JPS5867716A - Composition for preparing polyurethane foam - Google Patents

Abstract

PURPOSE:The titled composition, containing an organic polyisocyanate compound, a compound containing an active hydrogen atom, a foaming agent and a piperazinoalkylsilane catalyst, capable of giving a foam without defects, e.g. color shading, and having improved uniformity. CONSTITUTION:A composition obtained by reacting (A) an organic polyisocyanate compound, e.g. 4,4'-diphenylmethane diisocyanate, with (B) a compound having one active hydrogen atom determined by the Zerewitnoff method, e.g. a polyether polyol such as glycerol, and (C) a foaming agent, e.g. trichloromonofluoromethane, or water, and (D) a piperazinoalkylsilane catalyst of the formula (R1, R2 and R3 are alkyl, vinyl, aryl or phenyl; R4 is -CH2- or -CH2CH2-).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing polyurethane foam.
The present invention relates to a composition containing an effective catalyst.

Conventionally, amine compounds such as triethylenediamine (1,4-diaza-bicyclo(2,2,2)
octane), N-methylmorpholine, N,N-dimethylethanolamine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine% 1,8-
Diazabicyclo(5,4,0)undecene-7, N-methylpiperidine, etc., and organic tin compounds such as dibutyltin laurate, diptyltin diacetate, etc. have been used.

Polyurethane foams are generally manufactured by Zelevitinoff (Ze
A compound having at least one active hydrogen atom determined by the rewitinoff method (hereinafter referred to as a compound having an active hydrogen atom), water and a fluorocarbon blowing agent, and the above catalyst were mixed. It is obtained by mixing liquid A and liquid B containing an organic polyisocyanate compound as a main component.

However, due to the poor compatibility with the conventional catalyst and the organic polyisocyanate compound, a uniform foam could not be obtained unless both liquids A and B were sufficiently mixed during the production of polyurethane foam. Here, if the mixing is insufficient, there is a drawback that color unevenness tends to occur inside the resulting foam.

An object of the present invention is to provide a composition for producing polyurethane foam, which does not have the above-mentioned drawbacks and can obtain a foam with excellent uniformity.

The composition for producing polyurethane foam of the present invention for the above-mentioned purpose is an organic polyisocyanate compound, a compound having an active hydrogen atom;
s is an alkyl group, a vinyl group, or an aryl group, and the diagonal phenyl group I84 contains a piperazinoalkylsilane catalyst represented by -CH2- or 扛CH2CH2- as an essential component.

The composition of the present invention has good compatibility with the catalytic organic polyisocyanate compound contained therein, and can solve the drawbacks of the prior art.

The present inventors have repeatedly conducted various experiments on catalysts for promoting urethanization reactions that are highly compatible with organic polyisocyanate compounds. As a result, a piperazinoalkylsilane compound represented by the following general formula (where %R1eR2*R1 is an alkyl group, a vinyl group, an aryl group, and a phenyl group IRa is 10H2- or -CHz-CH2) can be used as an organic polymer. The present inventors discovered that they have good compatibility with isocyanate compounds and also have an excellent reaction promoting effect, leading to the present invention.

Examples of the piperazinoalkylsilane compounds used in the present invention include piperazinomethyltrimethylsilane, piperazinomethyldimethylvinyl Vlan, piperazinomethyldimethylazylvlan, piperazinomethyldimethylphenylsilane, and Viperazinomethyldimethylvinyl Vlan. dinomethylpterdimethylsilane,
Examples include 2-biperazinoethyltrimethylsilane, 2-biperazinoethyldimethylvinylsilane, 2-piperazinoethylphenyldimethylsilane, and 2-piperazinoethylbutyldimethylsilane.

The above piperazinoalkylsilane is the following 20) (2)
As shown in , it can be obtained by subjecting chloromethylsilane (I) or chloroethylsilane (I) to a heating reaction (80 to 150°C) in an anhydrous solvent such as dioxane.

The compatibility with the catalytic organic polyisocyanate compound of the present invention is good, and as a result, the obtained foam uniformity is better than that obtained when conventionally used catalysts are generally used. The reason why the catalyst of the present invention has excellent compatibility with organic polyisocyanate compounds is thought to be due to the presence of alkylsilane in the molecule, but the details are unknown.

The use of the above-mentioned catalyst in the present invention is not particularly limited and can be varied over a wide range, but it is usually 0.01 to 5.0 parts by weight per 100 parts by weight of the compound that absorbs active hydrogen atoms.
(Especially Oy1 to Oy3 heavy electrical parts). Of course, it is possible to use more than this, but it is not economical.

Of particular importance among the piperazinoalkylsilanes mentioned above are the piperazinomethyltrimethylsilane and 2-piperazinoethyltrimethylsilane. This is because these have particularly good compatibility with organic polyisocyanate compounds and high catalytic activity.

Compound t! with active hydrogen atom association used in the present invention! , J.
, Iruma, Chew, Soc, vol. 49, p. 3181 (1
It is defined as a compound that can be defined by the method reported by Turevitinoff in 927). Typical compounds include polyether polyols, polyester polyols, polyester thioethers, polycarboxylic acids, and water. Among these, particularly important compounds are polyether polyols, specific examples of which are glycerin and trimethylolpropane.

Triethanolamine, pentaerythritol.

diglycerin, bisphenol A, bisphenol F,
Compounds with alkylene oxides (ethylene oxide, propylene oxide, butylene oxide) added to polyhydric alcohols such as sorbitol and sucrose, ammophores, monoethanolamine, jetanolamine, ethylenediamine 4,4'-diaminodiphenylmethane, and tolylene diamine compounds. There are compounds with alkylene oxide added to amine compounds, phenol novolacs, and compounds with alkylene oxide added to cresol novolac.

Mixtures of these can also be used if desired.

Organic borisonanate compounds that can be used in the present invention include aliphatic polyisocyanates, cycloaliphatic polyisocyanates, and aromatic polyisocyanates. Among these, particularly important are phosgene added to the reaction product of aniline and formaldehyde. MDI (4, a'
diphenylmethane diisocyanate) type compound.

This includes not only yDI alone, but also isocyanates similar to it, ie, compounds generally called crude MDI, such as polyphenylene polymethylene polyisocyanate and carbodiimidized MDI. moreover,
Also of interest are xylylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate and the propolymers obtained with these compounds. The blending amount curve is α5 to 1.5, particularly preferably α9 to 1.3 in terms of isocyanate index.

The catalyst of the present invention can be used alone, but it can also be used in combination with the following conventionally known compounds that have catalytic properties. Specific examples thereof include triethylenediamine, dimethylethanolamine, morpholine compound, imidazole compound, 1,8-diazabicyclo(5,
4,0) undecene-7 and its prenchetedate salt, an organotin compound.

In addition to water and foam, blowing agents used in the present invention include low-boiling organic liquid compounds such as trichlorofluoromethane and methylene chloride, and compounds that decompose to generate nitrogen gas such as azobisisobutyronitrile. . By changing this amount, foams with different densities can be obtained. Among these, helogenated hydrocarbons with a low boiling point (0 to 60°C) are liquid and therefore easy to handle, and are particularly important.

In the present invention, a surfactant may be added as needed. Typical examples of these include combs, oxyalkylene copolymers of polydimethylsiloxane, and fluorine thread compounds.

Other shrines that can be used in the present invention include:
There are fillers, pigments, dyes, flame retardants, and ultraviolet absorbers. These materials can be blended in advance into a compound having an active hydrogen atom or an organic polyisocyanate compound, or can be mixed during foam production.

In order to produce polyurethane foam using the composition of the present invention, it is preferable to mix a liquid A containing a compound having an active hydrogen atom as a main component and a liquid B containing an organic polyisocyanate compound as a main component. In general, it is preferable to mix the catalyst-free blowing agent and other compounds in Liquid A in advance.The mixing method is not particularly limited, but it is recommended to use a high-speed stirrer, a high-pressure impact mixing type blowing machine, etc. I can do it. It is possible to foam in a suitable open mold, or the mixture can be foamed in a closed mold to produce a so-called integral skin foam with a dense skin.

In any case, when the composition of the present invention, especially the catalyst, is used, the following form can be obtained with excellent uniformity compared to the conventional composition vl:IVc.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, and comparative examples will also be described to prove its effects.

Before explaining the Examples and Comparative Examples, a test conducted on the solubility of the catalyst of the present invention and the catalyst of the prior art will be described.

The solubility of the catalyst in crude 1iDI (NGO content = 515 wtX) was tested.

Take Crude MDI 100t as bee force, and there,
Two portions of piperazinomethyltrimethylsilane were added and stirred for 5 seconds using a magnetic stirrer. After 5 seconds, the piperazinomethyltrimethylsilane was completely dissolved.

The solubility of 2-piperazinoethyltrimethylsilane, piperazinomethyldimethylphenylsilane, and 2-piperazinoethylbutyldimethylsilane in carbodiimidized MDI and TDI crude MDI was tested in the same manner. As a result, it was found that all the particles were dissolved in the organic polyisocyanate compound 5 seconds after stirring.

On the other hand, when similar tests were conducted on conventional catalysts such as triethylene diamine and dibutyltin dilaurate, it took 15 seconds or more for them to dissolve in the organic polyisocyanate compound.

Examples using the catalyst of the present invention and comparative examples using a conventional catalyst will be described with reference to Table 8.

Example 1 The composition shown in Kaede of Example 1 of Example 1 of 1 → Shichika 1 Clothing (the blending ratio is shown in parts by weight below), that is, PO (propylene oxide) of monoethanolamine as a compound with an active hydrogen atom. Adduct (OH value: 6 soxon II
l#/I) 40 fit parts, Po adduct of 4.4'diaminodiphenylmethane (OH value=440KOH(Il
#/#) Solution A is made by adding 6ON Sumire, 2 foam stabilizers, 2 foaming agents, and 1.5 heavy metals of piperazinomethyltrimethylsilane as a catalyst, and crude MDI (NCO-containing Mine: 5α5wtX) as an organic polyisocyanate compound. ) A polyurethane foam was produced using 144 parts by weight of liquid B.

A total of 2 oz of liquids A and B (however, the blending ratio of each material was as described above) was placed in a 500-1 polyethylene container and stirred for 5 seconds using a lab stirrer (rotation speed: 3 ooorpm). Cream time (time until foaming started) was 4 seconds, and quiz time (time until foaming was completed) was 45 seconds.

As a result of cutting the obtained foam 1 and observing the internal state, it was confirmed that a foam having uniform cells without color unevenness was produced.

Example 2 Using the composition shown in Example m2 of the pottery pot◇ sauce table,
A polyurethane foam was produced in the same manner as in Example 1. Cream time 1210 seconds, quiz time 1 minute 2
It was 0 seconds.

As a result of cutting the obtained foam and observing the internal condition, it was confirmed that the foam had no uneven color and had a uniform radius.

Examples 3 to 8 Polyurethane foams were produced in the same manner as in Example 1 using the compositions shown in the columns of Example floors 3 to 8 of the heat chart. Cream thyme lamps of Examples 5-8, respectively 5, 5.5.7. 55, 4, 4.5 seconds, quiz time, 50,43゜62.40,38, respectively.
It was 42 seconds.

The obtained foam was cut and the internal state was observed.
In both cases, it was confirmed that there was no uneven color and a uniform form was generated.

Comparative Example 1, 2.3 Comparative Example of Hat Row Mutsu Table - 1, 2,! Polyurethane foam was produced in the same manner as in Example 1 using the composition shown in each column of t (using a conventional catalyst wire). Comparative examples 1 and 2
．． The cream times of No. 3 were 8, 6, and 45 seconds, respectively. Rise time was 55, 50° and 48 seconds for Comparative Examples 1, 2, and 5, respectively.

When the obtained foam was cut and the internal state was observed, it was found that the inside of each foam had white or brown stains, and some cells were large in some places, and lacked uniformity.

As described above, the catalyst dibiherazinoalkyl ν-ran of the present invention has a feature of good compatibility with organic polyisocyanate compounds, which was a drawback of conventional catalysts, and in addition, the present invention When this composition is used, the homogeneity of the resulting foam is improved compared to compositions using conventional catalysts.

Furthermore, the polyurethane foam obtained using the composition of the present invention has extremely excellent heat insulation properties, dimensional stability, and mechanical properties. It is particularly suitable for the production of structural parts where

Claims (1)

[Claims] Organic polyisocyanate compound;
rewitinoff) method; a blowing agent; and a piperazinoalkylsilane catalyst represented by the following general formula. A composition for producing polyurethane foam. 5 where % R1* Rll * R1 is an alkyl group, vinyl group, aryl group, or phenyl group I Ra is -C
H2-ma9 is -CHz-CH2-.