JPS6011522A - Production of polyurethane material - Google Patents

Abstract

PURPOSE:To produce a polyurethane material excellent in strength, rubber elasticity, etc., by polymerizing a polyisocyanate with a specified polyhydroxyl compound substantially grafted with a vinyl monomer. CONSTITUTION:Use is made of a polyhydroxyl compound obtained by reacting a polyether-polyol, e.g., poly(oxyethylene/oxypropylene) glycol, with itaconic acid at 170-230 deg.C to form a polyester by esterification, thermal polymerization and isomerization, and graft-polymerizing a vinyl compound (e.g., styrene) with the polyester. Namely, a polyisocyanate (e.g., 2,4-toluylene diisocyanate) is mixed with the above polyhydroxyl compound, a catalyst, a blowing agent, a foam stabilizer, etc., and the mixture is expanded by reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed 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. Although methods such as partially grafting a vinyl polymer onto a polyol have been carried out (Japanese Patent Publication No. 44-8230, Japanese Patent Publication No. 47-15108), the polyurethane materials obtained using these polyols are not fully satisfactory. Physical properties have not yet been demonstrated.

In other words, the polyurethane obtained by the methods described in these publications has an extremely low degree of Riohe grafting, or is simply a mixture of vinyl polymer and polyether polyol, and during storage or in the premix (polyol, urethanization catalyst, foaming catalyst, Because the vinyl polymer separates during preparation (mixtures of foam stabilizers, etc.) or during the urethanization reaction,
The resulting polyurethane material will be non-uniform, and furthermore, cell roughness will occur during the production of polyurethane foam. In addition, even in polyurethane materials obtained by carefully controlling the vinyl polymer so that it does not separate, the vinyl polymer is essentially contained only as a mixture, and the physical properties may vary. We cannot expect much improvement.

As a method to improve this drawback, the grafting rate of vinyl polymers was improved by reacting vinyl monomers with unsaturated ester polyols obtained by reacting polyether polyols with unsaturated dibasic acids. Although there are methods for obtaining polyhydroxyl compounds (Japanese Patent Publication No. 51-40914, Japanese Patent Publication No. 51-40915), thickening and gelation occur during the polymerization reaction of vinyl monomers, making it difficult to obtain the desired product. It is difficult.

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. Particularly used for soft urethane foam 3
An intramolecular diester formed from a functional polyether and a dicarboxylic acid becomes monofunctional and acts as a terminator for polymerization when reacting with a polyisocyanate.

In polyhydroxyl compounds obtained by conventional methods, contamination with monofunctional or low-functional hydroxyl compounds 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, the purpose of the present invention is to provide a polyurethane material that is particularly excellent in physical properties such as strength and rubber elasticity. , a 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: %Formula%(1) (where A is the active hydrogen atom-containing compound residue, R15- is an alkylene group, and nl is the number of polymerized oxyalkylene groups) The hydroxyl value of polyniteripolyol is 1
It is preferable that the number is 00 to 25 qKOH/f, and n1 may be different for each chain, and fl is 1
Alternatively, it is 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 2 to 6. ) or a mixture thereof.

Examples of compounds corresponding to the above general formula are alcohol,
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 (e.g. nitrimethylolbenzene), polyhydric phenols (e.g. (phenol 6-rumin initial condensate).

Moreover, (R10) in the above general formula. For example, 1 is OH.

"Polyoxypropylene chain represented by (-OH2-○H-0-)n, (-0H2-OH
A polyoxybutylene chain represented by 2-CH2-OH2-0-)n or a polyoxybutylene chain obtained by polymerization of butylene oxide, a polyoxyalkylene chain obtained by copolymerization or block polymerization of ethylene oxide and propylene oxide etc.

Thermal polymerization, isomerization, and addition reactions of itaconic acid esters are described in J.
Polymer, Sci, Part 0.111
7-1137 (1969),
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°C, i.e., thermal polymerization and isomerization at the same time as esterification,
The point is that polyester obtained by proceeding with an addition reaction 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 improves 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.

First step in obtaining the polyhydroxyl compound of the present invention
The reaction step between polyether polyol and itaconic acid is carried out at 170°C to 230°C.

At temperatures lower than 170°C, the above-mentioned ester modification reaction does not proceed. Further, at temperatures higher than 230°C, the polyether polyol deteriorates and good results cannot be obtained.

The charging ratio of itaconic acid and polyether polyol may be any ratio, but in consideration of the efficiency of the reaction tank, the viscosity of the product, etc., it is preferably 0.1 to 0.9 mol:1 mol.

The catalyst may be one commonly used, such as sulfuric acid,
Examples include para-toluenesulfonic acid, tin chloride, tetraisopropyl titanate, and the like.

The second step, the polymerization of vinyl monomers, is usually carried out in polyether polyol, and the amount of the above-mentioned modified ester used at this time is preferably 5 to 100 parts per 95 to 0 parts of polyether polyol.

The vinyl groups to be graft copolymerized by the method of the present invention include methyl vinyl ether, isopropyl vinyl ether, ethyl vinyl ether, imbutyl vinyl ether, n-p+9-ruvinyl 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 phthyl vinyl ether, 1.3-dimethylbutyl vinyl ether, diisopropyl methyl vinyl ether, 1-methyl hebutyl vinyl ether, n-nonyl vinyl ether% n-7
Vinyl ethers such as silvinyl ether, 1-71f /l/ -4-ethyloctyl vinyl ether, n-tetradecyl vinyl ether, n-hexatecyl vinyl ether, n-octadecyl vinyl ether, oleyl vinyl ether; vinyl acetate, monochlorovinyl acetate, dichloroacetic acid Vinyl, methoxyvinyl acetate, vinyl thioacetate, vinyl phenylacetate, isopropiovinyl acetate, α-cyanovinyl acetate, vinyl formate, vinyl chloroformate, vinyl propionate, vinyl butyrate, vinyl trimethyl acetate, vinyl 10-α-ethyl caproate , vinyl laurate, vinyl stearate, vinyl acrylate, 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; methacrylic acid, methyl methacrylate, methacrylic acid Ethyl, n-propyl methacrylate, isopropyl methacrylate,
Methacrylic acid or its esters such as isobutyl methacrylate, isobutyl methacrylate, rgtert-butyl methacrylate; styrene, methylstyrene, dimethylstyrene, ethylstyrene, methoxystyrene, divinylbenzene, α-methylstyrene, isopropenyltoluene, 4- Kistyrene derivatives such as acetyl-α-methylstyrene, β-methylstyrene, chlorstyrene, 2,5-dichlorostyrene, and α-chlorostyrene; examples include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, or substituted products thereof .

The vinyl monomer can be used in any proportion to the polyester and polyether polyol if present, but in order to obtain a good polyurethane foam, it is preferably 5 to 40% by weight, preferably 5 to 40% by weight. 50% by weight
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 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, 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 polyhydroxyl 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 include catalysts and foaming regulators (foam stabilizers)
, colorants, fillers, flame retardants, etc.

15- Here, preferred polyisocyanates are those represented by the general formula (where ○ is a benzene ring or naphthalene ring, -Neo is a nuclear-substituted isocyanate group, a nuclear-substituted halogen atom, an alkyl having 3 or less carbon atoms, Alkoxyl group n/
diisocyanate (e.g. 2,4-) ylene diisocyanate, 2,6-tolylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, 1゜5- phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-isopropylbenzo-2,
4-diisocyanate) general formula (where ○ is a benzene ring or naphthalene ring, -(OH2)mN00 is a nuclear-substituted alkylene isocyanate group, X is a nuclear-substituted halogen atom or an alkyl having 14-3 or less carbon atoms, is an alkoxyl group, m is 1 or 2,
diisocyanate (e.g. ω, ω'-diisocyanate-1,2-dimethylpenzole, ω, ω'-diisocyanate-1,3-dimethylpenzole) represented by the general formula (n' is 0, 1 or 2) ) % Formula % (Here, A' is an alkylene group having 5 or less carbon atoms such as 101' (2-, OH, -0-OH, etc., ○ is a benzene ring or naphthalene ring, and X is a substituted halogen atom. Or carbon number 3
Diisocyanates represented by the following alkyl or alkoxyl groups (m/ and n, respectively, 0, 1 or 2) (e.g.
4,4'-diphenylmethane diisocyanate-1., 2.
2'-dimethyldiphenylmethane-4,4'-diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, 3,3'-dichlorodiphenyldimethylmethane-4,4'-di (here or with nuclear substitution). rogen atom or alkyl or alkoxyl group having 3 or less carbon atoms,
m" is 0 or 1, n'" is 0,1 or 2) diisocyanate (e.g. biphenyl-2,4'-diisocyanate, 5,5'-dimethylpiphenyl-4°4'
-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate) diphenylsulfone-4,4'-diisocyanate, benzene-1,2,4
- triisocyanate, 2. A, 6-) diisocyanate, 4.4',4''-triphenylmethane triisocyanate, 2,4.4'-triisocyanate diphenyl ether, polyisocyanate in which about 3 phenyl isocyanates are linked via a methylene bridge, the above isocyanate Diisocyanates such as those obtained by hydrogenating aromatic rings contained in −
dimethylbenzene): A diisocyanate containing a substituted 16-substituted urea group obtained by the reaction of 2 mol of diisocyanate and 1 mol of water (e.g., 1 mol of water and 2
Urea diisocyanate obtained by reaction with 2.4-mol ole diisocyanate): Examples include uretdione diisocyanate obtained by bimolecular polymerization of aromatic diisocyanate by a known method.

Aliphatic polyisocyanates can also be used.

Preferred blowing agents include halogenated lower hydrocarbons, such as monofluorotrichloromethane, difluorodichloromethane,
Examples include monofluorodichloromethane, difluoromonochloromethane, difluorodibromomethane, tetrafluorodichloroethane, and difluorobromoethane.

Examples of the foam stabilizer include conventionally known polydimethylsiloxanes, or so-called silicone oils such as compounds containing polydimethylsiloxane chains and polyoxyethylene chains.

17- Catalysts that promote the reaction of the -No○ group above include, for example, tertiary amine catalysts (e.g., N-dimethylpiperazine, endoethylenepiperazine, N-ethylmorpholine, triethylenediamine), tin-based catalysts (e.g., dibutyltin, dilaurate, dibutyltin diethylhexoate, stannous octoate, stannous oleate), and the like.

Examples and comparative examples are listed below.

All "parts" on each side represent "parts by weight", and the units of hydroxyl value and acid value are qKOH/r.

Production of polyhydroxyl compound 1, esterification reaction [Production Example-1] 4700 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 56 and 6 itaconic acid in a flask
5 parts, and 15 parts of para-toluenesulfonic acid, and heated under nitrogen at 170-180°C and normal pressure for 10 hours at the same temperature, 50+U
+lF! The reaction was carried out at 15 g for 18 hours. Table 1 shows the collection and analysis results of the product.

[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. The results are shown in Table-1.

2. Vinyl monopolymerization reaction [Production Example-D] 30 parts of the ester obtained in Production Example-1, poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 35 5
A flask was charged with 0 parts of styrene, 20 parts of styrene, and 0.5 parts of benzoyl peroxide, and reacted at 80 to 120°C for 5 hours, followed by degassing at 100 to 120°C for 1 hour at 10 to Hg or less. The resulting product was a homogeneous white emulsion. The analysis results are shown in Table-2.

[Manufacturing example - ■ ~ v, t3 comparative manufacturing example - engineering ~ ■] Manufacturing example -
Production examples -π to ■ in the same manner as I.

(2) Comparative Production Example - The product of (2) was obtained. Table 2 of the results
Shown below.

[Manufacturing example - ■]

A flask was charged with 50 parts of poly(oxyethylene-oxypropylene) glycerol having a hydroxyl value of 35 and 1.0 part of lauroyl peroxide, and 30 parts of the ester obtained in Production Example-2,
20 parts of styrene was added dropwise over 5 hours to cause a reaction. The reaction temperature was kept at 70-110°C. Then 1 [10-110℃
Deaeration was performed to obtain a uniform white emulsion.

The analysis results of this product are shown in Table-2.

Production of polyurethane material [Examples-1 to 8. Comparative Examples 1 to 2] The polyhydroxyl compounds produced in Production Examples - Technique - ■ and Comparative Production Examples - m and v, other polyhydroxyl compounds, blowing agents, foam stabilizers, and catalysts were placed in a container, stirred, and mixed. This was designated as component A, and the compound containing an isocyanate group was designated 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-6.

25- 166-

Claims (1)

[Claims] When producing a polyurethane material using a polyisocyanate and a polyhydroxyl compound as 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. 1. A method for producing a polyurethane material, which comprises using a polyhydroxyl compound obtained by graft polymerizing a radically polymerizable monovinyl monomer to a polyester obtained by isomerization and addition reactions.