JPH0238083B2 - HORIHIDOROKISHIRUKAGOBUTSUNOSEIZOHOHO - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improved method for producing polyhydroxyl 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. 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. 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. An object of the present invention is to provide a method for producing polyhydroxyl compounds 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 polyhydroxyl 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 the ester obtained by reacting a polyether polyol with a dicarboxylic acid having a mercapto group or a reactive derivative thereof and a polyhydric carboxylic acid other than these or a reactive derivative thereof has a vinyl compound capable of radical polymerization. The purpose is to graft polymerize monomers to produce polyhydroxyl compounds. The polyether polyol used to obtain the polyhydroxyl compound of the present invention can be appropriately selected from a group of conventionally known polyether polyols, and examples of one typical group of compounds include compounds having active hydrogen atoms. The general formula obtained by reacting alkylene oxide with alkylene oxide: A [(R ₁ O) _o1 H] _f1 (1) (where A is the active hydrogen atom-containing compound residue, 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 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, but particularly preferably 2 to 6. ) is 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-hydroxylcyclohexyl)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, (R ₁ O) _o1 in the above general formula 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 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, 2,4-dimercapto Pentanedioic acid, 2,5-dimercaptohexane dioxylated acid, mercaptomethylbutadiene dioxylated acid, 2,3
- Dimercaptobutane dioxydzate, 2-
Examples include mercapto-2-methylbutane dioxydide and the like. 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 acids. 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 carried out under commonly used conditions. The amount of each derivative is per 1.0 mol of polyether polyol.
It is preferable to use 0.05 to 0.95 mol, or 0.95 to 0.05 mol.
Considering the efficiency of the reaction tank, the viscosity of the produced ester, etc., 0.1 to 0.9 mol and 0.5 to 0.05 mol are preferable, respectively. The total amount of both carboxylic acids is preferably 0.15 to 0.95 mol. The catalyst may be one commonly used, such as para-toluenesulfonic acid, sulfuric acid, tin chloride, etc. Reaction temperature is 60~160℃,
Preferably the temperature is 90 to 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. Note that reaction components other than mercaptodicarboxylic acid and polyvalent carboxylic acid, such as other carboxylic acids, (poly)isocyanates, etc., may be added and reacted within the scope of the purpose of the present invention. 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-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-ethyl octyl vinyl ether, n
- Vinyl ethers such as tetradecyl vinyl ether, n-hexadecyl vinyl ether, n-octadecyl vinyl ether, oleyl vinyl ether; vinyl acetate, monochlorovinyl acetate, dichlorovinyl acetate, methoxyvinyl acetate, thiovinyl acetate, phenyl vinyl acetate, isopropiovinyl acetate , α-cyanovinyl acetate, vinyl formate,
Vinyl chloroformate, vinyl propionate, vinyl butyrate, vinyl trimethyl acetate, vinyl alpha-ethyl caproate, vinyl laurate, vinyl stearate, vinyl acrylate, vinyl crotonate, vinyl oleate, vinyl cyclohexylcarboxylate, vinyl benzoate , vinyl esters such as divinyl terephthalate; acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-acrylate
Acrylic acid or its esters such as butyl, α-chloroacrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid Methacrylic acid or its esters such as tert-butyl; styrene, methylstyrene, dimethylstyrene, ethylstyrene, methoxystyrene, divinylbenzene, α-methylstyrene, isopropenyltoluene, 4-acetyl-α-methylstyrene, β-methyl styrene,
Chlorstyrene, 2,5-dichlorostyrene, α
- Styrene derivatives such as chlorstyrene; examples include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide or substituted products thereof. The vinyl monomer can be used in any ratio relative to the above ester and polyether polyol if used, but if a good polyurethane foam is to be obtained, preferably 3 to 60% by weight relative to the ester and polyether polyol. %, particularly preferably from 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, polyurethane substances are 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, such as those obtained by A total prepolymer method is used 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 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 addition, all "parts" in each example represent "parts by weight", and the units of hydroxyl value and acid value are mgKOH/g.
It is. 1 Esterification reaction production example 1 A flask was charged with 4700 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 36, 45 parts of thiomalic acid, 44 parts of adipic acid, and 24 parts of p-toluenesulfonic acid, and heated under a nitrogen stream for 120 to 30 minutes. 130
Dehydration was carried out at 50° C. and normal pressure for 5 hours and then at 50 mmHg for 1 hour. The obtained product has an acid value of 2.3 and a hydroxyl value
It was a pale yellow viscous liquid. Production Examples 2-6, Comparative Production Examples 1-2 Products of Production Examples 2-6 and Comparative Examples 1-2 were obtained in the same manner as Production Example 1. The results are shown in Table-1.

[Table] Production example 7 Poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 36 in a flask 4700, 2-
66 parts of mercaptononane dioxylic acid, 44 parts of adipic acid, and 25 parts of para-toluenesulfonic acid were charged, and the mixture was treated under the same conditions as in Production Example 1. The obtained product was a pale yellow viscous liquid with an acid value of 2.8 and a hydroxyl value of 20. Production example 8 4800 parts of poly(oxyethylene/oxypropylene) trimethylolpropane with a hydroxyl value of 36, 2-
Mercaptopentanedioic acid 49 parts, adipic acid 44 parts, tetraisopropyl titanate 25 parts
A portion was prepared and treated under the same conditions as in Production Example 1.
The obtained product was a yellowish brown viscous liquid with an acid value of 3.2 and a hydroxyl value of 19. 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, lauroyl peroxide
0.5 part was placed in a flask and reacted at 70-110°C for 4 hours, followed by degassing at 100-110°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: 24 Viscosity (25°C): 2100 CPS Examples ~, Comparative Example 1 ~ 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: 65 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 35, lauroyl peroxide
1.0 part was 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. The reaction temperature was kept at 70-110°C. then 100
Degassing was performed at ~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.

[Table] 3 Polyurethane material manufacturing usage examples 1 to 8 and comparative usage example 1 The polyhydroxyl compounds and other polyhydroxyl compounds produced in Examples to Comparative Examples, a blowing agent, a foam stabilizer, and a catalyst were placed in a container. The mixture was stirred and mixed, and this was used as the A component, and the compound containing an isocyanate group was used as the B component.
Components A and B were rapidly mixed, charged into a mold, and reacted to foam to produce a foam. Display the results -
Shown in 3.

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Claims (1)

[Claims] 1. It is characterized by graft polymerizing a radically polymerizable vinyl monomer to an ester of a polyether polyol, a dicarboxylic acid having a mercapto group, or a reactive derivative thereof, and a polycarboxylic acid other than these, or a reactive derivative thereof. A method for producing a polyhydroxyl compound.