JPS6011521A - Production of polyurethane material - Google Patents

Abstract

PURPOSE:To produce a polyurethane material excellent in strength, rubber elasticity, etc., by polymerizing a polyisocyanate with a specified polyhydroxy compound substantially grafted with a vinyl monomer. CONSTITUTION:Use is made of a polyhydroxyl compound obtained by reacting a polyether-polyol, e.g., poly(oxyethylene/oxypropylene) glycol, with a mercapto group-containing dicarboxylic acid (e.g., thiomalic acid) and a different polycarboxylic acid (eg., adipic acid) to form an ester, and graft-polymerizing a vinyl compound (e.g., styrene) with the above ester compound. Namely, a polyisocyanate (e.g., 2,4-toluylene diisocyanate) is mixed with the above polyhydroxyl compound, a catalyst, a blowing agent, a foam stabilizer, etc., and the mixture is expanded by reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to an improved method of making polyurethane materials.

More specifically, the present invention relates to a method for producing a polyurethane material using a polyether polyol substantially graft-polymerized with a vinyl monomer.

Conventionally, methods for improving physical properties such as strength and rubber-like elasticity of polyurethane materials include methods of dispersing vinyl polymers in polyether polyols, methods of polymerizing vinyl monomers in polyether polyols, and methods of using polyether polyols. Methods such as partially grafting a vinyl polymer onto a polyol have been carried out (Japanese Patent Publication No. 44-8250, Japanese Patent Publication No. 15108/1982), but the polyurethane materials obtained using these polyols are not fully satisfactory. It has not yet reached the point where it has shown any physical properties.

In other words, the polyols obtained by the methods described in these publications have extremely low grafting rates, or are simply a mixture of vinyl polymer and polyether polyol, and may be used during storage or in a premix (polyol, urethanization catalyst, foaming catalyst, etc.). Because the vinyl polymer separates during the preparation (mixture of foam stabilizers, etc.) or during the urethanization reaction, the resulting polyurethane material is non-uniform, and furthermore, cell cracking etc. occur during the production of polyurethane foam. It happens. In addition, even in polyurethane materials obtained by carefully controlling the vinyl polymer so that it does not separate, the vinyl polymer is essentially contained only as a mixture, and the physical properties may vary. We cannot expect much improvement.

As a method to improve this drawback, a polyether polyol is reacted with an unsaturated dibasic acid, and the resulting unsaturated ester polyol is reacted with a vinyl monomer, thereby improving the grafting rate of the vinyl polymer. There are methods for obtaining hydroxyl compounds (Japanese Patent Publications No. 51-40914 and 51-40915), but thickening and gelation occur during the polymerization reaction of vinyl monomers, making it difficult to obtain the desired product. O′l? If the amount of unsaturated acid used is lowered to avoid gelation, the grafting rate will decrease and the product will be non-uniform. There is also a method of using an ester obtained by using a large amount of saturated acid or a vinyl monomer in combination with an unsaturated acid with low copolymerizability, but this essentially reduces the amount of unsaturated acid used. It is difficult to obtain homogeneous and low viscosity polyhydroxyl compounds. The physical properties of polyurethane materials obtained using such polyols are not fully satisfactory.

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing polyurethane materials that overcomes the drawbacks of the conventional methods. More specifically, an object of the present invention is to provide a polyurethane material that is particularly excellent in physical properties such as strength and rubber elasticity.

The requirements of the structure of the present invention are that when producing a polyurethane τ using a polyisocyanate and a polyhydroxyl compound as main reaction components, at least one component of the polyhydroxyl compound is a polyether polyol and a dicarboxylic acid having a mercapto group, or a dicarboxylic acid having a mercapto group. It is possible to use a polyhydroxyl compound obtained by graft polymerizing a radically polymerizable vinyl monomer to an ester obtained by reacting a reactive derivative and a polycarboxylic acid other than these or a reactive derivative thereof.

The polyether polyol used to obtain the polyhydroxyl compound used in the present invention can be appropriately selected from the conventionally known polyether polyol groups, but examples of one representative group of compounds include active hydrogen atoms. General formula as obtained by reacting a compound and alkylene oxide: %Formula%(1) (where A is a residue of a compound containing an active hydrogen atom, R1 is an alkylene group, and nl is a number indicating the number of polymerized oxyalkylene groups) The hydroxyl value of the polyether polyol is 100~
It is preferable that the number is 254KOH/r,
Also, n1 is for each chain [may be different, fl is 1 or 1
The above number is the same value as the number of functional groups in A, preferably 2 on average.
-6, but particularly preferably 2-6.

) or a mixture thereof.

5- Examples of compounds corresponding to the above general formula Chunin are alcohol,
Alkanediols (e.g. ethylene glycol, propylene gellicol), alkanetriols (e.g. glycerin, trimethylol 7'0/<n, hexanetriol), alkane polyols (e.g. pentaerythritol, xylitol, sorbitol), cycloaliphatic Polyhydric alcohols (e.g. inositol, 2,2-bis-(4-hydroxylcyclohexyl)furopane), monosaccharides or their derivatives (e.g. methylglucoseed), aromatic polyhydric alcohols (e.g. trimethylolbenzene) , polyhydric phenol (
Example: phenol-formalin initial condensate).

In the above general formula, (R10)nl is, for example, OR.

Polyoxypropylene chain represented by (-0H,, -0H-OL)n, (-C town-aH2
-a112- oa2-〇-)n Polyoxybutylene chain or polyoxybutylene chain such as obtained by polymerization of butylene oxide, polyoxyalkylene obtained by copolymerization or block polymerization of ethylene 6-oxide and propylene oxide Chains, etc.

Examples of the dicarboxylic acid having a mercapto group used in the present invention include thiomalic acid, 2-mercaptononanedioic acid, 2-mercaptopentanedioic acid, 2-mercaptohexadecanedioic acid, and 2,4-dimercaptopentanedioic acid. acid,
Examples include 2.5-dimercaptohexanedioic acid, mercaptomethylbutanedioic acid, 2.3-dimercaptobutanedioic acid, and 2-mercapto-2-methylbutanedioic acid. The polyhydric carboxylic acids used in the present invention include saturated aliphatic dicarboxylic acids such as adipic acid, oxalic acid, succinic acid, azelaic acid, sebacic acid, and chlorosuccinic acid; aromatic dicarboxylic acids such as phthalic acid and terephthalic acid; Preferred examples include aromatic tricarboxylic acids such as mellitic acid. Examples of the reactive derivatives include derivatives that react in the same manner as carboxylic acids under reaction conditions, such as lower alcohol esters.

The esterification reaction, which is the first step in obtaining the polyhydroxyl compound of the present invention, may be carried out under commonly used conditions, and the mercapto group-containing dicarboxylic acid used or its reactive derivative and the polyhydric carboxylic acid or its reaction may be used. The amount of the derivative is preferably 0.05 to 0.95 mol and 0.95 to 0.05 mol, respectively, per 1.0 mol of polyether polyol. Considering the efficiency of the reaction tank, the viscosity of the produced ester, etc., the amounts of 0.1 to 0.9 mol and 0.5 mol, respectively
~0.05 Solu is preferred. The total amount of both carboxylic acids is 0
．． It is preferably 15 to 0.95 mol. The catalyst may be any commonly used catalyst, such as para-toluenesulfonic acid, sulfuric acid, tin chloride, etc.

Reaction temperature is 60-160°C, preferably 90-140°C
is good.

The second step, the polymerization of vinyl monomers, is usually carried out in a polyether polyol, and the amount of the above-mentioned ester used is 5 parts by weight per 95 to 0 parts by weight of the polyether polyol.
~100 parts by weight is good. However, within the scope of the purpose of the present invention, reaction components other than mercaptodicarboxylic acid and polyvalent carboxylic acid, such as other carboxylic acids, (poly)isocyanates, etc., may be added and reacted.

Vinyl monomers to be graft copolymerized by the method of the present invention include methyl vinyl ether, isopropyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, 2-chloroethyl vinyl ether, 2-ethylhexyl vinyl ether,
2-methoxyethyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl butyl vinyl ether, 1. S-dimethylbutyl vinyl ether, diisopropyl methyl vinyl ether, 1
-Methyl hebutyl vinyl ether, n-nonyl vinyl ether, n-decyl vinyl ether, 1-meth9-thyl-4-ethyloctyl vinyl ether, n-tetradecyl vinyl ether, n-hexadecyl vinyl ether, n-octadecyl vinyl ether, oleyl vinyl ether Vinyl acetate, vinyl monochloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl thioacetate, vinyl phenylacetate, isopropiovinyl acetate, α-cyanovinyl acetate, vinyl formate, vinyl chloroformate, vinyl propionate, butyric acid Vinyl esters such as vinyl, vinyl trimethyl acetate, vinyl α-ethyl caproate, vinyl laurate, vinyl stearate, vinyl acrylate, vinyl crotonate, vinyl oleate, vinyl cyclohexylcarboxylate, vinyl benzoate, and divinyl terephthalate. Acrylic acids such as acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, α-chloroacrylate 6 or 10 - esters thereof; methacrylic acid or its esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate; ;Styrene, methylstyrene, dimethylstyrene, ethylstyrene, methoxystyrene, divinylbenzene, α-methylstyrene, isopropenyltoluene, 4-acetyl-α-methylstyrene, β-methylstyrene, chlorstyrene, 2
．． Examples include kystyrene derivatives such as 5-dichlorostyrene and α-chlorostyrene; acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, or their diluted derivatives.

The vinyl monomer can be used in any ratio relative to the above ester and polyether polyol if used, but in order to obtain a good polyurethane foam, preferably 5 to 6% vinyl monomer relative to the ester and polyether polyol.
It is preferred to use vinyl monomers in a proportion of 0% by weight, particularly preferably 5 to 40% by weight. The grafting reaction may be carried out by a conventionally known method, and an appropriate catalyst may also be used.

Further, depending on the case, a polyether polyol or the like may be added during or after the reaction.

As is well known, a polyurethane substance is made by using polyisocyanate or a reactive substance such as polyisocyanate and a polyhydroxyl compound or this and other reactive substances as reaction raw materials and reacting them in an appropriate manner depending on the purpose. For example, in the case of polyurethane foams, polyisocyanates and polyhydroxyl compounds are reacted in one step in the presence of blowing agents and suitable auxiliaries, or By a total prepolymer method in which a prepolymer obtained by reacting an excess amount of polyisocyanate and a polyhydroxyl compound is reacted with water in the presence of a suitable auxiliary agent, or by a total prepolymer method in which a prepolymer obtained by reacting an excess amount of polyisocyanate and a polyhydroxyl compound is reacted, or an excess amount of polyisocyanate and a polyhydroxyl compound are reacted. It can be obtained by a semi-prepolymer method, etc., in which a prepolymer obtained by reacting a prepolymer with an additional amount of a polyhydroxyl compound is allowed to react in the presence of a blowing agent and other suitable auxiliaries. The blowing agent here includes reactive blowing agents such as water, but non-reactive blowing agents such as low boiling point halogenated hydrocarbons are preferable in consideration of the physical properties of the resulting foam, especially brittleness. . Other auxiliary agents include catalysts and foaming regulators (foam stabilizers)
, colorants, fillers, flame retardants, etc.

Preferred polyisocyanates are those in the general formula where 〇 and 〇 are benzene rings or naphthalene rings, and -neo is a nuclear-substituted incyanate group, or a nuclear-substituted halogen atom, or an alkyl or alkoxyl group having 3 or less carbon atoms. base n/
is 0.1 or 2) (for example, 2.4-) Louis diisocyanate, 2.6-) Louis diisocyanate, 1,4-naphthylene diisocyanate, 1.5
- Naphthylene diisocyanate, 1゜3-phenylene diisocyanate, j, 4-phenylene diisocyanate, 1-isopropylbenzo-2,4-diisocyanate) (where ○ is a benzene ring or naphthalene ring, -(OH2) mNOO is a nuclear-substituted alkylene isocyanate group, X is a nuclear-substituted halogen atom or an alkyl or alkoxyl group having 3 or less carbon atoms, m is 1 or 2, n'
is 0, 1 or 2) (e.g. ω
, ω'-diisocyanate-1゜2-dimethylpenzole, ω,ω'-diisocyanate-1,S-dimethylpenzole) General formula ()% Formula% 3 or less alkylene group, ○ is a benzene ring or 14-phthalene WTh x is a nuclear-substituted norogen atom or an argyl or alkoxyl group having 3 or less carbon atoms, m' and n"
are respectively 0.1 or 2) (Example a4.4/-diphenylmethane diisocyanate, 2.
2'-dimethyldiphenylmethane-4,4'-diincyanate, diphenyldimethylmethane-4,4'-diisocyanate, 5. ri'-dichlorodiphenyldimethylmethane-4,4'-diisocyanate) general formula (herein or with nuclear substitution), a rogen atom or an alkyl or alkoxyl group having 3 or less carbon atoms, m" is 0 or 1, m′
diisocyanate (w is 0, 1 or 2) (e.g.
Biphenilu 2.47-diisocyanate, 3.3'
-dimethylbiphenyl-4,4'-diisocyanate, S,5'-dimethoxybiphenyl-4,4'-diincyanate) diphenylsulfone-4,4'-diisocyanate, benzene-1,2,4-triisocyanate , 2,4.6-) diisocyanate, 4.4',4
“-triphenylmethane triisocyanate), 2,4.
4" triisocyanate diphenyl ether, polyisocyanate in which about 3 phenyl isocyanates are bonded via a methylene bridge, diisocyanate such as that obtained by hydrogenating the aromatic ring contained in the above isocyanate (e.g. dicyclohexane-4,4'-diisocyanate, ω, ω′
-diisocyanate) -1,2-dimethylbenzene, ω
, ω'-diisocyanate (1°3-dimethylbenzene): A diisocyanate containing a substituted urea group obtained by the reaction of 2 mol of diisocyanate and 1 mol of water (e.g.
Urea diisocyanate obtained by the reaction of 1 mol of water and 2 mol of 2.4-) ylene diisocyanate: Uretdione diisocyanate obtained by bimolecular polymerization of aromatic diisocyanate by a known method.

Aliphatic polyisocyanates can also be used.

Preferred blowing agents include halogenated lower hydrocarbons, such as monofluorotrichloromethane, difluorodichloromethane,
Examples include monofluorodichloromethane, difluoromonochloromethane, difluorodibromomethane, tetrafluorodichloroethane, and difluorobromoethane.

Examples of the foam stabilizer include conventionally known polydimethylsiloxanes, or so-called silicone oils such as compounds containing polydimethylsiloxane chains and polyoxyethylene chains.

Examples of catalysts that promote the reaction of the -NOO group include tertiary amine catalysts (e.g., N-dimethylpiperazine, endoethylenepiperazine, M-ethylmorpholine, triethylenediamine), tin-based catalysts (e.g., dibutyltin dilaurate, dibutyl Examples include tin diethylhexoate, stannous octoate, stannous oleate) and the like.

Examples and comparative examples are listed below.

All "parts" on each side represent "parts by weight," and the units of hydroxyl value and acid value are mgKOH/t.

1. Esterification reaction [Production example-1] 4700 parts of poly(oxyethylene/oxypropylene) glycerol with a flask pressure hydroxyl value of 36, 45 parts of thiomalic acid, adipine i! ! ? 44 parts of p-toluenesulfonic acid and 24 parts of para-toluenesulfonic acid were added, and dehydration was carried out under a nitrogen stream at 120 to 130°C and normal pressure for 5 hours, and then at 50 nmHg for 1 hour. The obtained product was a pale yellow glazed liquid with an acid value of 2.3 and a hydroxyl value of 22.

[Production Examples 2 to 6, Comparative Production Examples 1 to 2] Products of Production Examples 2 to 6 and Comparative Production Examples 1 to 2 were obtained in the same manner as Production Example 1. The results are shown in Table-1.

18- [Production Example-7] A flask was charged with 4700 parts of poly(oxyethylene/oxypropylene) glycerol having a hydroxyl value of 36, 66 parts of 2-mercaptononanedioic acid, 44 parts of adipic acid, and 25 parts of para-toluenesulfonic acid. Manufacturing example-1
It was treated under the same conditions. The obtained product has an acid value of 2.8
It was a pale yellow glaze liquid with a hydroxyl value of 20.

[Production Example-8] 4800 parts of poly(oxyethylene/oxypropylene) trimethylolpropane with a hydroxyl value of 36, 49 parts of 2-mercaptopentanedioic acid, 44 parts of adipic acid
and 25 parts of tetraisopropyl titanate were charged, and the mixture was treated under the same conditions as in Production Example-1. The obtained product was a yellowish brown glaze liquid with an acid value of 3.2 and a hydroxyl value of 19.

2 Vinyl sheep background polymerization reaction [Production Example-Process] 30 parts of the ester obtained in Production Example-1, 50 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 20-35, 20 parts of styrene, 0 lauroyl peroxide
．． 5 parts were placed in a flask and reacted at 70 to 110°C for 4 hours, followed by degassing at 100 to 110°C and below 10 tzHg for 1 hour. The obtained product was a homogeneous white emulsion, and the analysis results of this product were as follows.

Hydroxyl value 24 Adhesive (25°C) 2,100 ape [Production Examples - π to ■, Comparative Production Examples - I to π] Production Examples - π to ■, Comparative Production Examples - ~π product was obtained. The results are shown in Table-2.

[Manufacturing example - ■]

65 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 35 and 1.0 part of lauroyl peroxide were placed in a flask, and 15 parts of the ester obtained in Production Example-6 and 20 parts of styrene were added dropwise over 5 hours to react. I let it happen. The reaction temperature was kept at 70-110°C. Then 100-110℃
, deaeration was carried out under 21-21 degrees of Bg or more. The obtained product was a uniform white emulsion, and the analysis results of this product are shown in Table 2.

22- B Manufacture of polyurethane material [Actual journey examples-1 to 8 and comparative example T1] Manufacture examples-I to ■ and comparison! 1! ,! The polyhydroxyl compound produced by Example-■, other polyhydroxyl compounds, a blowing agent, a foam stabilizer, and a catalyst are placed in a container, stirred and mixed, and this is used as component A, which is a compound or component containing an incyanate group. And so. Components A and B were rapidly mixed, charged into a mold, and reacted to foam to produce a foam. The results are shown in Table-3.

Claims (1)

[Claims] When producing a polyurethane material using a polyisocyanate and a polyhydroxyl compound as main reaction components, at least one component of the polyhydroxyl compound is a polyether polyol, a dicarboxylic acid having a mercapto group, or a reactive derivative thereof, and a polycarboxylic acid other than these. A method for producing a polyurethane material, comprising using a polyhydroxyl compound obtained by graft polymerizing a radically polymerizable vinyl monomer to an ester thereof or a reactive derivative thereof.