JP2764873B2 - Catalyst composition for polyurethane production - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyurethane foaming catalyst having a retardation property using an organic carboxylate of a tertiary amine compound.

More specifically, a polyurethane foaming catalyst excellent in liquidity and aging stability obtained by adding an appropriate amount of a monoalcohol organic solvent, preferably methyl alcohol, ethyl alcohol, or isopropyl alcohol, to an organic carboxylate of a tertiary amine compound. About.

[Conventional technology]

A polyurethane foam is produced by reacting an organic polyisocyanate and a polyol in the presence of a blowing agent and a catalyst.

In recent years, demands for urethane catalysts at the time of polyurethane foam production have been increasing. For example, a catalyst having a low initial activity for increasing the fluidity of the foam in the mold due to a complicated product shape, and a catalyst having a high curability, that is, a high late activity for improving the productivity.

There has been a demand for the development of a so-called lagging catalyst in which the above requirements, that is, the initial activity is low and the activity increases with the progress of the reaction. As such a retarding catalyst, JP-A-54-1306 discloses
No. 97, JP-B-57-56491, and organic carboxylate salts of tertiary amine compounds are known.

The organic carboxylate of the tertiary amine compound does not show its original activity because the tertiary amine compound is blocked with the organic carboxylic acid in the initial stage of the polyurethane foam formation reaction, but the reaction heat gradually increases. The catalyst is decomposed, and the organic carboxylic acid reacts with the polyol to release a tertiary amine compound effective as a catalyst, thereby exhibiting the original catalytic activity.

Examples of the acid salt-based retarding catalyst having such properties include a conventional tertiary amine compound such as triethylenediamine and bis- (dimethylaminoethyl) ether and an organic carboxylic acid such as formic acid, acetic acid and 2-ethylhexanoic acid. Acid salts are known.

However, organic carboxylate salts of these tertiary amine compounds except for 2-ethylhexanoate generally have low compatibility with the tertiary amine compound and separate into two phases.
It was very difficult to use.

To solve this problem, as described in JP-A-60-6717, it becomes clear that a uniform catalyst can be used by adding an organic solvent having 2 to 4 hydroxyl groups. A solution was being planned.

[Problems to be solved by the invention]

However, when these organic solvents are used, dissociation of a specific formate catalyst of, for example, N, N, N ', N ", N" -pentamethyldiethylenetriamine proceeds at room temperature in a polyol, that is, in a premixed state. , From several hours to about 1
Problems such as an increase in the reaction activity in about a day and no manifestation of an effective delaying action were clarified.

[Means for solving the problem]

The present inventors have studied these retarding catalysts, and as a result, have found that effective retardation can be maintained extremely stably by using a monoalcohol-based organic solvent, and have completed the present invention.

That is, the present invention provides a polyurethane foaming catalyst having a retarding property, which is obtained by mixing a monoalcohol organic solvent with an organic carboxylate catalyst of a tertiary amine compound.

The use of the catalyst according to the invention makes it possible for the first time to use the catalyst in commercial production lines of urethane foam for a long time.

Since the catalyst of the present invention has a low initial activity at the time of the urethane foam molding reaction, it has excellent liquid flowability into the mold, and a molded article having good filling properties can be obtained. Furthermore, in the latter stage of the reaction, the decatalyzing time is not prolonged since the original catalytic activity of the tertiary amine compound is exhibited.

As the tertiary amine compound used in the present invention, for example, N-methylmorpholine, N-ethylmorpholine, 1,4
-Diazabicyclo [2,2,2] octane, N, N, N ', N'-tetramethyl-1,3-propylenediamine, N, N, N', N'-
Tetramethyl-1,6-hexanediamine, N, N, N ′, N ″,
N ″ -pentamethyldiethylenetriamine, bis- (2
-Dimethylaminoethyl) ether, N, N-dimethylethanolamine, N, N-dimethylbenzylamine, N, N, N
Compounds such as -trimethylaminoethylpiperazine.

The organic carboxylic acid used in the present invention is formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, 2-ethylhexanoic acid,
Caproic acid, cyanoacetic acid, pyruvic acid, benzoic acid and the like are used, but formic acid is preferred as the most effective one, and the amount of addition is 0.1 to 1.0 mol based on 1 mol equivalent of nitrogen of the tertiary amine compound. is there.

The monoalcohol-based organic solvent may be any linear or branched alcohol having 1 to 6 carbon atoms,
Particularly preferably, methyl alcohol, ethyl alcohol,
Isopropyl alcohol, butyl alcohol, etc., and the amount of addition is preferably 10 to 40% by weight, based on the organic carboxylate of the tertiary amine compound, with the sum of both being 100% by weight, and if it is more than this, it works as a terminator. In some cases, the influence of the monoalcohol is increased, and the physical properties of the urethane foam are reduced. On the other hand, if the addition amount is 10% by weight or less, the organic carboxylate of the tertiary amine compound is separated into two phases, or the acid salt is crystallized, making it difficult to use.

Polyols that can be used when producing polyurethane using the catalyst composition of the present invention include generally known polyester polyols, polyether polyols, and the like, for example, from normal dibasic acids and polyhydric alcohols. Polyester polyols produced, glycol, glycerin, pentaerythritol, trimethylolpropane, polyhydric alcohols such as sucrose, polyether polyols obtained by adding ethylene oxide or propylene oxide, or triethylenediamine, tolylenediamine, Examples thereof include amine polyols obtained by adding ethylene oxide or propylene oxide to a polyamine such as hexamethylenediamine or isophoronediamine.

The polyisocyanate that can be used when producing the polyurethane using the catalyst composition of the present invention may be any generally known polyisocyanate, for example, 2,4-tolylene diisocyanate,
4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,
Lysine diisocyanate, kylylene diisocyanate,
Cyclohexane diisocyanate, toluidine diisocyanate, p-phenylene diisocyanate, o-phenylene diisocyanate, m-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4-biphenyl diisocyanate, 3,3-dimethylbiphenyl-4,4
-Diisocyanate, 3,3-dimethoxybiphenyl-4,4
-Diisocyanate and the like.

In the production of the catalyst of the present invention, a tertiary amine compound and a monoalcohol-based organic solvent are mixed, and the mixture is stirred while cooling the vessel, and a predetermined amount of an organic carboxylic acid is added and mixed in several times. Is good.

The catalyst for polyurethane production of the present invention having a retardation produced in this manner can be used with a commonly used polyol.
It is used in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight, and can be used in combination with a usual tertiary amine compound or organotin compound as a cocatalyst.

In producing a using a catalyst composition polyurethanes of the present invention, as an additive as needed, blowing agents such as CFCl ₃ or CH ₂ Cl _2, surfactants such as organopolysiloxanes, halogenated alkyl compound , A flame retardant such as a phosphorus halide compound, and other additives. 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 these Examples.

The mixing ratio of the raw materials for polyurethane production was as shown in Table 1, and urethane foaming was carried out according to a usual procedure. That is, a polyol, water, a surfactant, a catalyst, a foaming agent, and a 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 is open.)

Example 1 In a 500 ml round bottom flask equipped with a mechanical stirrer
N, N, N ', N ", N" -pentamethyldiethylenetriamine 1
60 g and 40 g of methyl alcohol are added, and then, while cooling the flask, 40 g of 100% formic acid is added from a dropping funnel over about 15 minutes.

The obtained catalyst was a homogeneous pale yellow viscous solution, and was used in an amount of 3.0 parts with respect to 100 parts of the polyol.

Example 2 In the same manner as in Example 1, N, N, N ', N ", N" -pentamethyldiethylenetriamine (160 g), isopropyl alcohol (40 g), and formic acid (40 g) were mixed, stirred, and used in an amount of 3.0 parts.

Example 3 In the same manner as in Example 1, N, N, N ', N ", N" -pentamethyldiethylenetriamine 160 g and hexyl alcohol 40
g and further 40 g of formic acid were mixed and stirred, and 3.0 parts were used.

Comparative Example 1 160 g of N, N, N ', N ", N" -pentamethyldiethylenetriamine and octyl alcohol 40 were prepared in the same manner as in Example 1.
g and further 40 g of formic acid were mixed and stirred, and 3.0 parts were used.

Comparative Example 2 N, N, N ', N ", N" -pentamethyldiethylenetriamine (160 g) and ethylene glycol 10 were prepared in the same manner as in Example 1.
0 g and further 40 g of formic acid were mixed and stirred, and 3.8 parts were used.

Comparative Example 3 In the same manner as in Example 1, N, N, N ', N ", N" -pentamethyldiethylenetriamine (160 g), dipropylene glycol (100 g), and formic acid (40 g) were mixed, stirred, and used in an amount of 3.8 parts.

Using the catalysts obtained in Examples 1 to 3 and Comparative Examples 1 to 3, a urethane foam was molded,
The cream time (CT), the gel time (GT), and the rise time (RT) after 30 minutes, 1 day, and 2 weeks were measured, and the retardation of the catalyst was evaluated.

 Table 2 shows the results.

<Cream time (CT)> Refers to the time from the start of mixing and stirring of raw materials until immediately before foaming starts.

<Gel Time (GT)> When a sharp object is brought into contact with the surface of the polyurethane foam and subsequently released, it refers to the time required for sufficiently increasing the molecular weight until the yarn is pulled from the polyurethane foam.

<Rise time (RT)> Indicates the time from the start of stirring to the end of foaming.

Results From the above results, when a long-chain alcohol or glycol is used as the solvent as in the comparative example, the gel time tends to be reduced by about 5 to 9 seconds after one day.

In contrast, when a short-chain monoalcohol was used as in the example, the change was extremely small, and it was confirmed that the formate catalyst was stably present in the premix (mixture of raw materials other than isocyanate). .

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshio Nozawa 2710-209, Miho-cho, Midori-ku, Yokohama-shi, Kanagawa (56) References JP-A-50-85590 (JP, A) JP-A-1-168717 (JP, A) JP-A-60-6717 (JP, A) JP-A-58-96657 (JP, A) JP-A-56-57859 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) ) C08G 18/00-18/87

Claims (2)

(57) [Claims] 1. An organic carboxylate salt of one or more tertiary amine compounds, and a monoalcohol organic solvent having 1 to 6 carbon atoms, and 10 to 40% by weight of the sum of both being 100% by weight. A catalyst composition for producing polyurethane. 2. The organic carboxylate of a tertiary amine compound is produced using 0.1 to 1.0 equivalent of a monobasic organic carboxylic acid with respect to the nitrogen equivalent of the tertiary amine compound. The catalyst composition for producing a polyurethane according to the above.