyurethane polymerization - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a catalyst used for producing polyurethane such as flexible, rigid, semi-rigid foam or elastomer.

More specifically, rigid foam mainly for electric refrigerators,
The present invention relates to a catalyst for urethane production which accelerates the curing speed of an elastomer represented by a soft or semi-rigid foam used for an automobile interior material or a shoe sole or an automobile bumper.

[Problems to be solved by conventional technology and invention]

Conventionally, as a catalyst for polyurethane production, tin-based or iron-based organic metals and tertiary amines are used, and tertiary amines are particularly preferred. For example, compounds such as N-methylmorpholine, N-ethylmorpholine, triethylenediamine, tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, trimethylaminoethylpiperazine, dimethylcyclohexylamine, and bis- (dimethylaminoethyl) ether are used for producing polyurethane. Used as a catalyst.

In recent years, demands for urethane catalysts during polyurethane production have been increasing. For example, a catalyst that can be filled in a low-viscosity state in order to increase the fluidity of the foam in the mold with a small amount of resin to increase the size and complexity of the product, and to shorten the demolding time to improve the productivity It is a highly curable catalyst system.

However, in general, when a catalyst that reduces the initial resinification activity is used alone to improve the resin fluidity and the filling property, the latter resinification activity is also reduced at the same time, and the demolding time is prolonged. On the other hand, when a catalyst for improving the late-stage resinification activity is used alone, the initial-stage resinification activity is simultaneously increased and the resin fluidity is deteriorated.

In order to solve such a problem, a so-called lagging catalyst has been considered in which the initial activity is low and the activity increases as the reaction proceeds.

Such catalysts for simultaneously satisfying the initial fluidity and the later-stage curability include tertiary amines as described in JP-A-54-130697 and JP-B-57-56491. Are known.

The tertiary amine organic carboxylate does not show its original activity at the beginning of the polyurethane foam formation reaction because the tertiary amine is blocked with the organic carboxylic acid, but is decomposed by the gradually increasing reaction heat, The organic carboxylic acid reacts with the isocyanate to produce a tertiary amine which is effective as a catalyst, thereby exhibiting the original catalytic activity. Examples of the tertiary amine organic carboxylate catalyst having such properties include, for example, triethylenediamine and bis-diamine.
(Dimethylaminoethyl) ether or N, N, N ', N', N "
Salts of common tertiary amines such as -pentamethyldiethylenetriamine and organic carboxylic acids such as formic acid, acetic acid and 2-ethylhexanoic acid are known.

However, these tertiary amine organic carboxylate catalysts have a remarkable improvement in fluidity due to the delay of the initial reaction, but have little effect on shortening the demolding time due to the improvement in curability. Therefore, a more effective catalyst, that is, a resin fluidity and a filling property are improved by delaying an initial resinification activity in a reaction between an isocyanate and a polyol, and further promote a later resinization activity to shorten a final curing time. A shorter catalyst system was desired.

[Means for solving the problem]

The present inventors have conducted intensive studies on catalysts that simultaneously improve the above two performances, and as a result, by combining a specific quaternary ammonium salt compound with a specific ratio in an organic carboxylate catalyst of a tertiary amine, It has been found that the curability is improved without impairing the initial fluidity and that the demolding time can be significantly reduced,
The present invention has been reached.

That is, the present invention relates to a salt of an organic carboxylic acid having 1 to 8 carbon atoms of a tertiary amine compound, a quaternary ammonium salt compound having an oxyalkylene group, and 5 to 50 wt. % Of the catalyst composition for polyurethane polymerization.

In the catalyst of the present invention, when the addition amount of the quaternary ammonium salt is less than 5% by weight, the effect is hardly seen,
If it exceeds 50% by weight, the so-called flyability of the resin surface will increase and the adhesion to the surface material will be hindered. Preferably it is 30 to 45% by weight.

That is, the catalyst of the present invention is a polyurethane polymerization catalyst obtained by combining a tertiary amine organic carboxylate with a quaternary ammonium salt compound and simultaneously improving initial retardation and late curing properties.

Examples of the tertiary amine organic carboxylate used in the present invention and the tertiary amine used in the quaternary ammonium salt compound include N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N, N , N ', N'-
Tetramethyl-1,3-propylenediamine, N, N, N ', N'
-Tetramethylhexamethylenediamine, N, N, N ', N',
N ″ -pentamethyldiethylenetriamine, bis- (2
-Dimethylaminoethyl) ether, N, N-dimethylethanolamine, N, N-dimethylbenzylamine, N, N,
N'-trimethylaminoethylpiperazine, N, N ', N "-
Tris (3-dimethylaminopropyl) hexahydro-
Compounds such as S-triazine are exemplified.

The organic carboxylic acid having 1 to 8 carbon atoms used in the production of the organic carboxylic acid salt of a tertiary amine used in the present invention is formic acid,
Acetic acid, propionic acid, butyric acid, caprylic acid, 2-ethylhexanoic acid, caproic acid, pyruvic acid, benzoic acid, and the like are used. Formic acid, acetic acid, and propionic acid are particularly preferably used, and the amount added is the tertiary amine. 0.1 to 1.0 molar equivalent is used per 1 molar equivalent of nitrogen.

The quaternary ammonium salt compound used in the present invention has an oxyalkylene group, and after an inorganic acid or an organic acid is allowed to act in the presence of a tertiary amine, 1 mol or more per 1 mol of the tertiary amine, Preferably, it is produced by reacting 1 to 3 moles of alkylene oxide.

As the kind of the alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide and the like are preferably used.

In producing the catalyst of the present invention, a tertiary amine is
If necessary, after mixing a polar organic solvent represented by a glycol system, the mixture is stirred while cooling the vessel, and a predetermined amount of an organic carboxylic acid is added and mixed in several times. After cooling, a predetermined amount of a quaternary ammonium salt compound may be added and mixed.

The composite catalyst of the present invention thus produced is used in an amount of 0.5 to 5.0 parts based on 100 parts of a commonly used polyol, and can be used in combination with a normal tertiary amine or an organotin compound as a cocatalyst. .

When producing a polyurethane using the novel catalyst of the present invention, as an additive, if necessary, a blowing agent such as CFCl ₃ or CH ₂ Cl _2, a surfactant such as an organic polysiloxane, a halogenated alkyl compound, Flame retardants such as halogenated phosphorus compounds,
Other additives can be used.

The types and amounts of these additives can be sufficiently used in the types and ranges usually used.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples.

The mixing ratio of the raw materials for polyurethane production was set as shown in Table 1, and urethane foaming was carried out according to a usual procedure. That is, the polyol, water, surfactant, catalyst, blowing agent, and polyisocyanate kept at 20 ° C. were mixed and stirred, and poured into a paper cup to form a urethane foam (the upper part of the paper cup was open).

This time the flyability evaluation was based on ASTM C421-61. ···················· FIG. ... Table 3 In the evaluation of the curability, dynamic viscoelasticity measurement (vibron method) was used to continuously track and evaluate the curing behavior of the resin central portion. .. FIG. 2 DF in FIG. 2 is a value serving as an index of resin hardness.

Example 1 One mole of N, N, N ', N', N "-pentamethyldiethylenetriamine was neutralized with 1 mole of 2-ethylhexanoic acid, and then 1 mole of propylene oxide was added to obtain a quaternary ammonium salt compound. After dissolving triethylenediamine in twice the amount of dipropylene glycol, formic acid was added in an equimolar amount to triethylenediamine, and the mixture was stirred, cooled, and then compounded so that the ratio of the quaternary ammonium salt compound to formate was 4/6. did.

Using this catalyst, foaming was carried out based on the above-mentioned formulation.

 The results are shown in Table 3, FIG. 1, and FIG.

Example 2 The same operation as in Example 1 was performed except that the ratio of the quaternary ammonium salt compound to formate was 1/9.

 The results are shown in Table 3 and FIG.

Example 3 The same operation was performed as in Example 1 except that formic acid was changed to 2-ethylhexanoic acid.

 The results are shown in Table 3 and FIG.

Example 4 The same operation as in Example 1 was performed except that formic acid was added in a 2-fold molar amount.

 The results are shown in Table-3.

Example 5 The same operation as in Example 1 was performed except that propylene oxide of the quaternary ammonium salt compound was changed to ethylene oxide.

 The results are shown in Table 3 and FIG.

Comparative Example 1 Using N, N, N ', N', N "-pentamethyldiethylenetriamine as a catalyst, foaming was carried out according to the above-mentioned formulation.

 The results are shown in Table 3 and FIG.

Comparative Example 2 Foaming was carried out using triethylenediamine as a catalyst according to the above-mentioned formulation.

 The results are shown in Table 3 and FIG.

Comparative Example 3 In Example 1, foaming was performed using only the formate catalyst.

 The results are shown in Table 3 and FIG.

Comparative Example 4 In Example 1, foaming was performed using only the quaternary ammonium salt compound.

 The results are shown in Table 3 and FIG.

Comparative Example 5 Foaming was carried out using a composite of the quaternary ammonium salt compound and the formate catalyst used in Example 1 in a ratio of 7/3 as a catalyst.

 The results are shown in Table 3 and FIG.

Table 2 summarizes the blending of the catalysts of the above Examples and Comparative Examples.

In the table, the gel time refers to the time required for sufficiently increasing the molecular weight until a thread is drawn from the polyurethane foam when a sharp object is brought into contact with the surface of the polyurethane foam and subsequently released.

[Effect of the Invention] The composite catalyst of the present invention can improve the filling property at the time of foaming and promote the curability. For example, Table-3
In Comparative Example 3, it is clear that the packing property is excellent, but in Example 1 in which the quaternary salt is combined, the packing property is similarly excellent. From FIG. 2, it can be seen that the evaluation of the curing behavior shows that Comparative Example 3 is not inferior to Comparative Example 2 showing the highest curability as a tertiary amine alone. For the first time, it was quantitatively found that the composite with a quaternary salt further exceeded the curability as in Example 1.

 From the above, the effect of the catalyst of the present invention is clear.

In addition, in the evaluation of flyability by using a quaternary salt catalyst, it is desirable to combine the upper limit of about 50% as shown in FIG.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the flyability and the ratio of the quaternary salt in the catalyst, and FIG. 2 is a graph showing the curing behavior of the catalyst.

Claims (2)

(57) [Claims] 1. A quaternary ammonium salt compound having an oxyalkylene group, based on a salt of an organic carboxylic acid having 1 to 8 carbon atoms of a tertiary amine compound, of 5 to 50 wt. % Catalyst composition for polyurethane polymerization. 2. The organic carboxylic acid salt of a tertiary amine compound is present in an amount of 0.1 to 1.0 with respect to the nitrogen equivalent of the tertiary amine compound.
The polyurethane polymerization catalyst composition according to claim 1, which is produced using an equivalent amount of a monobasic organic carboxylic acid.