JPH0238084B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD This invention relates to an improved method for producing hydroxyl compounds. More specifically, the present invention relates to a method for producing a polyether polyol substantially graft-polymerized with a vinyl monomer suitable for producing polyurethane materials. 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. 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 in order to avoid thickening and gelation, the grafting rate will decrease and the product will become non-uniform. There is also a method of using a large amount of saturated acid or an ester obtained by using a combination of vinyl monomer and unsaturated acid with low copolymerizability, but essentially the method is to reduce the amount of unsaturated acid used. Therefore, it is difficult to obtain a uniform, low-viscosity polyhydroxyl compound. An object of the present invention is to provide a method for producing a hydroxyl compound that overcomes the drawbacks of such conventional methods. More specifically, it is an object of the present invention to provide a method for producing a hydroxyl compound suitable for producing a polyurethane material with particularly excellent physical properties such as strength and rubber elasticity. The requirements for the structure of the present invention are that an ester obtained by reacting a polyether polyol with a monocarboxylic acid having a mercapto group or a reactive derivative thereof, and optionally a polyhydric carboxylic acid or a reactive derivative thereof is capable of radical polymerization. The objective is to produce a hydroxyl compound obtained by graft polymerizing vinyl monomers. The polyether polyol used to obtain the hydroxyl compound of 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, R ₁
is an alkylene group, n ₁ 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 n ₁ is different for each chain. f ₁ is a number of 2 or more than 2 and has the same value as the number of functional groups in A, preferably an average number of 2 to 6, and particularly preferably a number of 3 to 6. ) is 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 alcohols (e.g. inositol, 2,
2-bis-(4-hydroxylhexyl)propane), monosaccharides or their derivatives (e.g. methyl glucoseed), aromatic polyhydric alcohols (e.g. trimethylolbenzene), polyhydric phenols (e.g. phenol-formalin initial stage) condensates). 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 polycarboxylic acids include adipic acid, oxalic acid, succinic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic 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 one commonly used, 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, and the amount of the above-mentioned ester used is
5 to 100 parts by weight is better compared to 95 to 0 parts by weight. 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, and 2-methoxyethyl vinyl ether. , n-hexyl vinyl ether,
n-octyl vinyl ether, 1-methyl-2,
2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, 1,3-dimethylbutyl vinyl ether, diisopropylmethyl vinyl ether, 1-methylheptyl vinyl ether,
n-nonyl vinyl ether, n-decyl vinyl ether, 1-methyl-4-ethyloctyl vinyl ether, n-tetradecyl vinyl ether, n
- Vinyl ethers such as 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, α-
Vinyl esters such as vinyl ethyl caproate, vinyl laurate, vinyl stearate, vinyl acrylate, vinyl crotonate, vinyl oleate, vinyl cyclohexylcarboxylate, vinyl benzoate, and divinyl terephthalate; acrylic acid,
Acrylic acid or its esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, α-chloroacrylate; methacrylate acids, methacrylic acid or its esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate; styrene, methylstyrene, dimethyl Styrene, ethylstyrene, methoxystyrene, divinylbenzene, α-methylstyrene, isopropenytoluene, 4-acetyl-α-methylstyrene, β-methylstyrene, chlorstyrene, 2,5-dichlorostyrene, α-chlorostyrene. Styrene derivatives such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, or substituted products thereof. Vinyl monomers can be used in any proportion to the above esters, and in some cases esters and polyether polyols.When trying to obtain a good polyurethane foam, it is preferable to use esters and polyether polyols in some cases. The vinyl monomer is preferably used in an amount of 3 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. Examples and comparative examples are listed below. In each example, "part" represents "part by weight", and the units of the hydroxyl value and acid value are mgKOH/g. Production of polyhydroxyl compound 1 Esterification reaction production example 1 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 were charged in a flask. Under nitrogen, 80-130
℃, normal pressure for 5 hours, then 110-130℃, 100-50
Degassing was performed at mmHg for 1 hour. The resulting product was a pale yellow viscous liquid. The yield, analysis results, etc. are shown in Table 1. Production Examples 2 to 5, Comparative Production Examples 1 to 3 Products of Production Examples 2 to 5 and Comparative Production Examples 1 to 3 were obtained in the same manner as in Production Example 1. The results are shown in Table-1.

[Table] 2 Vinyl monomer polymerization reaction 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 placed in a flask and reacted at 80-120°C for 5 hours, followed by degassing at 100-110°C and below 10 mmHg for 1 hour. The obtained product was a uniform white emulsion, and the analysis results of this product are shown in Table 2. Examples ~, Comparative Examples ~ The products of Examples ~ and Comparative Examples ~ were obtained in the same manner as in the Examples. The results are shown in Table-2. 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】

[Table] Polyurethane material manufacturing usage examples 1 to 7, comparative usage example 1 The hydroxyl compounds and other polyhydroxyl compounds, blowing agents, foam stabilizers, and catalysts produced in Examples ~ and Comparative Examples were placed in a container, After stirring and mixing, this was used as component A, and the 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】

【table】

Claims (1)

[Claims] 1. It is characterized by graft polymerizing a radically polymerizable vinyl monomer to an ester of a polyether polyol, a monocarboxylic acid having a mercapto group, or a reactive derivative thereof, and optionally a polyhydric carboxylic acid or a reactive derivative thereof. A method for producing a hydroxyl compound.