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CN-117142991-B - Method for preparing polyol carboxylic acid ester, polymerizable composition and adhesive

CN117142991BCN 117142991 BCN117142991 BCN 117142991BCN-117142991-B

Abstract

The application provides a preparation method of polyol carboxylic ester, which comprises the steps of carrying out esterification reaction on polyol and a carboxylic acid composition under the action of a catalyst and a water-carrying agent to obtain the polyol carboxylic ester, wherein the carboxylic acid composition is selected from 3-mercaptopropionic acid and 3,3 '-thiodipropionic acid, and the content of the 3,3' -thiodipropionic acid in the carboxylic acid composition is 0.01-1wt%. The application also provides a polymer composition and an adhesive. According to the adhesive provided by the application, the carboxylic acid composition is used for replacing 3-mercaptopropionic acid as a reaction raw material of the polyol carboxylic acid ester, so that the adhesive property of the adhesive is improved.

Inventors

  • CHENG ZHEN
  • LIANG WANGEN
  • ZHANG JIANLIN
  • CUI WEIHUA
  • YI XIANJUN
  • WU YUQIANG

Assignees

  • 益丰新材料股份有限公司

Dates

Publication Date
20260512
Application Date
20230830

Claims (9)

  1. 1. A method of preparing a polyol carboxylic acid ester comprising: The method comprises the steps of (1) carrying out esterification reaction on polyol and carboxylic acid composition under the action of a catalyst and a water-carrying agent to obtain polyol carboxylic ester; the carboxylic acid composition is selected from 3-mercaptopropionic acid and 3,3 '-thiodipropionic acid, and the content of the 3,3' -thiodipropionic acid in the carboxylic acid composition is 0.01-1wt%; The polyol is selected from pentaerythritol.
  2. 2. The preparation method according to claim 1, wherein the catalyst is selected from an acidic catalyst selected from one or more of sulfuric acid, hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trichloroacetic acid, tetrabutyl titanate, zinc acetate, supported phosphotungstic acid, supported zirconic acid and supported heteropolyacid, and the water-carrying agent is selected from one or more of petroleum ether, benzene, toluene, xylene, nitrobenzene, chlorobenzene, dichlorobenzene, anisole, diphenyl ether and cyclohexane dichloroethane.
  3. 3. The production method according to claim 1 or 2, wherein the catalyst is 0.5 to 5wt% of the polyol and the carboxylic acid composition, and the water-carrying agent is 0.5 to 3 times the total mass of the polyol and the carboxylic acid composition.
  4. 4. The method according to claim 1, wherein the molar ratio of the polyol to the carboxylic acid composition is (0.8 to 1.2): 1, based on the molar ratio of the hydroxyl group of the polyol to the 3-mercaptopropionic acid of the carboxylic acid composition.
  5. 5. A polymerizable composition comprising a polyol carboxylic acid ester produced by the production method according to any one of claims 1 to 4 and an acrylate compound.
  6. 6. The polymerizable composition according to claim 5, wherein the acrylate compound is one or more selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl methacrylate, cyclohexyl acrylate, isooctyl (meth) acrylate, isodecyl acrylate, tetrahydrofurfuryl acrylate, 4-t-butylcyclohexyl acrylate, isobornyl methacrylate, 2-phenoxyethyl acrylate, 1, 6-hexanediol diacrylate, tricyclodecanedimethanol diacrylate, tripropane trimethacrylate, trimethylol propane triacrylate, triallyl isocyanurate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, tricyclodecane dimethanol diacrylate, tripropane trimethacrylate, tripropylene glycol triacrylate, and triallyl isocyanurate.
  7. 7. An adhesive comprising the polymerizable composition according to any one of claims 5 to 6.
  8. 8. The adhesive of claim 7, further comprising a photoinitiator selected from the group consisting of t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy benzoate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4- (2-hydroxyethoxy) -2-methylpropenyl propanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl), 4-benzoyl-4 '-methyl-diphenyl sulfide, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinyl) -1-propanone, 1' - (1, 4-dimethylbenzylidene-2-hydroxy-2-dimethylbenzylidene-2-dimethyl-2-butanone, 2-bis [2, 6-dimethylbenzylidene-2, 2-dimethoxybutanone-2-dimethyl-2-butanone, 3-bis [ 2-methylbenzophenone ] 2-3-fluoro-2-butanone-titanium-2-butanone, methyl benzoate, benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, methyl o-benzoylbenzoate, ethyl 4-dimethylaminobenzoate, isooctyl p-dimethylaminobenzoate, 4' -bis (diethylamino) benzophenone, isopropyl thioxanthone, 2, 4-diethyl thioxanthone, and 2-ethyl anthraquinone.
  9. 9. The adhesive of claim 8, wherein the molar ratio of SH groups in the polyol carboxylic acid ester to c=c groups in the acrylate compound is (0.3-2.0): 1, and the photoinitiator is 0.2-1 wt% of the total mass of the adhesive.

Description

Method for preparing polyol carboxylic acid ester, polymerizable composition and adhesive Technical Field The invention relates to the technical field of adhesives, in particular to a preparation method of polyol carboxylic ester, a polymerizable composition and an adhesive. Background The adhesive has various types and is widely applied to various fields of medical treatment, sanitation, aviation, electronics, printing, optical instruments and the like. The acrylic adhesive is one of the most widely applied adhesive varieties, has many advantages such as good ageing resistance, difficult yellowing, good transparency, can be used for bonding glass and transparent plastics, and has super-strong ultraviolet resistance, ozone resistance, water resistance and the like. The pure acrylic ester system has the problems of oxygen polymerization inhibition, influences the adhesive property, and has longer curing time due to lower initial viscosity. The introduction of mercaptan can not only effectively solve the problem of oxygen polymerization inhibition, but also endow the adhesive with photo-curing property, and can be quickly cured at normal temperature, so that the adhesive can be widely applied to a thermosensitive system, such as the fields of optical lens bonding, nail polish, quantum dot films and the like. In order to solve the problems of low crosslinking density and poor adhesive property of monofunctional and difunctional thiols, the thiol is usually trifunctional or tetrafunctional macromolecular thiol, and the acrylic ester is prepared by the reaction of polyhydric alcohol and mercaptocarboxylic acid such as mercaptopropionic acid. Researchers have conducted many studies on the curing system performance of the polythiol-acrylate system, for example, china patent publication No. CN105384906B reports that the storage stability of adhesives can be improved after the polythiol is modified by isocyanate, china patent publication No. CN114395361B studies on improving the bonding and peeling reusability performance of adhesives, china patent publication No. CN105706264B studies on the influence of acrylic resin residues on the generation of a large amount of outgas during curing or on the deterioration of adhesion and transparency of cured products, and China patent publication No. CN113943420B reports that the heat resistance and moisture resistance of adhesives are improved by non-ester thiols. However, for the adhesive property of the ester polythiol-acrylate system adhesive, the literature report is less, and the adhesive property of the adhesive is critical to the application performance of the adhesive. Disclosure of Invention The application solves the technical problem of providing an adhesive, which has excellent adhesive property. In view of this, the present application provides a process for preparing a polyol carboxylic acid ester comprising: The method comprises the steps of (1) carrying out esterification reaction on polyol and carboxylic acid composition under the action of a catalyst and a water-carrying agent to obtain polyol carboxylic ester; The carboxylic acid composition is selected from 3-mercaptopropionic acid and 3,3 '-thiodipropionic acid, and the content of the 3,3' -thiodipropionic acid in the carboxylic acid composition is 0.01-1wt%. Preferably, the polyol is selected from pentaerythritol or trimethylolpropane. Preferably, the catalyst is selected from an acidic catalyst, the acidic catalyst is selected from one or more of sulfuric acid, hydrochloric acid, phosphoric acid, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trichloroacetic acid, tetrabutyl titanate, zinc acetate, carrier-supported phosphotungstic acid, carrier-supported zirconic acid and carrier-supported heteropolyacid, and the water carrying agent is selected from one or more of petroleum ether, benzene, toluene, xylene, nitrobenzene, chlorobenzene, dichlorobenzene, anisole, diphenyl ether and cyclohexane dichloroethane. Preferably, the catalyst is 0.5-5wt% of the polyol and the carboxylic acid composition, and the water-carrying agent is 0.5-3 times of the total mass of the polyol and the carboxylic acid composition. Preferably, the molar ratio of the polyhydric alcohol to the carboxylic acid composition is (0.8 to 1.2): 1, based on the molar ratio of the hydroxyl group of the polyhydric alcohol to the 3-mercaptopropionic acid of the carboxylic acid composition. The application also provides a polymerizable composition comprising a polyol carboxylic acid ester and an acrylate compound, wherein the polyol carboxylic acid ester is prepared by the preparation method. Preferably, the acrylate compound is selected from one or more of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl methacrylate, cyclohexyl acrylate, isooctyl (meth) acrylate, isodecyl acrylate, tetrahydrofurfuryl acrylate, 4-t-butylcyclohexyl acrylate, isobornyl methacrylate, 2