JPH0238082B2 - - 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 improvements in physical properties cannot be achieved. I can't expect much. As a method to improve this drawback, 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 the compound (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 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. 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 of the structure of the present invention are that a polyhydroxyl compound is produced by graft polymerizing a radically polymerizable vinyl monomer to an ester obtained by reacting a polyether polyol with a dicarboxylic acid having a mercapto group or a reactive derivative thereof. There is a particular thing. 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. General formula as obtained by reacting and alkylene oxide: A [(R ₁ O ₁ ) _o1 H] _f1 ...... (1) (where A is the active hydrogen atom-containing compound residue, R ₁
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 may be 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 a number of 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). Thor, 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), and polyhydric phenols (e.g., 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 -
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 thiolingo residue, 2-mercaptononane dioxygen acid, 2-mercaptopentanedioic acid, 2-mercaptohexadecane dioxygen acid, and 2,4-dimer Mercaptopentanedioic acid, 2,5-
dimermelt hexane dioxydzacide, mercaptomethylbutane dioxydzacide, 2,3
- Dimercaptobutane dioxydzate, 2-
Examples include mercapto-2-methylbutane dioxydide 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 polyhydroxyl compound of the present invention, may be carried out under commonly used conditions, and the amount of dicarboxylic acid having a mercapto group or its reactive derivative used may be adjusted to suit the polyether polyol. For 1.0 mole,
It is preferable to use 0.05 to 1.0 mol. reactor efficiency,
Considering the viscosity of the generated ester, it is 0.1~
0.9 mol is preferred. The catalyst may be one commonly used, such as paratoenesulfonic acid,
Examples include sulfuric acid and tin chloride. Reaction temperature is 60~
160°C, preferably 90-140°C. The two-stage polymerization of vinyl polymers is usually carried out in polyether polyols, and the amount of the above-mentioned esters used is
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 polymers 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,
-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
- Vinyl ethers such as decyl vinyl ether, 1-methyl, 4-ethyloctyl vinyl ether, n-tetradecyl vinyl ether, n-hexadecyl vinyl ether, n-octadecyl vinyl ether, oleyl vinyl ether; vinyl acetate, monochlorovinyl acetate, dichlorovinyl acetate, methoxy Vinyl 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 esters such as vinyl stearate, vinyl acrylate, vinyl crotonate, vinyl oleate, vinyl cyclohexycarboxylate, vinyl benzoate, divinyl terephthanate; acrylic acid, methyl acrylate, ethyl acrylate, n-acrylate Acrylic acid or its esters such as propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, α-chloroacrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid Methacrylic acid or its esters such as n-propyl, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate; styrene, methylstyrene, dimethylstyrene, ethylstyrene, methoxystyrene, divinylbenzene, α -Methylstyrene, isopropenyltoluene, 4-acetyl-α-methylstyrene, β-methylstyrene, chlorstyrene,
Examples include styrene derivatives such as 2,4-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. means a polymer containing a large number of urethane condensations, such as those obtained by the one-shot process in which polyisocyanate and polyhydroxyl compound are applied in one step in the presence of a blowing agent and suitable auxiliaries in the case of polyurethane foams. Alternatively, 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 with water in the presence of a suitable auxiliary agent, or by an excess amount of polyisocyanate and It can be obtained by a semi-prepolymer method, etc., in which a prepolymer obtained by reacting a polyhydroxyl compound with an additional amount of a polyhydroxyl compound is reacted in the presence of a blowing agent and other auxiliary agents. 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 (OH value) and acid value are mg.
KOH/g. 1 Esterification reaction production example 1 A flask was charged with 4700 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 36, 75 parts of thiomalic acid, and 24 parts of paratoluenesulfonic acid, and the mixture was heated at 130 to 140°C under a nitrogen stream at normal pressure. 5 hours,
Dehydration was further performed at 50 mmHg 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 1 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.

[Table] Production example 5 Add 36 hydroxyl value poly(oxyethylene) to the flask.
4,700 parts of oxypropylene glycerol, 110 parts of 2-mercapto-nonane dioxylic acid, and 24 parts of para-toluenesulfonic acid were charged and treated under the same conditions as in Production Example 1. The product obtained has an acid value
It was a yellow sticky liquid with a hydroxyl value of 3.1 and 23. Production Example 6 4700 parts of poly(oxyethylene/oxypropylene) glycerol having a hydroxyl value of 36, 82 parts of 2-mercapto-pentanedioic acid, and 20 parts of tetraisopropyltitanate were charged and treated under the same conditions as in Production Example 1. The obtained product has an acid value of 2.5,
It was a yellowish brown viscous liquid with a hydroxyl value of 24. 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 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 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, 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.

【table】

[Table] 3 Production of polyurethane materials Usage Examples 1 to 8 and Comparative Usage Examples 1 to 2 Polyhydroxyl compounds and other polyhydroxyl compounds produced by Examples to and Comparative Examples, blowing agents, foam stabilizers, catalysts were placed in a container and stirred to mix.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. The results are shown in Table-3.

【table】

【table】

Claims (1)

[Claims] 1. A method for producing a polyhydroxyl compound, which comprises graft polymerizing a radically polymerizable vinyl monomer to an ester of a polyether polyol and a dicarboxylic acid having a mercapto group or a reactive derivative thereof.