JPH01319521A - Catalyst composition for polymerizing polyurethane - Google Patents

Abstract

PURPOSE:To obtain the subject composition, useful for producing polyurethane, such as rigid foam, of electric refrigerators, etc., and capable of improving resin fluidity, etc., and curing in a short time by compounding an organic carboxylate of a tertiary amine with a specific amount of a quaternary ammonium salt compound. CONSTITUTION:The objective composition obtained by mixing (A) a tertiary amine (e.g., N-methylmorpholine) with, as necessary, a polar organic solvent, stirring the resultant mixture while cooling a container, adding and mixing an organic carboxylic acid (preferably formic, acetic acid, etc.) in an amount of 0.1-1.0 equiv. based on 1 equiv. N of the tertiary amine in divided several portions, cooling the resultant mixture and compounding (B) 5-50wt.% quaternary ammonium salt compound (obtained by reacting an acid in the presence of a tertiary amine and then reacting an alkylene oxide in an amount of >=1mol based on 1mol tertiary amine) so as to provide 100wt.% total amount of both components (A) and (B).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a catalyst used in the production of polyurethanes such as soft, hard, semi-rigid foams or elastomers.

More specifically, it relates to catalysts for the production of urethane that accelerate the curing speed of hard foams mainly used in electric refrigerators, soft and semi-rigid foams used in automobile interior materials, and elastomers such as shoe soles and automobile bumpers. It is.

[Prior art and problems to be solved by the invention] Conventionally, tin-based, iron-based, and other organic metals and tertiary amines have been used as catalysts for producing polyurethane, with tertiary amines being particularly preferred. ing. For example, N-methylmorpholine,
Compounds such as N-ethylmorpholine, l-lyethylenediamine, tetramethylhexamethylenediamine, pencmethyldiethylenetriamine, trimethylaminoethylpiperazine, dimethylcyclohexylamine, and bis-(dimethylaminoethyl)ether are used as catalysts for polyurethane production. It is being

In recent years, demands on urethane catalysts during polyurethane production have become more sophisticated. For example, a catalyst that can be filled in a low viscosity state to increase the fluidity of the foam in the mold and with a small amount of resin as the product becomes larger and has a more complex shape.
Furthermore, it is a highly curable catalyst system that shortens demolding time to improve productivity.

However, normally, when a catalyst that lowers the initial resin forming activity is used alone in order to improve resin fluidity and filling property, the latter stage resin forming activity is also reduced at the same time, resulting in an extension of demolding time. On the other hand, if a catalyst that improves the late-stage resinization activity is used alone, the initial resinization activity also increases, resulting in poor resin fluidity.

In order to solve these problems, so-called retarded catalysts, which have low initial activity and increase in activity as the reaction progresses, have been considered.

As a catalyst intended to simultaneously satisfy such initial fluidity and late curing properties, Japanese Patent Application Laid-Open No. 54-13069
Organic carboxylic acid salts of tertiary amines are known as described in Japanese Patent Publication No. 7 and Japanese Patent Publication No. 57-56491.

Organic carboxylic acid salts of tertiary amines do not exhibit their original activity at the beginning of the polyurethane foam forming reaction because the tertiary amines are blocked by organic carboxylic acids, but they are decomposed by the heat of reaction that gradually increases, and An organic carboxylic acid reacts with incyanate to form a third compound that is effective as a catalyst.
The original catalytic activity is expressed to produce a class amine.

Examples of tertiary amine organic carboxylate catalysts having such properties include triethylene diamine, bis-(dimethylaminoethyl) ether, N, N, N, N, etc.
, Salts of ordinary tertiary amines such as N-pentamethyldiethylenetriamine and organic carboxylic acids such as formic acid, acetic acid, and 2-ethylhexanoic acid are known.

However, although these tertiary amine organic carboxylate catalysts significantly improve fluidity due to the retardation of the initial reaction, they have little effect on shortening demolding time due to improved curability. Therefore, a more effective catalyst, namely,
There is a need for a catalyst system that improves resin fluidity and filling properties by delaying the initial resinization activity in the reaction between incyanate and polyol, and further promotes the late resinization activity to shorten the final curing time. Ta.

[Means to solve the problem]

The present inventors have intensively investigated a catalyst that improves the above two performances at the same time. As a result, the initial flow rate was improved by compounding a quaternary ammonium salt compound with a tertiary amine organic carboxylate catalyst at a specific ratio. The inventors have discovered that the curing properties can be improved without impairing the properties and the demolding time can be significantly shortened, and the present invention has been achieved.

That is, the present invention is a compound in which 5 to 50% by weight of a quaternary ammonium salt compound is combined with a salt of an organic carboxylic acid having 1 to 8 carbon atoms of a tertiary amine compound, with the sum of both being 100% by weight. A catalyst composition for polyurethane polymerization is provided.

In the catalyst of the present invention, when 5% by weight of the quaternary ammonium salt is added without vortexing, almost no effect is observed;
If it exceeds 0% by weight, the resin surface will become loose, so-called flyability, and 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 that simultaneously improves initial retardation and late curing properties, which is made by combining an organic carboxylate of a tertiary amine with a quaternary ammonium salt compound.

Examples of the tertiary amine used in the organic carboxylate of a tertiary amine and the quaternary ammonium salt compound used in the present invention include N-methylmorpholine, N-ethylmorpholine, triethylenediamine, N,N , N, N-
Tetramethyl-1,3-propylenediamine, N, N
, N, N-tetramethylhexamethylenediamine,
N,N,N,N,L-pentamethyldiethylenetriamine, bis-(2-dimethylaminoethyl)ethenope
N,N-dimethylethanolamine, N,N-dimethylbenzylamine, N,N,N-)IJ methylaminoethylpiperazine, N,N,N-to'Js(3-dimethylaminopropyl)hexahydro-S Examples include compounds such as triazine.

The organic carboxylic acids having 1 to 8 carbon atoms used in the production of organic carboxylic acid salts of tertiary amines used in the present invention are formic acid, acetic acid, propionic acid, acetic acid, caprylic acid, 2-ethylhexanoic acid, caprone. Acids such as pyruvic acid and benzoic acid are used, but formic acid, acetic acid, and propionic acid are particularly preferably used, and the amount added is from 0.1 to 1.0 molar equivalent per 1 molar equivalent of nitrogen of the tertiary amine. .

The quaternary ammonium salt compound used in the present invention may be an inorganic acid or an organic acid in the presence of the tertiary amine; It is produced by reacting 3 moles of alkylene oxide.

As the alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc. are preferably used.

In producing the catalyst of the present invention, the tertiary amine is mixed with a polar organic solvent, such as a glycol-based solvent, if necessary, and then stirred while cooling the container. Add acid and mix. 4th after cooling
What is necessary is to add and mix a predetermined amount of a class ammonium salt compound.

The composite catalyst of the present invention produced in this way is used in an amount of 0.5 to 5.0 parts when the commonly used polyol is 100B, and can also be used in combination with a common tertiary amine or an organic tin compound as a cocatalyst. I can do it.

When producing polyurethane using the novel catalyst of the present invention, additives such as CFCl3 and CH2C may be used as necessary.
Foaming agents such as l2, surfactants such as organic polysiloxane,
Flame retardants such as halogenated alkyl compounds and halogenated phosphorus compounds, and other additives can be used.

The types and amounts of these additives can be sufficiently used within the types and ranges commonly used.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited only to these Examples.

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

This time, the flyability evaluation was ASTM C42l-
61. ...Figure 1 Fillability was evaluated based on the length of the molded product using an inverted-shaped foam panel whose temperature was controlled at 40°C. ...Table 3 In addition, in the evaluation of curability, the curing behavior of the resin center was continuously tracked and evaluated using dynamic viscoelasticity measurement (Hybron method). ...Figure 2 Note that DF in Figure 2 is a value that is an index of resin hardness.

Table-1 Example I II, N, l'l''J'J''-1 mol of pentamethyldiethylenetriamine was neutralized with 1 mol of 2-ethylhexanoic acid, and then 1 mol of propylene oxide was added to form a quaternary ammonium salt. It was made into a compound. On the other hand, after dissolving triethylenediamine in twice the amount of dipropylene glycol, formic acid was added in the same molar amount as triethylenediamine, and after stirring and cooling, the ratio of the quaternary ammonium salt compound to formate was 4/4.
It was combined to become 6.

Using this catalyst, foaming was carried out based on the above recipe.

The results are shown in Table 3, Figures 1 and 2.

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

The results are shown in Table 3 and Figure 1.

Example 3 In Example 1, formic acid was changed to 2-ethylhexanoic acid,
A similar operation was performed.

The results are shown in Table 3 and Figure 2.

Example 4 The same operation as in Example 1 was performed except that twice the mole of formic acid was added.

The results are shown in Table-3.

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

The results are shown in Table 3 and Figure 2.

Comparative Example 1 Foaming was carried out according to the above recipe using N, N, N, N, N-pentamethyldiethylenetriamine as a catalyst.

The results are shown in Table 3 and Figure 2.

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

The results are shown in Table 3 and Figure 2.

Comparative Example 3 Foaming was carried out in Example 1 using only the formate catalyst.

The results are shown in Table 3 and Figure 1.

Comparative Example 4 Foaming was carried out in Example 1 using only the quaternary ammonium salt compound.

The results are shown in Table 3 and Figure 1.

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

The results are shown in Table 3 and Figure 1.

Table 2 summarizes the catalyst formulations of the above Examples and Comparative Examples.

In the table, gel time refers to the time required for the polymerization to sufficiently proceed before a string is pulled from the polyurethane foam when a sharp object is brought into contact with the surface of the polyurethane foam and then removed.

Table-2 Catalyst blending example GT Nigel time...set to 55 seconds TBDA: triethylenediamine P), IDBTA: pentamethyldiethylene trir
Min FA: formic acid εH8 2-ethylhexanoic acid Po: propylene oxide
In addition, curability can be promoted.

For example, in Table 3, it is clear that Comparative Example 3 has excellent filling properties, but Example 1 in which a quaternary salt was combined with Comparative Example 3
The filling properties are also excellent. Also Figure-2
Therefore, when the curing behavior is evaluated, it can be seen that Comparative Example 3 is not inferior to Comparative Example 2, which exhibits the highest curability as a single tertiary amine. By combining this with quaternary salt, Example 1
For the first time, it has been quantitatively shown that the curability is even higher than that of the previous one.

From the above, the effects of the catalyst of the present invention are clear.

Also, when evaluating the fryability by using a quaternary salt catalyst, it is desirable to combine the fryability with an upper limit of about 50% as shown in Figure 1.

[Brief explanation of the drawing]

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

Claims (1)

[Scope of Claims] 1. 5 to 50% by weight of a quaternary ammonium salt compound is combined with a salt of an organic carboxylic acid having 1 to 8 carbon atoms of a tertiary amine compound, with the sum of both being 100% by weight. A catalyst composition for polyurethane polymerization. 2 A salt of an organic carboxylic acid of a tertiary amine compound is
2. The catalyst composition for polyurethane polymerization according to claim 1, which is produced using 0.1 to 1.0 equivalent of the monobasic organic carboxylic acid relative to the nitrogen equivalent of the primary amine compound.