JPS6020923A - Production of polyurethane material - Google Patents

Abstract

PURPOSE:To produce a polyurethane material excellent in strength and rubber elasticity, by reacting a polyisocyanate with a specified hydroxyl compound. CONSTITUTION:A polyhydroxyl compound is obtained by graft-polymerizing 97-40wt% ester obtained by reacting 1mol of a polyether polyol with 0.05-3mol of a mercapto group-containing monocarboxylic acid or its reactive derivative (e.g., thioglicolic acid) and, optionally, 0.95-0mol of a polycarboxylic acid or its reactive derivative (e.g., adipic acid) at 60-160 deg.C, with 3-60wt% radical-polymerizable vinyl monomer (e.g., methyl vinyl ether). A polyisocyanate (e.g., 2,4- toluylene diisocyanate) is reacted with the above polyhydroxyl compound in the presence of a blowing agent (e.g., monofluorotrichloromethane), a foam stabilizer, a catalyst, etc.

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 monomer.

Conventionally, methods for improving the physical properties such as strength and rubber-like elasticity of polyurethane materials include methods of dispersing vinyl monomers in polyether polyols, methods of polymerizing vinyl monomers in polyether polyols, Methods such as partially grafting a vinyl polymer onto a polyether polyol have been carried out (Japanese Patent Publication No. 44-8230, Japanese Patent Publication No. 47-15108), but the polyurethane materials obtained using these polyols are It has not yet reached the point where it shows fully 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 polymer and polyether polyol, and may be used during storage or as a premix (polyol, urethanization catalyst, 1 foaming). Because the vinyl polymer separates during preparation (mixtures of foam stabilizers, foam stabilizers, etc.) or during the urethanization reaction, the resulting polyurethane material is non-uniform, and furthermore, during the production of polyurethane foam, cell cracking, etc. may occur. occurs. In addition, even in polyurethane materials obtained by carefully controlling the vinyl polymer so that it does not separate,
Essentially, the vinyl polymer is merely contained as a mixture, and no significant improvement in physical properties can be expected.

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 is also a method for obtaining hydroxyl compounds (Japanese Patent Publication No. 51-40914,
5l-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 to avoid thickening and gelation, the grafting rate will decrease and the product will become non-uniform.

In addition, the amount of esthetics obtained by using a large amount of saturated acid or a vinyl monomer in combination with an unsaturated acid with low copolymerizability is reduced, making it difficult to obtain a uniform and low-viscosity polyhydroxyl compound. be.

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 of the structure of the present invention are that when producing a polyurethane material using a polyisocyanate and a hydroxyl compound as the main reaction components, at least one component of the hydroxyl compound is a polyether polyol and a monocarboxylic acid having a mercapto group or its reactivity. The purpose is to use a hydroxyl compound obtained by graft polymerizing a radically polymerizable vinyl monomer to an ester obtained by reacting a derivative and optionally a polycarboxylic acid or a reactive derivative thereof.

The borie 2-methyl polyol used to obtain the hydroxyl compound used in the present invention can be appropriately selected from the conventionally known polyether polyol group, but typical examples of one group of compounds include compounds having active hydrogen atoms. General formula as obtained by reacting with alkylene oxide: %Formula%(1) (where A is a residue of a compound containing an active hydrogen atom, R1 is an alkylene group, and nl is a number indicating the number of polymerized oxyalkylene groups. The hydroxyl value of polyether polyol is 100~
The number is preferably such that 25'WKOH/y, and nl may be different for each chain.
These numbers are the same as the number of functional groups in A, preferably 2 to 6 on average, and particularly preferably 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), alkanetriols (e.g., glycerin, trimethylolpronochloride, hexanetriol), alkane polyols (e.g., hentaerythritol, 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 Examples of alcohol C include nitrimethylolbenzene) and polyhydric phenols (eg, phenol-formalin initial condensate).

In addition, in the general formula (R10), a polyoxypropylene chain represented by nl, (-OH2-OH,, -OH,
, -0H2-0-')n or polyoxybutylene chains such as those obtained by polymerization of butylene oxide, polyoxy/alkylene chains obtained by copolymerization or block polymerization of ethylene oxide and propylene oxide. etc.

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 polyhydric carboxylic acids include adipic acid, oxalic acid, succinic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, and trimellitic acid. 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 carried out under the conditions commonly used, and the amounts of the mercapto group-containing monocarboxylic acid and polycarboxylic acid used are 1.0% of the polyether polyol. It is preferably 0.05 to 3 mol and 0.95 to 0 mol, respectively. Considering the efficiency of the reaction tank, the viscosity of the ester produced, etc., 0.1 to 1.0 mol and 0.5 to 0 mol are preferable, respectively.

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

Reaction temperature is 60-160°C, preferably 90-140°C
is good.

The second step, the polymerization of vinyl monomers, is usually carried out in a polyether polyol, and the amount of the above-mentioned ester used is 5 parts by weight per 95 to 0 parts by weight of the polyether polyol.
~100 parts by weight is good.

Vinyl monomers to be graft copolymerized by the method of the present invention include methyl vinyl ether, isopropyl vinyl ether, ethyl vinyl ether, inbutyl 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 phthyl vinyl ether, 1,3-dimethylbutyl vinyl ether, diimpropyl methyl vinyl ether, 1
-Methyl hephthyl vinyl ether, n-nonyl vinyl ether, n-decyl vinyl ether, 1-methyl-4-
Vinyl ethers such as ethyl octyl vinyl ether, n-tetradecyl vinyl ether, n-hexadecyl vinyl ether, n-octadecyl vinyl ether, oleyl vinyl ether; vinyl acetate, monochlorovinyl acetate, dichlorovinyl acetate, methoxyvinyl acetate, thiovinyl acetate, phenylacetic acid Vinyl, impropiovinyl acetate, α-cyanovinyl acetate, vinyl formate, vinyl chloroformate, vinyl propionate, vinyl butyrate, vinyl trimethyl acetate, vinyl α-ethylcaproate, vinyl laurate, vinyl stearate, vinyl acrylate, croton Vinyl esters such as vinyl acid, vinyl oleate, vinyl cyclohexylcarboxylate, vinyl benzoate, and divinyl terephthalate; acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-acrylate Acrylic acid or its esters such as butyl, isobutyl acrylate, tert-butyl acrylate, a-chloroacrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, impropyl methacrylate, methacrylate Methacrylic acid or its esters such as n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate; styrene, methylstyrene, dimethylstyrene, ethylstyrene, methoxystyrene, divinylbenzene, α-methylstyrene, isopropenyltoluene, 4 -acetyl-alpha-methylstyrene, beta-methylstyrene, chlorstyrene, 2,5-dichlorostyrene, a-chlorostyrene derivatives such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide or substituted products thereof; It will be done.

Vinyl monomers can be used in any proportion to the above esters, and in some cases esters and polyether polyols, but when trying to obtain a good polyurethane foam, vinyl monomers should be used in combination with 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.
A suitable catalyst can 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, polyincyanate 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 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 with water. 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 auxiliary agents. The blowing agent here includes reactive blowing agents such as water, but the obtained 7
Considering the physical properties of Ohm, especially its brittleness, it has a low boiling point...
Non-reactive blowing agents such as logenated hydrocarbons are preferred. Other auxiliary agents used include catalyst 9 foaming regulators (foam stabilizers), colorants, fillers, flame retardants, and the like.

A preferred polyincyanate is a general formula (where ◯ is a benzene ring or a naphthalene ring, -Ne.

is a nuclear-substituted incyanate group, or a nuclear-substituted halogen atom, or an alkyl or alkoxyl group having 3 or less carbon atoms, n
' is o, 1 or 2) diisocyanate (e.g. 2.4-) ylene diisocyanate, 2.6-
) Louis diisocyanate, 1,4-naphthylene diisocyanate, j, 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, -(C!H,,1mNco
is a nuclear-substituted alkylene isocyanate group, or a nuclear-substituted halogen atom or a carbon number 4-)-1,2-dimethylpenzole, ω, ω'-diisocyanate 1,3-
Dimethylpenzole) 2 General formula K A' is an alkylene group having 5 or less carbon atoms such as 10H2-, OH, -c-OH3), ○ is a benzene ring or naphthalene ring, xI''i is a halogen atom substituted with the nucleus or an alkyl or alkoxyl group with carbon number of 3 or less, m' and n''
Diisocyanate C represented by 0 and 1 digits 2) Example: 4,4'-diphenylmethane diisocyanate, 2
, 2'-dimethyldiphenylmethane-4,4'-diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, s,3''-dichlorodiphenyldimethylmethane-4,4'-diisocyanate) (wherein or Nuclear substitution halogen atom or alkyl or alkoxyl group having 5 or less carbon atoms, m'fJO or 1, n''
' is 0, 1 or 2) diisocyanate (e.g.
Bifecol-2,4'-diincyanate, 6,3'-
Dimethylbiphenyl-4,4'-diisocyanate, 6
,5'-dimethoxybipheny/l/4 + 4'-cy7cyanate)nidiphenyl, ;z, Ruhoy -4
+4'-diisocyanate, benzene-1,2,4-)
Diisocyanate, 2.4.6-) Diisocyanate, 4,4', 4''-) Riphenylmethane triisocyanate, 2,4.4'-) Riisocyanate Cyphenyl ether, Approximately 3 phenyl isozoanates are added to methylene Bridge-bonded polyisocyanates, diisocyanates such as those obtained by hydrogenating the aromatic ring contained in the above iso-5 cyanate (e.g. dicyclohexane-4,4'-diisocyanate, ω,ω'-diincyanate-1,2- Dimethylbenzene, ω, ω′-diisocyanate 1.3
−? methylbenzene): 2 moles of diisocyanate and 1
Diincyanates containing substituted urea groups obtained by reaction of moles of water (e.g. 1 mole of water and 2 moles of 2.4-)
Urea diisocyanate obtained by reaction with silane diisocyanate); uretdione diisocyanate obtained by bimolecular polymerization of aromatic diisocyanate by a known method, and the like.

Incidentally, aliphatic polyinsyanates can also be used.

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

Examples of catalysts that promote the reaction of -NCO groups include tertiary amine catalysts (e.g., N-dimethylpiperazine, endoethylenepiperazine, N-ethylmorpholine, triethylenediamine), tin-based catalysts (e.g., dibutyltin dilaurate, dibutyl tin diethylhexoate, stannous octoate, stannous oleate), and the like.

Examples and comparative examples are listed below.

In addition, "r part" on each side all represents "1 part by weight", and the unit of hydroxyl value and acid value is "9KOH/S'.

Production of polyhydroxyl compound 1, Esterification reaction [Production Example-1] In a flask, 4,700 parts of poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 36, 18 parts of thioglycolic acid, 58 parts of adipic acid, paratoluenesulfone 15 parts of acid were charged, and dehydration was carried out under nitrogen at 80-160°C and 100-soimHg for 1 hour.

The resulting product was a pale yellow viscous liquid.

The yield 1 analysis results 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.

2. Vinyl monomer polymerization reaction [Production example-■] 60 parts of the ester obtained in Production example-1, poly(oxyethylene/oxypropylene) glycerol with a hydroxyl value of 35 5
0 parts, 20 parts of styrene, and 0.5 parts of benzoyl peroxide were charged into a flask, and reacted at 80 to 120°C for 5 hours.
Then 100-110°C.

Degassing was performed for 1 hour at 10 ηHg or less. The obtained product was a uniform white emulsion, and the analysis results of this product are shown below.
Shown in 2.

[Manufacturing examples - ■ ~ V, ■, Comparative manufacturing examples - ■ ~ ■] Manufacturing examples -
Production examples -■ to V, ■, Comparative production example-I using the same method as in ■
A product of ~■ was obtained.

The results are shown in Table-2.

[Manufacturing example - ■]

Poly(oxyethylene/oxypropylene) glycerol SOW with a hydroxyl value of 35, 0.5 part of benzoyl peroxide was placed in a flask, and 50 parts of the ester obtained in Production Example-3,
20 parts of styrene was added dropwise to react for 5 hours. The reaction temperature was kept at 80-120°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.

Production of polyurethane materials [Examples-1 to 7, Comparative Example-1] Polyhydroxyl compounds and other polyhydroxyl compounds produced by Production Examples-I to ■ and Comparative Production Example-■ 1 Foaming agent, foam stabilizer, catalyst were placed in a container and mixed by stirring to prepare the A component, and the incyanate group-containing compound as the B component.

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.

Claims (1)

[Claims] When producing a polyurethane material using a polyisocyanate and a hydroxyl compound as main reaction components, at least one component of the hydroxyl compound is a polyether polyol, a monocarboxylic acid having a mercapto group, or a reactive derivative thereof, and optionally a polyhydric carboxylic acid or A method for producing a polyurethane material, comprising using a hydroxyl compound obtained by graft polymerizing a radically polymerizable vinyl monomer to an ester with a reactive derivative thereof.