JPH0240092B2 - - Google Patents

Description

[Detailed description of the invention]

This invention relates 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. There have been methods such as partially grafting a vinyl polymer onto
15108), but polyurethane materials obtained using these polyols have not yet shown sufficiently satisfactory physical properties. In other words, the polyols obtained by the methods described in these publications have extremely low grafting rates, or are simply mixtures of vinyl polymers and polyether polyols. Because the vinyl polymer separates during the preparation (mixtures of foam stabilizers, etc.) or during the urethanization reaction, the resulting polyurethane material becomes non-uniform, and furthermore, cell roughness occurs during the production of polyurethane foam. In addition, even in polyurethane materials obtained by careful manipulation so that the vinyl polymer does not separate, the vinyl polymer is essentially contained only as a mixture, and its physical properties are 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 to obtain hydroxyl compounds (Japanese Patent Publications No. 51-40914, No. 51-40915), but thickening and gelation occur during the polymerization reaction of vinyl monomers.
It is difficult to obtain the desired object. If the amount of unsaturated acid used is reduced in order to avoid thickening and gelation, the grafting rate will decrease and the product will become non-uniform. Furthermore, when the amount of vinyl monomer used is reduced, the reaction rate decreases and only low-molecular polymers can be obtained.
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, it is an object of the present invention to provide a polyurethane material that is particularly excellent in physical properties such as strength and rubber elasticity. The requirements for the structure of the present invention are that polyisocyanate and polyhydroxyl compound are the main reaction components,
When producing a polyurethane material, a radically polymerizable vinyl monomer is grafted onto an ester obtained by reacting a polyether polyol with a dicarboxylic acid having a mercapto group or a reactive derivative thereof, as at least one component of a polyhydroxyl compound. The purpose is to use a polyhydroxyl compound obtained by polymerization. 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: A[(R ₁ O) _o1 H] _f1 (1) (where A is a compound residue containing an active hydrogen atom,
_R1 is an alkylene group, n1 is a number indicating the number of polymerized oxyalkylene groups, and is preferably a number such that the hydroxyl value of the polyether polyol is 100 to 25 mgKOH/g, and n1 is different for each chain. f1 is 1 or a number of 1 or more and has the same value as the number of functional groups in A, preferably an average of 2 to 6, and particularly preferably 2 to 6. ) or a mixture thereof. Examples of compounds corresponding to A in the above general formula are alcohols, alkanediols (e.g. ethylene glycol, propylene glycol), alkane triols (e.g. glycerin, trimethylolpropane, hexanetriol), alkane polyols (e.g. pentaerythritol, xylitol, sorbitol), alicyclic polyhydric alcohols (e.g. inositol, 2,2-bis-(4-hydroxylhexyl)propane), monosaccharides or their derivatives (e.g. methyl glucoseed), aromatic polyhydric alcohols Examples include alcohol (eg, trimethylolbenzene) and polyhydric phenol (eg, phenol-formalin initial condensate). In addition, in the above general formula, (R ₁ O) _o1 is, for example, A polyoxypropylene chain represented by (-CH ₂ -
CH ₂ —CH ₂ —CH ₂ —O—) _o Polyoxybutylene chains or polyoxybutylene chains such as those obtained by polymerization of butylene oxide, copolymerization or block polymerization of ethylene oxide and propylene oxide polyoxyalkylene chains etc. obtained by Examples of dicarboxylic acids having a mercapto group used in the present invention include thiomalic acid, 2-mercaptononane dioxygen acid, 2-mercaptopentanedioic acid, 2-mercaptohexadecane dioxychloride acid, and 2,4-dimercapto Pentanedioic acid, 2,5-dimercaptohexane dioxylated acid, mercaptomethylbutane dioxylated acid, 2,3-dimercaptobutane dioxylated acid, 2-mercapto-2-methylbutane dioxylated acid etc. can be mentioned. Examples of 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 performed under commonly used conditions, and the amount of the dicarboxylic acid having a mercapto group or its reactive derivative used is 1.0 mol of the polyether polyol. against, 0.05
It is best to use ~1.0 mol. Considering the efficiency of the reaction tank, the viscosity of the produced ester, etc., the amount is preferably 0.1 to 0.9 mol. The catalyst may be one commonly used, such as para-toluenesulfonic acid, sulfuric acid, tin chloride, etc. Reaction temperature is 60~
160°C, preferably 90-140°C. The second step, the polymerization of the vinyl monomer, is usually carried out in a polyether polyol, the amount of the above ester used being 95%
It is preferably 5 to 100 parts by weight to 0 parts by weight. Incidentally, within the scope of the present invention, reaction components other than mercaptodicarboxylic acid, such as other carboxylic acids,
(Poly)isocyanates and the like 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, 1,3-dimethylbutyl vinyl ether, diisopropyl methyl vinyl ether, 1-methylheptyl vinyl ether, n-nonyl vinyl ether, n-decyl vinyl ether, 1-methyl-4-ethyloctyl vinyl ether, n-tetradecyl vinyl ether, Vinyl ethers such as n-hexadecyl vinyl ether, n-octadecyl vinyl ether, oleyl vinyl ether; vinyl acetate, monochlorovinyl acetate, dichlorovinyl acetate, methoxyvinyl acetate, vinyl thioacetate, phenyl vinyl acetate, isopropiovinyl acetate, α-cyanovinyl acetate , vinyl formate, vinyl chloroformate, vinyl propionate, vinyl butyrate, vinyl trimethyl acetate, vinyl α-ethyl caproate, vinyl laurate, vinyl stearate, vinyl acrylate,
Vinyl esters such as vinyl crotonate, vinyl oleate, vinyl cyclohexylcarboxylate, vinyl benzoate, divinyl terephthalate; acrylic acid, methyl acrylate, ethyl acrylate,
Acrylic acid or its esters such as n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, α-chloroacrylate; methacrylic acid, methyl methacrylate, methacrylic acid Ethyl, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert methacrylate
- Methacrylic acid or its esters such as butyl; styrene, methylstyrene, dimethylstyrene, ethylstyrene, methoxystyrene, divinylbenzene, α-methylstyrene, isopropenyltoluene, 4-acetyl-α-methylstyrene, β-methylstyrene , chlorstyrene, 2,
Examples include styrene derivatives such as 5-dichlorostyrene and α-chlorostyrene; acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, and substituted products thereof. The vinyl monomer can be used in any proportion to the ester, but if you want to obtain a good polyurethane foam, preferably 3
Vinyl monomers are preferably used in proportions of up to 60% 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 a blowing agent and suitable auxiliaries, or by a one-shot process. The method is carried out 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 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 hydroxyl compound with an additional amount of a polyhydroxyl compound is reacted 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 used include catalysts, foaming regulators (foam stabilizers), colorants, fillers, flame retardants, and the like. Here, preferred polyisocyanates have the general formula (Here, 〇 is a benzene ring or naphthalene ring, -
NCO is a nuclear-substituted isocyanate group; , 2,6-toluylene diisocyanate, 1,4-naphthylene diisocyanate,
1,5-naphthylene diisocyanate, 1,3-
Phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-isopropylbenzole-2,4-diisocyanate): General formula (Here, 〇 is a benzene ring or naphthalene ring, -
(CH ₂ ) _n NCO is a nuclear-substituted alkylene isocyanate group, X is a nuclear-substituted halogen atom or alkyl or alkoxyl group having 3 or less carbon atoms, m is 1 or 2, and n' is 0, 1 or 2 The indicated diisocyanate (e.g. ω, ω′-diisocyanate-1,2
-dimethylbenzole, ω,ω'-diisocyanate-1,3-dimethylbenzole): General formula (Here A′ is -CH ₂ -,

[Manufacturing example 1]

4,700 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 36, 75 parts of thiomalic acid, and 24 parts of para-toluenesulfonic acid were placed in a flask, and the mixture was heated at 130 to 140°C under a nitrogen stream at normal pressure for 5 hours.
Dehydration was further performed at 50 mgHg for 1 hour. The obtained product was a yellow viscous liquid with an acid value of 2.1 and a hydroxyl value of 24. [Production Examples 2 to 4, Comparative Production Example 1] Products of Production Examples 2 to 4 and Comparative Production Example 1 were obtained in the same manner as Production Example 1. The results are shown in Table-1.

[Manufacturing example 5]

4,700 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 36 in a flask, 2
-Mercapto-Nonane Dioxide 110 parts,
Production example by adding 24 parts of para-toluenesulfonic acid.
It was treated under the same conditions as 1. The obtained product was a yellow viscous liquid with an acid value of 3.2 and a hydroxyl value of 23. [Production Example 6] 4700 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 36, 82 parts of 2-mercapto-pentanedioic acid, and 20 parts of tetraisopropyl titanate were charged, and the same conditions as in Production Example 1 were added. Processed. The product obtained has an acid value
It was a yellowish brown viscous liquid with a hydroxyl value of 2.5 and a hydroxyl value of 24. 2 Vinyl monomer polymerization reaction [Production Example 1] 30 parts of the ester obtained in Production Example-1, 50 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 35, 20 parts of styrene, lauroyl peroxide
0.5 part was charged into a flask and reacted at 70 to 100°C for 4 hours, followed by degassing at 100 to 110°C and below 10 mmHg for 1 hour. The obtained product was a homogeneous white emulsion, and the analysis results of this product were as follows. Hydroxyl value: 25 Acid value: 0.2 Viscosity (25°C): 2300CP [Production Example~, Comparative Production Example~] The products of Production Example -~ and Comparative Production Example~ were obtained in the same manner as in Production Example~. Table of results-2
Shown below. [Production example] 50 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 35, lauroyl peroxide
0.7 part was placed in a flask, and a mixture of 30 parts of the ester obtained in Production Example-1 and 20 parts of styrene was added dropwise over 5 hours to react. The reaction temperature was kept at 70-100°C.
Next, degassing was performed at 100-110°C and below 10 mmHg. The obtained product was a uniform white emulsion, and the analysis results of this product are shown in Table 2.

[Examples 1-8 and Comparative Examples 1-2]

The polyhydroxyl compounds produced in Production Examples - and Comparative Production Examples -, other polyhydroxyl compounds, blowing agents, foam stabilizers, and catalysts are placed in a container, stirred and mixed, and this is used as component A. A compound containing this was designated as component B. 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.

【table】

Claims (1)

[Claims] 1. When producing a polyurethane material using a polyisocyanate and a polyhydroxyl compound as main reaction components, at least one component of the polyhydroxyl compound can be radically polymerized into an ester of a polyether polyol and a dicarboxylic acid having a mercapto group or a reactive derivative thereof. 1. A method for producing a polyurethane material, the method comprising using a polyhydroxyl compound obtained by graft polymerizing vinyl monomers.