JPH0240245B2 - - 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 a mixture of vinyl polymer and polyether polyol, and may be used during storage or in a premix (polyol, urethanization catalyst, foaming catalyst, etc.). Since the vinyl polymer separates during the preparation (mixture of foam stabilizer, 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 may vary. We cannot expect much improvement. As a method to improve this drawback, polyhydroxyl, which improves the grafting rate of vinyl polymers, is produced by reacting an unsaturated ester polyol obtained by reacting a polyether polyol with an unsaturated dibasic acid and a vinyl monomer. Although there are methods to obtain compounds (Japanese Patent Publication No. 51-40914, Japanese Patent Publication No. 51-40915)
(No. Publication), thickening during the polymerization reaction of vinyl monomers,
Gelation occurs and it is 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. There is also a method of using an ester obtained by combining a large amount of saturated acid or a vinyl monomer with an unsaturated acid with low copolymerizability, but this essentially reduces the amount of unsaturated acid used and produces a uniform result. It is difficult to obtain polyhydroxyl compounds with low viscosity. Furthermore, in the reaction between a polyol and a dicarboxylic acid, the number of functional groups is reduced due to the formation of intramolecular esters. In particular, the intramolecular diester produced from trifunctional polyether and dicarboxylic acid, which is often used for flexible urethane foams, becomes monofunctional and acts as a terminator for polymerization when reacting with polyisocyanate. In polyhydroxyl compounds obtained by conventional methods, contamination of hydroxyl compounds with monofunctional or low functional groups is unavoidable, and the physical properties of polyurethane materials using these compounds are not 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, 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 for the structure of the present invention are that polyisocyanate and polyhydroxyl compound are the main reaction components,
Polyester obtained by treating polyether polyol and itaconic acid at 170 to 230°C and simultaneously performing esterification, thermal polymerization, isomerization, and addition reaction as at least one component of a polyhydroxyl compound when producing a polyurethane substance. The purpose of this invention is to use a polyhydroxyl compound obtained by graft polymerizing a radically polymerizable vinyl monomer. 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. You can leave it on. 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 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, propene glycol), alkanetriols (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 glycoseed), aromatic polyhydric alcohols Hydrolic alcohols (e.g. trimethylolbenzene) and polyhydric phenols (e.g. phenol-formalin initial condensate) can be mentioned. In addition, the above general formula K(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 Thermal polymerization, isomerization, and addition reactions of itaconic acid esters are described in J. Polymer. Sci. Part C, 1117-1137 (1969).
As reported in , this is already known, and in the conventional method, it was carried out at a relatively low temperature, for example, 150° C. or lower, in order to avoid the progress of reactions other than esterification. The feature of the present invention is that esters obtained by processing at 170 to 230℃, that is, thermal polymerization at the same time as esterification,
The point is that polyester obtained by proceeding with isomerization and addition reactions is used. More specifically, by proceeding with a reaction other than esterification at the same time as esterification, the purpose is to obtain a polyester that is polyfunctionalized and has a large polyether chain relative to the unsaturated bond that is the itaconic acid residue. It's about using it. That is, polyfunctionalization of esters contributes to increasing the crosslinking density of polyurethane, and the use of polyesters with large polyether chains for unsaturated bonds reduces gelation and high In addition to avoiding viscosity, it is possible to obtain a polyhydroxyl compound that is a more homogeneous and more stable graft polymer by increasing the affinity with other polyhydroxyl compounds, polyether polyols, and using this polyurethane material. Its physical properties are extremely high. The reaction between polyether polyol and itaconic acid, which is the first step in obtaining the polyhydroxyl compound of the present invention, is carried out at 170°C to 230°C. 170℃
At lower temperatures, the above-mentioned ester modification reaction does not proceed. Furthermore, if the temperature is higher than 230°C, the polyether polyol will deteriorate and good results will not be obtained. The charging ratio of itaconic acid and polyether polyol may be any ratio, but considering the efficiency of the reaction tank, the viscosity of the product, etc., it is 0.1 to 0.9 mol:
1 mol is preferred. The catalyst may be one commonly used, such as sulfuric acid, para-toluenesulfonic acid, tin chloride, tetraisopropyl titanate, and the like. The second step, the polymerization of the vinyl monomer, is usually carried out in a polyether polyol, and the amount of the above-mentioned characteristic ester used at this time is preferably 5 to 100 parts per 95 to 0 parts of the polyether polyol. 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, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-acrylate
Butyl, isobutyl acrylate, tert acrylate
- Acrylic acid or its esters such as butyl, α-chloroacrylic acid ester; methacrylic acid,
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, dimethylstyrene, Ethylstyrene, methoxystyrene, divinylbenzene, α-methylstyrene, isopropenyltoluene, 4-acetyl-α-methylstyrene, β-methylstyrene,
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 proportion to the above polyester and polyether polyol if present, but in order to obtain a good polyurethane foam, preferably 3 to 40% by weight, particularly preferably 5 to 30% by weight. It is preferable to use vinyl monomers in proportions of % 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 a one-shot process in which a mixed polyisocyanate of polyurethane foam and a polyhydroxyl compound are reacted in one step in the presence of a blowing agent and a suitable auxiliary agent. 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 preferred in view 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; , 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, diphenyldimethyl Methane-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, Diisocyanates such as those obtained by hydrogenating the aromatic ring contained in the above 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 mol of water and 2 mol of water) Urea diisocyanate obtained by reaction with 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, examples of which include molar trichloromethane, difluorodichloromethane, monofluorodichloromethane, difluoromonochloromethane, difluorodibromemethane, and tetrafluorodichloroethane. , difluoropromethane, and the like. Examples of the foam stabilizer 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, triethylenediamine), tin catalysts (e.g., dibutyltin dilaurate, Dibutyltin diethylhexoate, stannous octoate,
stannous oleate), etc. 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 Example of esterification reaction production 1 4700 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 36, 65 parts of itaconic acid, and 15 parts of paratoluenesulfonic acid were placed in a flask and heated at 170 to 180°C under nitrogen. The reaction was carried out at normal pressure for 10 hours and at the same temperature and 50 mmHg for 15 hours. product yield,
The analysis results are shown in Table-1. Production Examples 2 to 5, Comparative Production Examples 1 to 4 Products of Production Examples 2 to 5 and Comparative Production Examples 1 to 4 were obtained in the same manner as Production Example 1. Table 1 shows the results.
Shown below.

【table】

[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 80-120°C for 5 hours, followed by degassing at 100-120°C and below 10 mmHg for 1 hour. The resulting product was a homogeneous white emulsion. The analysis results 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 and 1.0 part of lauroyl peroxide were placed in a flask, and 30 parts of the ester obtained in Production Example-2 and 20 parts of styrene were added dropwise over 5 hours to react. Ta. The reaction temperature was kept at 70-110°C. Next, deaeration was performed at 100 to 110°C to obtain a uniform white emulsion. The analysis results of this product are shown in Table-2.

【table】

[Table] Production Examples 1 to 8 and Comparative Examples 1 to 2 of Polyurethane Materials Polyhydroxyl compounds and other polyhydroxyl compounds produced by Production Examples and Comparative Production Examples, blowing agents, foam stabilizers, Place the catalyst in a container, stir and mix to make this the A component,
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 results are shown in Table-3.

【table】

【table】

Claims (1)

[Claims] 1 When producing a polyurethane material using a polyisocyanate and a polyhydroxyl compound as the main reaction components, polyether polyol and itaconic acid are treated at 170°C to 230°C as at least one component of the polyhydroxyl compound to undergo thermal polymerization at the same time as esterification. A method for producing a polyurethane material, comprising using a polyhydroxyl compound obtained by graft polymerizing a radically polymerizable vinyl monomer to a polyester obtained by performing isomerization and addition reactions.