CN105694000B - A kind of vinyl ester resin and preparation method thereof - Google Patents
A kind of vinyl ester resin and preparation method thereof Download PDFInfo
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- CN105694000B CN105694000B CN201610079032.4A CN201610079032A CN105694000B CN 105694000 B CN105694000 B CN 105694000B CN 201610079032 A CN201610079032 A CN 201610079032A CN 105694000 B CN105694000 B CN 105694000B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/18—Polyesters; Polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/54—Substitutes for natural stone, artistic materials or the like
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Abstract
A kind of vinyl ester resin and preparation method thereof, belong to technical field of polymer materials, the problem of a kind of colourless apparent condition is unable to reach in the state of high tenacity for current vinyl ester resin, the vinyl ester resin of the present invention is using epoxy resin and 4, 4 dihydroxydiphenyl compounds carry out polyaddition reaction under the effect of specific catalyst system and catalyzing and obtain intermediate A, intermediate A carries out opening with unsaturated carboxylic acid, final addition compound product is diluted in products therefrom in response type diluent, it is as of the invention not only with high tenacity but also with the vinyl ester resin of water white transparency appearance.Use the molding glass fiber reinforced plastics product of vinyl ester resin provided by the invention, 10 times or more of service life of unsaturated polyester resin can be reached under identical corrosive environment, moulded products not will produce any variation by 36 months using product surface glossiness.It can be widely used for the fields such as mold, gel coat, fiberglass bathroom, automobile decoration, chemical industry repair, industrial coating.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of ethylene with high tenacity and water white transparency
Base ester resin and preparation method thereof.
Background technology
Vinyl ester resin refers to that unsaturated double-bond is contained in molecule end, and intermediate skeleton is a kind of spy of epoxy resin structural
Different unsaturated polyester resin is typically synthesized by esterification by ring opening with unsaturated monocarboxylic acid by epoxy resin, is provided simultaneously with ring
The characteristics of two kinds of thermosetting resins of oxygen resin and unsaturated polyester resin；Vinyl ester resin remains the basic knot of epoxy resin
Structure has the excellent machinability of unsaturated polyester resin concurrently, after can curing under optimum conditions, shows excellent mechanicalness
Energy, heat resistance and chemical resistance etc..
The preparation of vinyl ester resin is by the epoxy resin containing epoxy group and unsaturated carboxylic acid in specific catalysis
Under the conditions of carry out opening preparation.Due to being influenced by catalyst and reaction condition, obtained product colour jaundice,
Hazen colorations are more than 200, and toughness of products obtained is low in this way, limits the application of material.
In order to improve the toughness of vinyl ester resin.Initially, people's selection is replaced with saturated dicarboxylic acid during the reaction
It achieves the goal for part unsaturated carboxylic acid, but the introducing of saturated dicarboxylic acid can lead to the decline of double bond density, influence to set
The curing degree of fat reduces crosslink density, reduces the corrosion resistance after resin solidification.Also, the introducing of saturated dicarboxylic acid
The coloration of resin can not be reduced.
For increasing the toughness of vinyl ester resin, a kind of corrosion-resistant epoxy of high molecular weight of patent CN200410017573.1
Vinyl ester resin and its production method have delivered the epoxy vinyl ester resin for being used as catalyst by tertiary amine or quaternary ammonium salt
Preparation method, and produced by way of chain extension after first diluting.Although the product prepared has certain toughness,
This preparation process introduces toluene di-isocyanate(TDI), side reaction can be caused to increase, and molecule aggregation degree is difficult to control.
A kind of synthetic methods of high toughness epoxy vinyl ester resin of patent CN103951791A have been delivered in tin dilaurate
The catalysis of two fourth tin is lower to substitute the progress of part unsaturated carboxylic acid with epoxy resin opening using part isocyanates.It is made
Product have achieved the purpose that improve vinyl ester resin toughness, but catalyst dibutyltin dilaurate is metallorganic, final
The residual of product can do harm to huamn body.
A kind of high toughness epoxy vinyl ester resin synthesis technologies of patent CN200510110522.8 disclose leading-in end carboxylic
Base liquid nitrile rubber flexible group carrys out reinforced resin toughness with the cooperation of organic monounsaturated dicarboxylic acid.It disclosure satisfy that fiberglass production is used
The demand of the toughness of vinyl ester resin, but since section carboxyl liquid nitrile rubber is reacted with epoxy resin with unsaturated carboxylic acid
Competition, be easy to cause final products layering, and due to the introducing of nitrile rubber, product color is in reddish black, seriously
Limit the application range of resin.
Patent KR101406827 is applied to SMC polyurethane-reinforcements vinyl ester resin and its prepares elaborate to pass through vinyl
Ester resin improves the toughness of resin with the mixing of polyurethane resin and is successfully realized the application in the fields SMC, but polyurethane
Mixing introducing resin dispersion can be caused uneven, influence final molding product stability.
A kind of synthesis technologies of low-styrene-content high-temperature-resistance epoxy vinyl ester resin of patent CN200610029812.4
It has invented and has been made using amine system catalyst benzyl dimethylamine, benzyltrimethylammonium chloride benzyltriethylammoinium chloride cooperation polymerization inhibitor
Standby vinyl ester resin, but its product is faint yellow, is unable to reach colourless appearance.
Therefore, a kind of New Types of Vinyl Ester Resins is researched and developed, it is made to remain to reach water white transparency while with high tenacity
Appearance it is extremely important.
Invention content：
A kind of colourless apparent condition is unable to reach in the state of high tenacity for current vinyl ester resin, the present invention
It provides a kind of not only with high tenacity but also the vinyl ester resin with water white transparency appearance and preparation method.
The first object of the present invention is to provide a kind of vinyl ester resin that high tenacity is colourless.The vinyl ester resin exists
With water white transparency appearance while with high tenacity.
In vinyl ester resin of the present invention, the epoxy resin as skeleton structure can be selected from bisphenol-A type ring
One in oxygen resin (Bisphenol A Epoxy Resin), bisphenol f type epoxy resin (Bisphenol F Epoxy Resin)
Kind or several combinations.
Second object of the present invention is to provide a kind of preparation method of above-mentioned vinyl ester resin, and step is included in specific
Compound under catalyst system and catalyzing effect containing epoxy resin structural carries out polyaddition reaction with 4,4- dihydroxydiphenyl compounds
Intermediate A is generated, intermediate A carries out addition reaction with unsaturated carboxylic acid, and final addition compound product is diluted in response type diluent,
Its products therefrom is the vinyl ester resin of the present invention.
The specific catalyst system and catalyzing is the combination of phosphorus series catalysts, polymerization inhibitor, antioxidant.
Wherein phosphorus series catalysts are any one of three substitution phosphorus, five substitution phosphorus.
Wherein three substitution phosphorus are appointing in triphenyl phosphorus, benzyldiphenyl phosphorus, diphenyl phosphorus chloride, benzyl phenyl phosphorus chloride
Meaning is a kind of.
Wherein five substitution phosphorus are benzyltriphenylphosphonium chloride, benzyl triethyl ammonium phosphorus chloride, tribenzyl phenyl phosphorus chloride, benzyl
Any one in trimethyl ammonia chloride phosphorus.
Wherein polymerization inhibitor is any one in hydroquinone, catechol, resorcinol.
Wherein antioxidant is in phosphorous acid, dimethylphosphite, diethyl phosphite, dibutyl phosphite, vitamin E
Any one.
4, the 4- dihydroxydiphenyls compound is 4,4'- dihydroxy-diphenyl propanes, 4,4'- dihydroxydiphenyl first
Any one or the combination of several of them in alkane, 4,4'- dihydroxy-diphenyl sulfones, 4,4'- dihydroxydiphenyl second diketone.
It is described containing epoxy construction compound, be arbitrary asphalt mixtures modified by epoxy resin known to those skilled in the art, for use in the present invention
Fat such as can be selected from bisphenol A type epoxy resin (Bisphenol A Epoxy Resin), bisphenol f type epoxy resin
Any one or a few in (Bisphenol F Epoxy Resin).
In preparation method of the present invention, the equivalent of compound containing epoxy construction and 4,4- dihydroxydiphenyl compounds
Than being preferably 1:0.05~0.8 more preferably 1:0.1~0.6.
The polyaddition reaction condition is preferably to react 0.5~4 hour under the conditions of 120~160 DEG C.
The weight average molecular weight of the intermediate A is preferably 3000~8000.
In preparation method of the present invention, the equivalent proportion of intermediate A and unsaturated carboxylic acid is 1:0.8~1.2, preferably
1:0.95~1.05.
The unsaturated carboxylic acid is any one or a few the group in unsaturated monocarboxylic acid, unsaturated dicarboxylic acid
It closes.
The unsaturated monocarboxylic acid is acrylic acid (Acrylic acid), methacrylic acid (Methacrylic acid)
In any one or a few.
The unsaturated dicarboxylic acid is maleic acid (Maleic acid), fumaric acid (Fumarci acid), itaconic acid
(Itaconic acid), adipic acid (Adipic acid), suberic acid (Suberic acid), decanedioic acid (Sebacic Acid)
In any one or a few.
The ring-opening polymerization condition is preferably to react 1~6 hour under the conditions of 100~140 DEG C.
The response type diluent of vinyl ester resin of the present invention is selected from single unsaturated functional group monomer or how unsaturated
Any one or a few mixture in monomer；Wherein response type diluent weight accounts for vinyl ester resin gross weight
25%~75%, preferably 30%~70%.
Wherein, single unsaturated functional group monomer, including vinyltoluene (Methylstyrene), styrene
(Styrene), 2- phenyl -1- propylene (2-Phenyl-1-propene), acrylic acid (Acrylic acid), methyl acrylate
(Methyl acrylate), glycidyl acrylate (GMA, Glycidyl methacrylate), 2 hydroxy methacrylate of acrylic acid
(2-Hydroxyethyl acrylate), hydroxypropyl acrylate (Hydroxypropyl acrylate), 2- methacrylic acids
(Methacrylic acid), methacrylate (Methyl propiolate), glycidyl methacrylate
(Glycidyl methacrylate), 2 hydroxy methacrylate of methacrylic acid (Hydroxyethyl methacrylate), methyl-prop
Any one or a few mixture in olefin(e) acid hydroxypropyl acrylate (Hydroxy propyl methacrylate).
Wherein, how unsaturated monomer, including divinylbenzene (Divinylbenzene), dicyclopentadiene propylene
Acid esters (dicyclopentadienyl acrylate), tripropylene glycol diacrylate (Tripropylene glycol
Diacrylate), trimethylolpropane trimethacrylate (Trimethylolpropane triacrylate), trihydroxy methyl third
The mixing of any one monomer or several monomers in alkane diallyl ether (Trimethylolpropane diallylether)
Object.
Vinyl ester resin of the present invention can be cured by peroxide.
Vinyl ester resin of the present invention have colourless feature, wherein colorless appearance can by Hazen chrominance representations,
Its Hazen coloration is less than 200.
The weight average molecular weight of vinyl ester resin of the present invention is 3000~10000.
There is the solidfied material of vinyl ester resin of the present invention the feature of high tenacity, wherein high tenacity can be prolonged by fracture
Rate expression is stretched, fracture elongation is more than 8%.
The application of vinyl ester resin provided by the invention, the vinyl ester resin can be used for mold, gel coat, fiberglass
The fields such as bathroom, automobile decoration, chemical industry repair, industrial coating.
The purposes of vinyl ester resin provided by the invention, for carrying out artificial marble, the molding of light color glass fiber reinforced plastics product
When use.Light color m-phthalate unsaturated polyester resin is mainly used for light color glass fiber reinforced plastics product currently on the market, when being applied to
When in corrosive environment, product lacks the tolerance of soda acid, influences mechanical strength, and service life is less than 3 months.And use this
The molding glass fiber reinforced plastics product of vinyl ester resin provided is provided, unsaturated polyester (UP) tree can be reached under identical corrosive environment
10 times or more of service life of fat.
The purposes of vinyl ester resin provided by the invention, which is characterized in that carried out for the surface of ceramic sanitary ware sanitary ware
When corrosion-resistance treatment, after being molded using Natural ethylene base ester resin, it can be turned yellow using product surface by 1 month, greening,
Reduce surface gloss；And vinyl ester resin provided by the invention, moulded products glossiness itself are better than Natural ethylene base ester
Resin formed article not will produce any variation by 36 months using product surface.
Specific implementation mode
In order to further appreciate that the present invention, it is described in detail to various aspects of the present invention below, unless specific instructions, this hair
Bright each raw material can be obtained by market purchasing；Or it is prepared according to the conventional method of this field.Unless otherwise fixed
Justice or explanation, all professional and scientific terms used herein and meaning phase known to those skilled in the art
Together.It is understood that these descriptions are only the feature and advantage further illustrated the present invention, rather than to right of the present invention
It is required that limitation.
The present invention provides a kind of vinyl ester resin that high tenacity is colourless, the preparation method of the vinyl ester resin is
Compound under the effect of specific catalyst system and catalyzing containing epoxy resin structural carries out addition with 4,4- dihydroxydiphenyl compounds and gathers
Intermediate A is reacted to obtain in conjunction, and intermediate A carries out opening with unsaturated carboxylic acid, and final addition compound product is diluted in response type
In diluent.
Specific catalyst system and catalyzing of the present invention is the combination of phosphorus series catalysts, polymerization inhibitor, antioxidant.
Wherein phosphorus series catalysts are any one of three substitution phosphorus, five substitution phosphorus.
Wherein three substitution phosphorus are appointing in triphenyl phosphorus, benzyldiphenyl phosphorus, diphenyl phosphorus chloride, benzyl phenyl phosphorus chloride
Meaning is a kind of.
Wherein five substitution phosphorus are benzyltriphenylphosphonium chloride, benzyl triethyl ammonium phosphorus chloride, tribenzyl phenyl phosphorus chloride, benzyl
Any one in trimethyl ammonia chloride phosphorus.
Wherein polymerization inhibitor is any one in hydroquinone, catechol, resorcinol.
Wherein antioxidant is in phosphorous acid, dimethylphosphite, diethyl phosphite, dibutyl phosphite, vitamin E
Any one.
In vinyl ester resin of the present invention, the epoxy resin as skeleton structure can be selection bisphenol-A type ring
In oxygen resin (Bisphenol A Epoxy Resin), bisphenol f type epoxy resin (Bisphenol F Epoxy Resin)
Any one or a few.
4,4- dihydroxydiphenyl compounds in vinyl ester resin of the present invention are 4,4'- dihydroxydiphenyls
Appointing in propane, 4,4'- dihydroxydiphenyls methane, 4,4'- dihydroxy-diphenyl sulfones, 4,4'- dihydroxydiphenyl second diketone
Meaning is one or more of, wherein the equivalent proportion of the compound containing epoxy resin structural and 4,4- dihydroxydiphenyl compounds is 1:
0.05~0.8, preferably 1:0.1~0.6.
The weight average molecular weight of intermediate A of the present invention is preferably 3000~8000.
Unsaturated carboxylic acid in vinyl ester resin of the present invention is selected from unsaturated monocarboxylic acid, unsaturated binary carboxylic
Any one or a few in acid；Wherein unsaturated monocarboxylic acid be selected from methacrylic acid, acrylic acid any one or a few；
Unsaturated dicarboxylic acid is selected from fumaric acid (Fumaric acid), maleic acid (Maleic acid), itaconic acid (Itaconic
Acid), any one of adipic acid (Adipic acid), suberic acid (Suberic acid), decanedioic acid (Sebacic Acid)
Or it is several.
Wherein intermediate A and unsaturated carboxylic acid equivalent proportion are 1:0.8~1.2, preferably 1:0.95~1.05.
The response type diluent of vinyl ester resin of the present invention, selected from single unsaturated functional group monomer or how unsaturated
Any one or a few mixture in monomer；The weight of wherein response type diluent accounts for vinyl ester resin gross weight
25%~75%, preferably 30%~70%.
Wherein single unsaturated functional group monomer, including vinyltoluene (Methylstyrene), styrene (Styrene),
2- phenyl -1- propylene (2-Phenyl-1-propene), acrylic acid (Acrylic acid), methyl acrylate (Methyl
Acrylate), glycidyl acrylate (GMA, Glycidyl methacrylate), 2 hydroxy methacrylate (2- of acrylic acid
Hydroxyethyl acrylate), hydroxypropyl acrylate (Hydroxypropyl acrylate), 2- methacrylic acids
(Methacrylic acid), methacrylate (Methyl propiolate), glycidyl methacrylate
(Glycidyl methacrylate), 2 hydroxy methacrylate of methacrylic acid (Hydroxyethyl methacrylate), methyl-prop
Any one or a few mixture in olefin(e) acid hydroxypropyl acrylate (Hydroxy propyl methacrylate).
Wherein how unsaturated monomer, including divinylbenzene (Divinylbenzene), dicyclopentadiene propylene
Acid esters (dicyclopentadienyl acrylate), tripropylene glycol diacrylate (Tripropylene glycol
Diacrylate), trimethylolpropane trimethacrylate (Trimethylolpropane triacrylate), trihydroxy methyl third
The mixing of any one monomer or several monomers in alkane diallyl ether (Trimethylolpropane diallylether)
Object.
As needed, vinyl ester resin of the present invention can further include available additive, such as reaction suppression
Preparation arbitrarily may be implemented to inhibit the anti-of monomer autohemagglutination effect to inhibit the autohemagglutination of monomer, reaction suppressor not to have specific limitation
It answers inhibitor to can be used, such as tert-butyl hydroquinone, p-hydroxyanisole, but is not selected as limit with above-mentioned；With ethylene
Base ester resin is on the basis of 100 parts by weight, reaction suppressor highest dosage is up to 0.1 parts by weight.
In the preparation method of vinyl ester resin of the present invention, the compound containing epoxy construction and 4,4- dihydroxy hexichol
The equivalent proportion of base is preferably 1:0.05~0.8, more preferably 1:0.1~0.6.
The compound containing epoxy construction can be bisphenol A type epoxy resin (Bisphenol A Epoxy
Resin), in bisphenol f type epoxy resin (Bisphenol F Epoxy Resin) any one or a few, but not more than
Selection is stated to be limited.
In above-mentioned polyaddition reaction step, as long as it includes epoxide and 4,4- dihydroxy hexichol that can make
The reaction condition that base carries out addition polymerization all can be used, and polymeric reaction condition is without specific limitation, but preferably 120~160 DEG C anti-
It answers 0.5~4 hour.
In the preparation method of vinyl ester resin of the present invention, the equivalent proportion of intermediate A and unsaturated carboxylic acid is preferably
1：0.8~1.2, more preferably 1：0.95~1.05.
In above-mentioned ring-opening polymerization step, as long as intermediate A can be made to carry out ring-opening polymerisation with unsaturated carboxylic acid
The condition of reaction all can be used, and polymeric reaction condition is without specific limitation, but polymerisation 1~6 at preferably 100~140 DEG C
Hour.
Vinyl ester resin of the present invention can be cured by peroxide compound, wherein peroxide compound can
Be methyl ethyl ketone peroxide (Methyl Ethy Ketone Peroxide), benzoyl peroxide (Benzoyl peroxide),
Cumyl hydroperoxide (Cumene hydroperoxide), but it is not selected as limit with above-mentioned.
Vinyl ester resin of the present invention and preparation method thereof is carried out detailed below by specific embodiment and comparative example
Introduction and description, for a better understanding of the content of present invention it should be appreciated that following embodiments are not intended to limit this hair
Bright range.
Comparative example 1
Ring-opening polymerization is carried out using bisphenol A type epoxy resin and methacrylic acid, reaction product is again with styrene
Dilution, (model RIPOXY R-806, Shanghai Zhaohe High Molecule Co., Ltd. supply obtained bisphenol A-type vinyl ester resin
It sells).
Comparative example 2
Ring-opening polymerization is carried out using bisphenol f type epoxy resin and methacrylic acid, reaction product is again with styrene
Dilution, obtained bisphenol-f type vinyl ester resin.
Embodiment 1
It is acted in benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite using bisphenol A type epoxy resin and bisphenol-A
Lower carry out polyaddition reaction, product carry out esterification with methacrylic acid again, and equivalent proportion is bisphenol A epoxide resin：
Bisphenol-A：Methacrylic acid=1.0:0.25:0.75；Its reaction product is diluted with styrene again, obtained vinyl esters tree
Fat.
Embodiment 2
It is acted in benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite using bisphenol A type epoxy resin and Bisphenol F
Lower carry out polyaddition reaction, product carry out esterification with methacrylic acid again, and equivalent proportion is bisphenol A epoxide resin：
Bisphenol F：Methacrylic acid=1.0:0.25:0.75；Its reaction product is diluted with styrene again, obtained vinyl esters tree
Fat.
Embodiment 3
It is acted in benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite using bisphenol f type epoxy resin and bisphenol-A
Lower carry out polyaddition reaction, product carry out esterification with methacrylic acid again, and equivalent proportion is bisphenol A epoxide resin：
Bisphenol F：Methacrylic acid=1.0:0.25:0.75；Its reaction product is diluted with styrene again, obtained vinyl esters tree
Fat.
Embodiment 4
It is acted in benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite using bisphenol f type epoxy resin and Bisphenol F
Lower carry out polyaddition reaction, product carry out esterification with methacrylic acid again, and equivalent proportion is bisphenol A epoxide resin：
Bisphenol F：Methacrylic acid=1.0:0.25:0.75；Its reaction product is diluted with styrene again, obtained vinyl esters tree
Fat.
Embodiment 5
It is acted in benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite using bisphenol A type epoxy resin and bisphenol-A
Lower carry out polyaddition reaction, product carry out esterification with methacrylic acid again, and equivalent proportion is bisphenol A epoxide resin：
Bisphenol-A：Fumaric acid=1.0:0.25:0.75；Its reaction product is diluted with styrene again, obtained vinyl ester resin.
Embodiment 6
It is acted in benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite using bisphenol A type epoxy resin and Bisphenol F
Lower carry out polyaddition reaction, product carry out esterification with methacrylic acid again, and equivalent proportion is bisphenol A epoxide resin：
Bisphenol F：Fumaric acid=1.0:0.25:0.75；Its reaction product is diluted with styrene again, obtained vinyl ester resin.
Embodiment 7
It is acted in benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite using bisphenol f type epoxy resin and bisphenol-A
Lower carry out polyaddition reaction, product carry out esterification with methacrylic acid again, and equivalent proportion is bisphenol F epoxy resin：
Bisphenol-A：Fumaric acid=1.0:0.25:0.75；Its reaction product is diluted with styrene again, obtained vinyl ester resin.
Embodiment 8
It is acted in benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite using bisphenol f type epoxy resin and Bisphenol F
Lower carry out polyaddition reaction, product carry out esterification with methacrylic acid again, and equivalent proportion is bisphenol F epoxy resin：
Bisphenol F：Fumaric acid=1.0:0.25:0.75；Its reaction product is diluted with styrene again, obtained vinyl ester resin.
Embodiment 9
It is acted in benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite using bisphenol A type epoxy resin and bisphenol-A
Lower carry out polyaddition reaction, product carry out esterification with methacrylic acid again, and equivalent proportion is bisphenol A epoxide resin：
Bisphenol-A：Methacrylic acid=1.0:0.45:0.55；Its reaction product is diluted with styrene again, obtained vinyl esters tree
Fat.
Embodiment 10
It is acted in benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite using bisphenol A type epoxy resin and Bisphenol F
Lower carry out polyaddition reaction, product carry out esterification with methacrylic acid again, and equivalent proportion is bisphenol A epoxide resin：
Bisphenol F：Methacrylic acid=1.0:0.45:0.55；Its reaction product is diluted with styrene again, obtained vinyl esters tree
Fat.
Embodiment 11
It is acted in benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite using bisphenol f type epoxy resin and bisphenol-A
Lower carry out polyaddition reaction, product carry out esterification with methacrylic acid again, and equivalent proportion is bisphenol F epoxy resin：
Bisphenol-A：Fumaric acid=1.0:0.45:0.55；Its reaction product is diluted with styrene again, obtained vinyl ester resin.
Embodiment 12
It is acted in benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite using bisphenol f type epoxy resin and Bisphenol F
Lower carry out polyaddition reaction, product carry out esterification with methacrylic acid again, and equivalent proportion is bisphenol F epoxy resin：
Bisphenol F：Fumaric acid=1.0:0.45:0.55；Its reaction product is diluted with styrene again, obtained vinyl ester resin.
At normal temperatures, the vinyl ester resin prepared in comparative example and embodiment, according to GB/T 3143-1982 to liquid
Resin carries out coloration test；The compound accelerating agent for adding 0.5phr, after being mixed evenly, adds the peroxidating first of 1.5phr
Ethyl ketone (MEKPO, Akzo Noble companies) is simultaneously again stirring for uniformly, then pours resin-cast at the pure resin that thickness is 3mm
Note plate, the fracture elongation after test resin normal temperature cure 24 hours evaluates the toughness of resin, test result is shown in Table 1.
Table 1
From table 1 it follows that the Hazen colorations for the high tenacity vinyl ester resin that the present invention synthesizes are below 200, second
The fracture elongation of the solidfied material of alkenyl esters resin is more than 8%.
Specific embodiments of the present invention are described in detail above, but it is intended only as example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Instead of also all among scope of the invention.Therefore, the impartial conversion done in the case where not departing from the principle and scope of the present invention and
Modification, all should be contained within the scope of the invention.
Claims (15)
1. a kind of vinyl ester resin, the vinyl ester resin is using epoxy resin and 4,4- dihydroxydiphenyl compounds
Polyaddition reaction is carried out under the effect of specific catalyst system and catalyzing and obtains intermediate A, and intermediate A carries out open loop addition with unsaturated carboxylic acid
Reaction, final addition compound product are diluted in products therefrom in response type diluent.
2. a kind of preparation method of vinyl ester resin as described in claim 1, characterized in that the vinyl ester resin
The preparation method of intermediate A is for the compound containing epoxy resin structural with 4,4- dihydroxydiphenyls compound in specific catalytic body
System's effect is lower to carry out polyaddition reaction, and reaction temperature is 120~160 DEG C, and the time is 0.5~4 hour.
3. the preparation method of vinyl ester resin as claimed in claim 2, characterized in that the epoxy resin is selected from bis-phenol
One or more of combination in A types epoxy resin, bisphenol f type epoxy resin.
4. the preparation method of vinyl ester resin as claimed in claim 2, characterized in that described containing epoxy resin structural
The equivalent proportion of compound and 4,4- dihydroxydiphenyl compounds is 1:0.05~0.8.
5. the preparation method of vinyl ester resin as claimed in claim 2, characterized in that described containing epoxy resin structural
The equivalent proportion of compound and 4,4- dihydroxydiphenyl compounds is 1:0.1~0.6.
6. the preparation method of vinyl ester resin as claimed in claim 2, characterized in that the specific catalyst system and catalyzing is phosphorus system
The combination of catalyst, polymerization inhibitor, antioxidant；Wherein phosphorus series catalysts are any one of three substitution phosphorus, five substitution phosphorus, wherein
Three substitution phosphorus are any one in triphenyl phosphorus, benzyldiphenyl phosphorus, diphenyl phosphorus chloride, benzyl phenyl phosphorus chloride, wherein
Five substitution phosphorus are benzyltriphenylphosphonium chloride, benzyl triethyl ammonium phosphorus chloride, tribenzyl phenyl phosphorus chloride, benzyl trimethyl phosphorus chloride
In any one, wherein polymerization inhibitor is hydroquinone, catechol, any one in resorcinol, wherein antioxidant
For any one in phosphorous acid, dimethylphosphite, diethyl phosphite, dibutyl phosphite, vitamin E.
7. the preparation method of vinyl ester resin as claimed in claim 2, characterized in that in the vinyl ester resin
The weight average molecular weight of mesosome A is preferably 3000~8000.
8. a kind of preparation method of vinyl ester resin as described in claim 1, characterized in that the vinyl ester resin
Preparation method is that intermediate A and unsaturated carboxylic acid carry out ring-opening polymerization, and reaction temperature is 100~140 DEG C, and the reaction time is
1~6 hour.
9. the preparation method of vinyl ester resin as claimed in claim 8, characterized in that the intermediate A and unsaturation
The equivalent proportion of carboxylic acid is：1:0.8~1.2.
10. the preparation method of vinyl ester resin as claimed in claim 8, characterized in that the intermediate A and unsaturation
The equivalent proportion of carboxylic acid is：1:0.95~1.05.
11. the preparation method of vinyl ester resin as claimed in claim 8, characterized in that used unsaturated carboxylic acid choosing
From in unsaturated monocarboxylic acid, unsaturated dicarboxylic acid one of which or several combinations.
12. vinyl ester resin as described in claim 1, characterized in that the response type diluent of the vinyl ester resin
One of which in single unsaturated functional group monomer or how unsaturated monomer or several mixtures；Wherein react
The weight of type diluent accounts for the 25%~75% of vinyl ester resin gross weight.
13. vinyl ester resin as described in claim 1, characterized in that the response type diluent of the vinyl ester resin
One of which in single unsaturated functional group monomer or how unsaturated monomer or several mixtures；Wherein react
The weight of type diluent accounts for the 30%~70% of vinyl ester resin gross weight.
14. vinyl ester resin as described in claim 1, characterized in that its Hazen chromatic number of the vinyl ester resin is less than
200, weight average molecular weight is 3000~10000, and the fracture elongation after vinyl ester resin solidification is more than 8%.
15. a kind of application of vinyl ester resin as described in claim 1, the vinyl ester resin can be used for mold, glue
Clothing, fiberglass bathroom, automobile decoration, chemical industry repair, industrial coating field.
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| CN107312160B (en) * | 2017-06-28 | 2020-05-08 | 常州华日新材有限公司 | Composition of epoxy vinyl ester resin and formed product |
| CN112094489A (en) * | 2020-11-18 | 2020-12-18 | 佛山市南海乐宁卫浴设备有限公司 | Light high-toughness artificial stone bathroom product and preparation method thereof |
| CN112848628B (en) * | 2021-01-11 | 2023-02-03 | 贺雪宁 | Preparation method and application of high-strength glass fiber reinforced plastic composite board with good corrosion resistance |
| CN113441073A (en) * | 2021-07-30 | 2021-09-28 | 湖南吉晟防腐保温工程有限公司 | Novel environment-friendly special heavy-duty anticorrosive paint and manufacturing process thereof |
| CN114395093A (en) * | 2022-03-02 | 2022-04-26 | 常州天马集团有限公司（原建材二五三厂） | Thickening epoxy vinyl ester resin for prepreg composite material and preparation method thereof |
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| JPS62209121A (en) * | 1986-03-11 | 1987-09-14 | Showa Highpolymer Co Ltd | Production of curable resin |
| JP3360758B2 (en) * | 1993-10-14 | 2002-12-24 | 大日本インキ化学工業株式会社 | Method for producing resin composition for artificial marble and resin composition for artificial marble |
| GB0303257D0 (en) * | 2003-02-13 | 2003-03-19 | Hexcel Composites Ltd | Improvements in or relating to thermosetting resin compositions |
| CN100358931C (en) * | 2005-11-18 | 2008-01-02 | 华东理工大学华昌聚合物有限公司 | Tech. for synthesizing high toughness epoxy vinyl ester resin |
| CN100467512C (en) * | 2006-09-29 | 2009-03-11 | 华东理工大学华昌聚合物有限公司 | Technique for synthesizing resin of epoxy vinyl ester with low exothermal peak |
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| 拉挤用乙烯基酯树脂的固化行为及固化反应动力学研究;李建国;《中国优秀博硕士学位论文全文数据库（硕士） 工程科技Ⅰ辑》;20040315;第16页 * |
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Address after: 8333 Songze Avenue, Qingpu Industrial Park, Qingpu District, Shanghai, 201707 Patentee after: Lisennoco Polymer Materials (Shanghai) Co.,Ltd. Address before: 201707 No. 8333, Songze Avenue, Industrial Park, Qingpu District, Shanghai Patentee before: SHANGHAI SHOWA HIGHPOLYMER CO.,LTD. |