CN105694000A - Vinyl ester resin and preparation method thereof - Google Patents
Vinyl ester resin and preparation method thereof Download PDFInfo
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- CN105694000A CN105694000A CN201610079032.4A CN201610079032A CN105694000A CN 105694000 A CN105694000 A CN 105694000A CN 201610079032 A CN201610079032 A CN 201610079032A CN 105694000 A CN105694000 A CN 105694000A
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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
The invention relates to vinyl ester resin and a preparation method thereof, belongs to the technical field of polymer materials and aims to solve the problem that existing vinyl ester resin cannot be colorless in appearance while having high toughness.The vinyl ester resin with high toughness and colorless transparent appearance is obtained by: subjecting epoxy resin and 4,4-dihydroxydiphenyl compound to addition polymerization under the action of a particular catalytic system to obtain intermediate A, subjecting the intermediate A and unsaturated carboxylic acid to ring-opening additive reaction, and diluting a final addition product in a reactive diluent to obtain the product, the vinyl ester resin.The vinyl ester resin has both high toughness and colorless transparent appearance.A fiberglass product formed by using the vinyl ester resin provided herein is 10 times longer in service life than unsaturated polyester resin in the same corrosive environment, and a formed product has no change in surface gloss over 36 months of usage; the vinyl ester resin is widely applicable to the fields, such as mold and die, gel coat, fiberglass bathroom accessories, automobile decorations, chemical maintenance and industrial coatings.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to one and there is high tenacity and water white vinyl ester resin and preparation method thereof。
Background technology
Vinyl ester resin refers to that unsaturated double-bond is contained in molecule end, middle skeleton is the special unsaturated polyester resin of one of epoxy resin structural, usually synthesized by esterification by ring opening by epoxy resin and unsaturated monocarboxylic acid, be provided simultaneously with epoxy resin and the feature of two kinds of thermosetting resins of unsaturated polyester resin；Vinyl ester resin remains the basic structure of epoxy resin, has the excellent machinability of unsaturated polyester resin concurrently, after can solidifying under optimum conditions, shows the mechanical performance of excellence, thermostability and chemical resistance etc.。
The epoxy resin containing epoxide group of being prepared by of vinyl ester resin carries out opening under specific catalytic condition with unsaturated carboxylic acid and prepares。Due to the impact by catalyst and reaction condition, preparing product colour jaundice, Hazen colourity is more than 200, and the toughness of products passing through this mode prepared is low, the application of limiting material。
In order to improve the toughness of vinyl ester resin。At first, people select to achieve the goal with saturated dicarboxylic acid Substitute For Partial unsaturated carboxylic acid in course of reaction, but the introducing of saturated dicarboxylic acid can cause the decline of double bond density, affects the state of cure of resin, reduce crosslink density, reduce the decay resistance after resin solidifies。Further, the introducing of saturated dicarboxylic acid cannot reduce the colourity of resin。
For increasing the toughness of vinyl ester resin, patent CN200410017573.1 corrosion-resistant epoxy vinyl ester resin of high molecular and production method thereof have delivered the preparation method passing through tertiary amine or quaternary ammonium salt as the epoxy vinyl ester resin of catalyst, and are produced by the mode of chain extension after first diluting。Although the product of preparation has certain toughness, but this preparation process introduces toluene di-isocyanate(TDI), and side reaction can be caused to increase, and molecule aggregation degree is difficult to control to。
The synthetic method of a patent CN103951791A high toughness epoxy vinyl ester resin has been delivered and has been used part isocyanates Substitute For Partial unsaturated carboxylic acid to carry out same epoxy resin opening under dibutyl tin dilaurate catalysis。Its goods have reached to improve the purpose of vinyl ester resin toughness, but catalyst dibutyltin dilaurate is metallorganic, and human body can be worked the mischief by the residual at end article。
Patent CN200510110522.8 high toughness epoxy vinyl ester resin synthesis technique discloses leading-in end carboxyl liquid nitrile rubber flexible group and strengthens resin toughness with the cooperation of organic monounsaturated dicarboxylic acid。Disclosure satisfy that the demand of the toughness of fiberglass production vinyl ester resin, but due to the Competition that section carboxyl liquid nitrile rubber reacts with epoxy resin with unsaturated carboxylic acid, easily cause final products layering, and the introducing due to nitrile rubber, goods color is reddish black, the serious range of application limiting resin。
Patent KR101406827 is applied to SMC polyurethane-reinforcement vinyl ester resin and preparation elaborates to improve the toughness of resin by vinyl ester resin with the mixing of polyurethane resin and be successfully realized the application in SMC field, but the mixing introducing of polyurethane can cause resin dispersion uneven, affect final molding goods stability。
The synthesis technique of a patent CN200610029812.4 low-styrene-content high-temperature-resistance epoxy vinyl ester resin has invented use amine series catalysts benzyl dimethylamine, benzyltrimethylammonium chloride benzyltriethylammoinium chloride coordinates polymerization inhibitor to prepare vinyl ester resin, but its goods are faint yellow, it is impossible to reach colourless appearance。
Therefore, a kind of New Types of Vinyl Ester Resins of research and development so that it is remain to reach water white outward appearance while there is high tenacity extremely important。
Summary of the invention:
Being unable to reach a kind of colourless apparent condition when high tenacity for current vinyl ester resin, the present invention provides a kind of and not only has high tenacity but also have vinyl ester resin and the preparation method of water white transparency outward appearance。
The first object of the present invention is to provide the vinyl ester resin that a kind of high tenacity is colourless。Described vinyl ester resin has water white transparency outward appearance while having high tenacity。
In vinyl ester resin of the present invention, can be chosen from bisphenol A type epoxy resin (BisphenolAEpoxyResin), bisphenol f type epoxy resin (BisphenolFEpoxyResin) combination of one or more as the epoxy resin of framing structure。
The preparation method that second purpose of the present invention is to provide a kind of above-mentioned vinyl ester resin, step includes the compound and 4 under specific catalyst system and catalyzing effect containing epoxy resin structural, 4-dihydroxydiphenyl compound carries out polyaddition reaction and generates intermediate A, intermediate A and unsaturated carboxylic acid carry out additive reaction, final addition compound product is diluted in response type diluent, and its products therefrom is the vinyl ester resin of the present invention。
Described specific catalyst system and catalyzing is the combination of phosphorus series catalysts, polymerization inhibitor, antioxidant。
Wherein phosphorus series catalysts be three replacement phosphorus, five replace phosphorus any one。
Wherein three replacement phosphorus are any one in triphenyl phosphorus, benzyldiphenyl phosphorus, diphenyl phosphorus chloride, benzyl phenyl phosphorus chloride。
Wherein five replacement phosphorus are any one in BPP, benzyl triethyl ammonium phosphorus chloride, tribenzyl phenyl phosphorus chloride, benzyl trimethyl phosphorus chloride。
Wherein polymerization inhibitor is any one in hydroquinone, catechol, resorcinol。
Wherein antioxidant is any one in phosphorous acid, dimethylphosphite, diethyl phosphite, dibutyl phosphite, vitamin E。
Described 4,4-dihydroxydiphenyl compounds are any one or a few the combination in 4,4'-dihydroxy-diphenyl propanes, 4,4'-dihydroxydiphenyl methane, 4,4'-dihydroxy-diphenyl sulfones, 4,4'-dihydroxydiphenyl second diketone。
Described containing epoxy construction compound, be known by those skilled in the art, can be used for any epoxy resin of the present invention, any one or a few as being chosen from bisphenol A type epoxy resin (BisphenolAEpoxyResin), bisphenol f type epoxy resin (BisphenolFEpoxyResin)。
In preparation method of the present invention, the equivalent proportion containing epoxy construction compound and 4,4-dihydroxydiphenyl compounds is preferably 1:0.05～0.8 and is more preferably 1:0.1～0.6。
Described polyaddition reaction condition is preferably under 120～160 DEG C of conditions and reacts 0.5～4 hour。
The weight average molecular weight of described 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, it is preferred to 1:0.95～1.05。
Described unsaturated carboxylic acid is any one or a few the combination in unsaturated monocarboxylic acid, unsaturated dicarboxylic acid。
Described unsaturated monocarboxylic acid is any one or a few in acrylic acid (Acrylicacid), methacrylic acid (Methacrylicacid)。
Described unsaturated dicarboxylic acid is any one or a few in maleic acid (Maleicacid), fumaric acid (Fumarciacid), itaconic acid (Itaconicacid), adipic acid (Adipicacid), suberic acid (Subericacid), decanedioic acid (SebacicAcid)。
Described ring-opening polymerization condition is preferably under 100～140 DEG C of conditions and reacts 1～6 hour。
The response type diluent of vinyl ester resin of the present invention any one or a few mixture in single unsaturated functional group monomer or many unsaturated functional groups monomer；Wherein response type diluent weight accounts for the 25%～75% of vinyl ester resin gross weight, it is preferred to 30%～70%。
Wherein, single unsaturated functional group monomer, including vinyltoluene (Methylstyrene), styrene (Styrene), 2-phenyl-1-propylene (2-Phenyl-1-propene), acrylic acid (Acrylicacid), acrylic acid methyl ester. (Methylacrylate), glycidyl acrylate (GMA, Glycidylmethacrylate), acrylic acid 2 hydroxy methacrylate (2-Hydroxyethylacrylate), Hydroxypropyl acrylate (Hydroxypropylacrylate), 2-methacrylic acid (Methacrylicacid), methacrylate (Methylpropiolate), glycidyl methacrylate (Glycidylmethacrylate), methacrylic acid 2 hydroxy methacrylate (Hydroxyethylmethacrylate), any one or a few mixture in Hydroxypropyl methacrylate (Hydroxypropylmethacrylate)。
Wherein, many unsaturated functional groups monomer, including the mixture of any one monomer in divinylbenzene (Divinylbenzene), dicyclopentadiene acrylate (dicyclopentadienylacrylate), tripropylene glycol diacrylate (Tripropyleneglycoldiacrylate), trimethylolpropane trimethacrylate (Trimethylolpropanetriacrylate), trimethylolpropane allyl ether (Trimethylolpropanediallylether) or several monomer。
Vinyl ester resin of the present invention can be solidified by peroxide。
Vinyl ester resin of the present invention has colourless feature, and wherein colorless appearance can pass through Hazen chrominance representation, and its Hazen colourity is less than 200。
The weight average molecular weight of vinyl ester resin of the present invention is 3000～10000。
The solidfied material of vinyl ester resin of the present invention has the feature of high tenacity, and wherein high tenacity can be represented by fracture elongation, and its fracture elongation is more than 8%。
The application of vinyl ester resin provided by the invention, described vinyl ester resin can be used for the fields such as mould, gel coat, fiberglass bathroom, automobile decoration, chemical industry maintenance, industrial coating。
The purposes of vinyl ester resin provided by the invention, uses when being used for carrying out artificial marble, light color glass fiber reinforced plastics product molding。Mainly using light color neighbour's benzene-type unsaturated polyester resin for light color glass fiber reinforced plastics product currently on the market, when being applied in corrosive atmosphere, its goods lack the toleration of soda acid, affect mechanical strength, and service life was less than 3 months。And use the glass fiber reinforced plastics product of vinyl ester resin molding provided by the invention, the service life of more than 10 times of unsaturated polyester resin can be reached under identical corrosive atmosphere。
The purposes of vinyl ester resin provided by the invention, it is characterized in that, when corrosion-resistance treatment is carried out for the surface of ceramic sanitary ware sanitary equipment, after using Natural ethylene base ester resin to be shaped, use product surface can turn yellow, turn green through 1 month, reduce surface gloss；And vinyl ester resin provided by the invention, the glossiness of moulded products own is better than Natural ethylene base ester resin formed article, and the use product surface through 36 months will not produce any change。
Detailed description of the invention
In order to further appreciate that the present invention, being described in detail to various aspects of the present invention below, as no specific instructions, each raw material of the present invention all can be obtained by market purchasing；Or the conventional method according to this area prepares。Unless otherwise defined or described herein, the same meaning that all specialties used herein are familiar with scientific words and those skilled in the art。It is understood that these describe simply as further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention。
The invention provides the vinyl ester resin that a kind of high tenacity is colourless, the preparation method of described vinyl ester resin is the compound and 4 under specific catalyst system and catalyzing effect containing epoxy resin structural, 4-dihydroxydiphenyl compound carries out polyaddition reaction and obtains intermediate A, intermediate A and unsaturated carboxylic acid carry out opening, and final addition compound product is diluted in response type diluent。
Specific catalyst system and catalyzing of the present invention is the combination of phosphorus series catalysts, polymerization inhibitor, antioxidant。
Wherein phosphorus series catalysts be three replacement phosphorus, five replace phosphorus any one。
Wherein three replacement phosphorus are any one in triphenyl phosphorus, benzyldiphenyl phosphorus, diphenyl phosphorus chloride, benzyl phenyl phosphorus chloride。
Wherein five replacement phosphorus are any one in BPP, benzyl triethyl ammonium phosphorus chloride, tribenzyl phenyl phosphorus chloride, benzyl trimethyl phosphorus chloride。
Wherein polymerization inhibitor is any one in hydroquinone, catechol, resorcinol。
Wherein antioxidant is any one in phosphorous acid, dimethylphosphite, diethyl phosphite, dibutyl phosphite, vitamin E。
In vinyl ester resin of the present invention, can be any one or a few that select in bisphenol A type epoxy resin (BisphenolAEpoxyResin), bisphenol f type epoxy resin (BisphenolFEpoxyResin) as the epoxy resin of framing structure。
In vinyl ester resin of the present invention 4,4-dihydroxydiphenyl compound is 4,4'-dihydroxy-diphenyl propane, 4,4'-dihydroxydiphenyl methane, 4, any one or a few in 4'-dihydroxy-diphenyl sulfone, 4,4'-dihydroxydiphenyl second diketone, wherein contains the compound and 4 of epoxy resin structural, the equivalent proportion of 4-dihydroxydiphenyl compound is 1:0.05～0.8, it is preferred to 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 any one or a few in unsaturated monocarboxylic acid, unsaturated dicarboxylic acid；Wherein unsaturated monocarboxylic acid selected from methacrylic acid, acrylic acid any one or a few；Unsaturated dicarboxylic acid selected from fumaric acid (Fumaricacid), maleic acid (Maleicacid), itaconic acid (Itaconicacid), adipic acid (Adipicacid), suberic acid (Subericacid), decanedioic acid (SebacicAcid) any one or a few。
Wherein intermediate A and unsaturated carboxylic acid equivalent proportion are 1:0.8～1.2, it is preferred to 1:0.95～1.05。
The response type diluent of vinyl ester resin of the present invention, any one or a few the mixture in single unsaturated functional group monomer or many unsaturated functional groups monomer；Wherein the weight of response type diluent accounts for the 25%～75% of vinyl ester resin gross weight, it is preferred to 30%～70%。
Wherein single unsaturated functional group monomer, including vinyltoluene (Methylstyrene), styrene (Styrene), 2-phenyl-1-propylene (2-Phenyl-1-propene), acrylic acid (Acrylicacid), acrylic acid methyl ester. (Methylacrylate), glycidyl acrylate (GMA, Glycidylmethacrylate), acrylic acid 2 hydroxy methacrylate (2-Hydroxyethylacrylate), Hydroxypropyl acrylate (Hydroxypropylacrylate), 2-methacrylic acid (Methacrylicacid), methacrylate (Methylpropiolate), glycidyl methacrylate (Glycidylmethacrylate), methacrylic acid 2 hydroxy methacrylate (Hydroxyethylmethacrylate), any one or a few mixture in Hydroxypropyl methacrylate (Hydroxypropylmethacrylate)。
Wherein many unsaturated functional groups monomer, including the mixture of any one monomer in divinylbenzene (Divinylbenzene), dicyclopentadiene acrylate (dicyclopentadienylacrylate), tripropylene glycol diacrylate (Tripropyleneglycoldiacrylate), trimethylolpropane trimethacrylate (Trimethylolpropanetriacrylate), trimethylolpropane allyl ether (Trimethylolpropanediallylether) or several monomer。
As required, vinyl ester resin of the present invention can further include available additive, such as reaction suppressor, to suppress the autohemagglutination of monomer, reaction suppressor does not have specific restriction, arbitrarily can realize suppressing the reaction suppressor of monomer autohemagglutination effect all can use, for instance tert-butyl hydroquinone, MEHQ, but not be chosen as limit with above-mentioned；With vinyl ester resin for 100 weight portions for benchmark, the highest consumption of reaction suppressor is up to 0.1 weight portion。
In the preparation method of vinyl ester resin of the present invention, compound and the equivalent proportion of 4,4-dihydroxydiphenyl containing epoxy construction are preferably 1:0.05～0.8, more preferably 1:0.1～0.6。
The described compound containing epoxy construction, can be any one or a few of (BisphenolFEpoxyResin) in bisphenol A type epoxy resin (BisphenolAEpoxyResin), bisphenol f type epoxy resin, but not be chosen as limit with above-mentioned。
In above-mentioned polyaddition reaction step, as long as epoxide can make to include and 4,4-dihydroxydiphenyl carry out the reaction condition of addition polymerization and all can use, its polymeric reaction condition without specific restriction, but preferably 120～160 DEG C react 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 the condition that intermediate A and unsaturated carboxylic acid carry out ring-opening polymerization can be made all can to use, its polymeric reaction condition is without specific restriction, but polyreaction 1～6 hour at being preferably 100～140 DEG C。
Vinyl ester resin of the present invention can be solidified by peroxide compound, wherein, peroxide compound can be methyl ethyl ketone peroxide (MethylEthyKetonePeroxide), benzoyl peroxide (Benzoylperoxide), hydrogen phosphide cumene (Cumenehydroperoxide), but is not chosen as limit with above-mentioned。
Below by specific embodiment and comparative example, to vinyl ester resin of the present invention and preparation method thereof, it is described in detail and describes, so that being better understood from present invention it should be appreciated that, following embodiment is not limiting as the scope of the invention。
Comparative example 1
Using bisphenol A type epoxy resin and methacrylic acid to carry out ring-opening polymerization, its product is diluted with styrene again, obtained bisphenol A-type vinyl ester resin (model RIPOXYR-806, Shanghai Zhaohe High Molecule Co., Ltd. is for selling)。
Comparative example 2
Using bisphenol f type epoxy resin and methacrylic acid to carry out ring-opening polymerization, its product is diluted with styrene again, obtained bisphenol-f type vinyl ester resin。
Embodiment 1
Bisphenol A type epoxy resin and bisphenol-A is used to carry out polyaddition reaction under benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite effect, its product carries out esterification with methacrylic acid again, and its equivalent proportion is bisphenol A epoxide resin: bisphenol-A: methacrylic acid=1.0:0.25:0.75；Its product is diluted with styrene again, obtained vinyl ester resin。
Embodiment 2
Bisphenol A type epoxy resin and Bisphenol F is used to carry out polyaddition reaction under benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite effect, its product carries out esterification with methacrylic acid again, and its equivalent proportion is bisphenol A epoxide resin: Bisphenol F: methacrylic acid=1.0:0.25:0.75；Its product is diluted with styrene again, obtained vinyl ester resin。
Embodiment 3
Bisphenol f type epoxy resin and bisphenol-A is used to carry out polyaddition reaction under benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite effect, its product carries out esterification with methacrylic acid again, and its equivalent proportion is bisphenol A epoxide resin: Bisphenol F: methacrylic acid=1.0:0.25:0.75；Its product is diluted with styrene again, obtained vinyl ester resin。
Embodiment 4
Bisphenol f type epoxy resin and Bisphenol F is used to carry out polyaddition reaction under benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite effect, its product carries out esterification with methacrylic acid again, and its equivalent proportion is bisphenol A epoxide resin: Bisphenol F: methacrylic acid=1.0:0.25:0.75；Its product is diluted with styrene again, obtained vinyl ester resin。
Embodiment 5
Bisphenol A type epoxy resin and bisphenol-A is used to carry out polyaddition reaction under benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite effect, its product carries out esterification with methacrylic acid again, and its equivalent proportion is bisphenol A epoxide resin: bisphenol-A: fumaric acid=1.0:0.25:0.75；Its product is diluted with styrene again, obtained vinyl ester resin。
Embodiment 6
Bisphenol A type epoxy resin and Bisphenol F is used to carry out polyaddition reaction under benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite effect, its product carries out esterification with methacrylic acid again, and its equivalent proportion is bisphenol A epoxide resin: Bisphenol F: fumaric acid=1.0:0.25:0.75；Its product is diluted with styrene again, obtained vinyl ester resin。
Embodiment 7
Bisphenol f type epoxy resin and bisphenol-A is used to carry out polyaddition reaction under benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite effect, its product carries out esterification with methacrylic acid again, and its equivalent proportion is bisphenol F epoxy resin: bisphenol-A: fumaric acid=1.0:0.25:0.75；Its product is diluted with styrene again, obtained vinyl ester resin。
Embodiment 8
Bisphenol f type epoxy resin and Bisphenol F is used to carry out polyaddition reaction under benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite effect, its product carries out esterification with methacrylic acid again, and its equivalent proportion is bisphenol F epoxy resin: Bisphenol F: fumaric acid=1.0:0.25:0.75；Its product is diluted with styrene again, obtained vinyl ester resin。
Embodiment 9
Bisphenol A type epoxy resin and bisphenol-A is used to carry out polyaddition reaction under benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite effect, its product carries out esterification with methacrylic acid again, and its equivalent proportion is bisphenol A epoxide resin: bisphenol-A: methacrylic acid=1.0:0.45:0.55；Its product is diluted with styrene again, obtained vinyl ester resin。
Embodiment 10
Bisphenol A type epoxy resin and Bisphenol F is used to carry out polyaddition reaction under benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite effect, its product carries out esterification with methacrylic acid again, and its equivalent proportion is bisphenol A epoxide resin: Bisphenol F: methacrylic acid=1.0:0.45:0.55；Its product is diluted with styrene again, obtained vinyl ester resin。
Embodiment 11
Bisphenol f type epoxy resin and bisphenol-A is used to carry out polyaddition reaction under benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite effect, its product carries out esterification with methacrylic acid again, and its equivalent proportion is bisphenol F epoxy resin: bisphenol-A: fumaric acid=1.0:0.45:0.55；Its product is diluted with styrene again, obtained vinyl ester resin。
Embodiment 12
Bisphenol f type epoxy resin and Bisphenol F is used to carry out polyaddition reaction under benzyl phenyl phosphorus chloride, resorcinol, dibutyl phosphite effect, its product carries out esterification with methacrylic acid again, and its equivalent proportion is bisphenol F epoxy resin: Bisphenol F: fumaric acid=1.0:0.45:0.55；Its product is diluted with styrene again, obtained vinyl ester resin。
At normal temperatures, in comparative example and embodiment, the vinyl ester resin of preparation, carries out colourity test according to GB/T3143-1982 to liquid resin；Add the compound accelerator of 0.5phr, after mixing and stirring, add the methyl ethyl ketone peroxide (MEKPO of 1.5phr, AkzoNoble company) and it is again stirring for uniformly, then the virgin resin casting plate becoming thickness to be 3mm resin-cast, fracture elongation after test resin normal temperature cure 24 hours, the toughness of evaluating resin, test result is in Table 1。
Table 1
From table 1 it follows that the Hazen colourity of the high tenacity vinyl ester resin of present invention synthesis is below 200, the fracture elongation of the solidfied material of vinyl ester resin is more than 8%。
Above specific embodiments of the invention being described in detail, but it is intended only as example, the present invention is not restricted to particular embodiments described above。To those skilled in the art, any equivalent modifications that the present invention is carried out and replacement are also all among scope of the invention。Therefore, without departing from the impartial conversion made under the principle and scope of the present invention and amendment, all should contain within the scope of the invention。
Claims (12)
1. a vinyl ester resin, described vinyl ester resin is for adopting epoxy resin and 4,4-dihydroxydiphenyl compound carries out polyaddition reaction under specific catalyst system and catalyzing effect and obtains intermediate A, intermediate A and unsaturated carboxylic acid carry out opening, and final addition compound product is diluted in products therefrom in response type diluent。
2. the preparation method of a vinyl ester resin as claimed in claim 1, it is characterized in that, the preparation method of the intermediate A of described vinyl ester resin is the compound containing epoxy resin structural and 4,4-dihydroxydiphenyl compound carries out polyaddition reaction under specific catalyst system and catalyzing effect, reaction temperature is preferably 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, is characterized in that, described epoxy resin is the combination of one or more in bisphenol A type epoxy resin, bisphenol f type epoxy resin。
4. the preparation method of vinyl ester resin as claimed in claim 2, is characterized in that, the equivalent proportion of the described compound containing epoxy resin structural and 4,4-dihydroxydiphenyl compounds is preferably 1:0.05～0.8, more preferably 1:0.1～0.6。
5. the preparation method of vinyl ester resin as claimed in claim 2, is characterized in that, described specific catalyst system and catalyzing is the combination of phosphorus series catalysts, polymerization inhibitor, antioxidant；Wherein phosphorus series catalysts is three replacement phosphorus, five replace any one of phosphorus, wherein three replacement phosphorus are triphenyl phosphorus, benzyldiphenyl phosphorus, diphenyl phosphorus chloride, any one in benzyl phenyl phosphorus chloride, wherein five replacement phosphorus are BPP, benzyl triethyl ammonium phosphorus chloride, tribenzyl phenyl phosphorus chloride, any one in benzyl trimethyl phosphorus chloride, wherein polymerization inhibitor is hydroquinone, catechol, any one in resorcinol, wherein antioxidant is phosphorous acid, dimethylphosphite, diethyl phosphite, dibutyl phosphite, any one in vitamin E。
6. the preparation method of vinyl ester resin as claimed in claim 2, is characterized in that, the weight average molecular weight of the intermediate A of described vinyl ester resin is preferably 3000～8000。
7. the preparation method of a vinyl ester resin as claimed in claim 1, it is characterized in that, the preparation method of described vinyl ester resin is that intermediate A carries out ring-opening polymerization with unsaturated carboxylic acid, and reaction temperature is preferably 100～140 DEG C, and the response time is 1～6 hour。
8. the preparation method of vinyl ester resin as claimed in claim 7, is characterized in that, the equivalent proportion of described intermediate A and unsaturated carboxylic acid is: 1:0.8～1.2, it is preferred to 1:0.95～1.05。
9. the preparation method of vinyl ester resin as claimed in claim 7, is characterized in that, the unsaturated carboxylic acid adopted is selected from the one of which in unsaturated monocarboxylic acid, unsaturated dicarboxylic acid or several combinations。
10. vinyl ester resin as claimed in claim 1, is characterized in that, the response type diluent of described vinyl ester resin is selected from the one of which in single unsaturated functional group monomer or many unsaturated functional groups monomer or several mixture；Wherein the weight of response type diluent accounts for the 25%～75% of vinyl ester resin gross weight, it is preferred to 30%～70%。
11. vinyl ester resin as claimed in claim 1, it is characterized in that, its Hazen chromatic number of described vinyl ester resin is less than 200, and weight average molecular weight is 3000～10000, and the fracture elongation after vinyl ester resin solidification is more than 8%。
12. an application for ethylene polyester resin as claimed in claim 1, described vinyl ester resin can be used for the fields such as mould, gel coat, fiberglass bathroom, automobile decoration, chemical industry maintenance, industrial coating。
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| 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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