JPH0240246B2 - - 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 to improve physical properties such as strength and rubber-like elasticity. Methods such as partially grafting a vinyl polymer onto a polyol have been carried out (Japanese Patent Publication No. 8230/1983, Japanese Patent Publication No. 1983/1983).
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, 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 the physical properties cannot be improved. I can't expect much. 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. Although there are methods for obtaining hydroxyl compounds (Japanese Patent Publications No. 51-40914 and No. 51-40915), thickening and gelation occur during the polymerization reaction of vinyl monomers, making it difficult to obtain the desired product. If the amount of unsaturated acid used is lowered to avoid thickening and gelation, the grafting rate will decrease and the product will become 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. 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 material using a polyisocyanate and a hydroxyl compound as main reaction components, at least one component of the hydroxyl compound is a monocarboxylic acid having a polyether polyol and a mercapto group, or a reaction thereof. The purpose of the present invention is to use a hydroxyl compound obtained by graft polymerizing a radically polymerizable vinyl monomer to an ester obtained by reacting a reactive derivative and, if desired, a polycarboxylic acid or a reactive derivative thereof. The polyether polyol used to obtain the hydroxyl compound used in the present invention can be appropriately selected from the conventionally known polyether polyol groups, but typical examples of one group of compounds include compounds having active hydrogen atoms. General formula as obtained by reacting with alkylene oxide: A [(R ₁ O) _o1 H] _f1 (1) (where A is a residue of a compound 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. You can leave it on. f1 is a number of 2 or more and has the same value as the number of functional groups in A, preferably a number of 2 to 6 on average, and particularly preferably a number of 3 to 6. ) or a mixture thereof. Examples of compounds corresponding to A in the above general formula are alkanediols (e.g. ethylene glycol, propylene glycol), alkane triols (e.g. glycerin, trimethylolpropane, hexanetriol), alkane polyols (e.g. pentaerythritol, xylitol, Sorbitol, alicyclic polyhydric alcohol (e.g. inositol, 2,2
-bis-(4-hydroxylhexyl)propane), monosaccharides or their derivatives (e.g. methyl glycoseed), aromatic polyhydric alcohols (e.g. trimethylolbenzene), polyhydric phenols (e.g. phenol-formalin initial condensation) things). In addition, in the above general formula, (R ₁ O) _o1 is, for example, A polyoxypropylene chain represented by (-CH ₂ -
A polyoxybutylene chain represented by CH ₂ -CH ₂ -CH ₂ -O-) _or a polyoxybutylene chain such as that obtained by polymerization of butylene oxide, or a polyoxybutylene chain such as that obtained by copolymerization or block polymerization of ethylene oxide and propylene oxide. polyoxyalkylene chains etc. obtained by Examples of the monocarboxylic acid having a mercapto group used in the present invention include thioglycolic acid, mercaptopropionic acid, mercaptostearic acid, mercaptobutyric acid, and mercaptooctanoic acid. Examples of polyvalent carboxylic acids include adipic acid, oxalic acid, succinic acid, azelaic acid, sebacic acid, phthalic acid, terphthalic acid, trimellitic acid, and the like. 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 hydroxyl compound of the present invention, may be performed under commonly used conditions, and the amounts of the mercapto group-containing monocarboxylic acid and polycarboxylic acid used are 1.0 mol of the polyether polyol. 0.05~
3 mol, preferably 0.95 to 0 mol. Considering the efficiency of the reaction tank, the viscosity of the ester produced, etc., each is 0.1
-1.0 mol, preferably 0.5-0 mol. The catalyst may be any commonly used catalyst, such as sulfuric acid, para-toluenesulfonic acid, tin chloride, etc. The 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. Vinyl monomers to be graft copolymerized by the method of the present invention include methyl vinyl ether, isopropylene 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, isopropyl vinyl 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; methyl methacrylate, ethyl methacrylate , n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate,
Methacrylic acid or its esters such as isobutyl methacrylate and tert-butyl methacrylate; styrene, methylstyrene, dimethylstyrene, ethylstyrene, methoxystyrene, divinylbenzene, α-methylstyrene, isopropenyltoluene, 4-acetyl-α- Methylstyrene, β-
Examples include styrene derivatives such as methylstyrene, chlorostyrene, 2,5-dichlorostyrene, and α-chlorostyrene; acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, or substituted products thereof. The vinyl monomer can be used in any proportion to the ester and polyether polyol, but in order to obtain a good polyurethane foam, it is best to 3 to 60% by weight, particularly preferably 5 to 40% by weight, based on the ether polyol
It is preferable to use vinyl monomers in a proportion of . 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 is 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.
Alternatively, a semi-prepolymer method in which a prepolymer obtained by reacting an excess amount of polyisocyanate and a polyhydroxyl compound and an additional amount of the polyhydroxyl compound are reacted in the presence of a blowing agent and other suitable auxiliary agents. You can get it by twisting it. 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, foaming regulators (foam stabilizers), colorants,
Fillers, flame retardants, etc. are used. Here, preferred polyisocyanates have the general formula (Here 〇 is a benzene ring or naphthalene ring, -
NCO is a nuclear-substituted isocyanate group; Isocyanate, 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 −,

[Formula] An alkylene group having 3 or less carbon atoms, 〇 is a benzene ring or naphthalene ring, and X is a nuclear-substituted halogen atom or an alkyl or alkoxyl group having 3 or less carbon atoms,
m' and n'' are respectively 0, 1 or 2) diisocyanate (e.g. 4,4'-diphenylmethane diisocyanate, 2,2-dimethyldiphenylmethane-4,4'-diisocyanate, diphenyldimethylmethane) -4,4'-diisocyanate, 3,
3'-dichlorodiphenyldimethylmethane-4,
4'-Diisocyanate): General formula (Here, X is a nuclear-substituted halogen atom or an alkyl or alkoxyl group having 3 or less carbon atoms, m″ is 0
or 1, n is 0, 1 or 2) (e.g. biphenyl-2,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,
4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate): diphenylsulfone-4,4'-diisocyanate, benzene-1,2,4-triisocyanate, 2,4,
6-triisocyanate, 4,4',4''-triphenylmethane triisocyanate, 2,4,4'-triisocyanate diphenyl ether, polyisocyanate in which about 3 phenyl isocyanates are linked with a methylene bridge, the above Diisocyanates such as those obtained by hydrogenating aromatic rings contained in isocyanates (e.g. dicyclohexane-4,4'-diisocyanate, ω,ω'-diisocyanate-1,
2-dimethylbenzene, ω,ω'-diisocyanate-1,3-dimethylbenzene): Diisocyanate containing substituted urea groups obtained by reaction of 2 mol of diisocyanate and 1 mol of water (e.g. 1
Urea diisocyanate obtained by reaction of 2 moles of water with 2 moles of 2,4-toluylene diisocyanate): Uretdione diisocyanate obtained by bimolecular polymerization of aromatic diisocyanate by a known method. Incidentally, aliphatic polyisocyanates can also be used. Preferred blowing agents include halogenated lower hydrocarbons, such as monofluorochloromethane, difluorodichloromethane, monofluorodichloromethane,
Examples include difluoromonochloromethane, difluorodibromomethane, tetrafluorodichloroethane, difluorobromoethane, and the like. Examples of the blowing agent include conventionally known polydimethylsiloxanes, or so-called silicone oils such as compounds containing polydimethylsiloxane chains and polyoxyethylene chains. Catalysts that promote the reaction of the -NCO group include, for example, tertiary amine catalysts (e.g., N-dimethylpiperazine, endoethylenepiperazine, N-ethylmorpholine, triethyleneamine), tin-based catalysts (e.g., dibutyltin dilaurate), etc. , dibutyltin diethylhexoate, stannous octoate, stannous oleate), and the like. Examples and comparative examples are listed below. In addition, all "parts" in each example represent "parts by weight", and the units of hydroxyl value and acid value are mgKOH/g.
It is. Production of polyhydroxyl compound 1 Esterification reaction production example 1 A flask was charged with 4700 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 36, 18 parts of thioglycolic acid, 58 parts of adipic acid, and 15 parts of para-toluenesulfonic acid. 80~130℃ under nitrogen,
5 hours at normal pressure, then 110-130℃, 100-50mmHg
Dehydration was performed for 1 hour. The resulting product was a pale yellow viscous liquid. The yield and analysis results are shown in Table-1. Production Examples 2 to 5, Comparative Production Examples 1 to 3 Production Examples 2 to 5, in the same manner as Production Example 1,
Products of Comparative Production Examples-1 to 3 were obtained. The results are shown in Table-1.

[Table] 2 Vinyl monomer polymerization reaction production example 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, benzoyl peroxide
0.5 part was charged into a flask and reacted at 80 to 120°C for 5 hours, followed by degassing at 100 to 110°C and below 10 mgHg for 1 hour. The obtained product was a uniform white emulsion, and the analysis results of this product are shown in Table 2. Manufacturing example~, Comparative manufacturing example~ Manufacturing example~, using the same method as Manufacturing example~,
, Comparative Preparation Example - The products of ~ were obtained. The results are shown in Table-2. Production example: 50 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 35, benzoyl peroxide
0.5 part was placed in a flask, and 30 parts of the ester obtained in Production Example 3 and 20 parts of styrene were added dropwise to react over 5 hours. The reaction temperature was kept at 80-120°C. Then 100~
Degassing was performed at 110°C to obtain a uniform white emulsion.
The analysis results of this product are shown in Table 2.

[Table] Production Examples 1 to 7 and Comparative Example 1 of Polyurethane Substances The polyhydroxyl compounds and other polyhydroxyl compounds produced in Production Examples and Comparative Production Examples, blowing agents, foam stabilizers, and catalysts were placed in containers. The mixture was stirred and mixed to be used as component A, and a compound containing an isocyanate group was used as component B. Components A and B were rapidly mixed, charged into a mold, reacted, and foamed to produce a foam. The compositions of component A and component B and the physical properties of the obtained polyurethane foam are shown in Table 3.

【table】

Claims (1)

[Claims] 1. When producing a polyurethane material using a polyisocyanate and a hydroxyl compound as main reaction components, at least one component of the hydroxyl compound is a polyether polyol, a molar carboxylic acid having a mercapto group, or a reactive derivative thereof, and optionally a polyhydric carboxylic acid or A method for producing a polyurethane material, comprising using a hydroxyl compound obtained by graft polymerizing a radically polymerizable vinyl monomer to an ester with a reactive derivative thereof.