CN107090262A - A kind of good composition epoxy resin of transparency and its applied in automotive field - Google Patents

A kind of good composition epoxy resin of transparency and its applied in automotive field Download PDF

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Publication number
CN107090262A
CN107090262A CN201710463184.9A CN201710463184A CN107090262A CN 107090262 A CN107090262 A CN 107090262A CN 201710463184 A CN201710463184 A CN 201710463184A CN 107090262 A CN107090262 A CN 107090262A
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parts
epoxy resin
curing agent
organic clay
light stabilizer
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CN107090262B (en
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杨丽燕
吴平章
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Shanghai Dou Wei Photovoltaic Science And Technology Ltd
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Shanghai Dou Wei Photovoltaic Science And Technology Ltd
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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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a kind of transparency good composition epoxy resin, calculates by weight, including following components：30~70 parts of bisphenol A type epoxy resin；10 35 parts of organic clay modified epoxy；0.1 2 parts of light stabilizer；0.1 2 parts of antioxidant；10~25 parts of curing agent；0.1~15 part of diluent；20~40 parts of filler；0.5~1.5 part of coupling agent；0.5~3 part of thixotropic agent；Wherein, organic clay described in the organic clay modified epoxy is 2,4,6 trihydroxybenzoic acids of grafting dodecyl sodium sulfate and the complex composition of acrylic acid attapulgite；The curing agent is polysulfide alcohols curing agent and modified amine curing agent；The light stabilizer is composite polymer light stabilizer, the composite polymer light stabilizer is the grafting sulfonic acid of 2 phenylbenzimidazol 5 and 2,2' dihydroxy 4, the polyvinyl chloride of 4' dimethoxy-benzophenones and fumaric acid 2,2,6,6 tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters copolymers.

Description

A kind of good composition epoxy resin of transparency and its applied in automotive field
Technical field
The present invention relates to field of adhesive technology, in particular it relates to a kind of good epoxy composite of transparency Thing and its applied in automotive field.
Background technology
Epoxy resin refers to the epoxy radicals containing two or more, has with aliphatic, alicyclic or aromatic series etc. Machine compound is skeleton and can form the thermosetting polymer polymer with body shape network structure by the reaction of epoxy radicals.Gu Epoxy resin after change has good physics, chemical property, and its surface to metal and nonmetallic materials has excellent viscous Intensity is connect, dielectric properties are good, and set shrinkage factor is small, and product size stability is good, and hardness is high, it is soft preferable towards property, to alkali and greatly Partial solvent is stable.
Epoxyn is widely used, and has excellent cementitiousness to multiple material, high, electric with adhesion strength Function admirable, shrinkage factor are low, dimensionally stable, strong weatherability the advantages of.Many sulfydryl curing agent collocation Tertiary amine accelerators and asphalt mixtures modified by epoxy resin Fat uses cooperatively and shows water white transparency and the fast advantage of curing rate.
Water white transparency fast-curing epoxy resin adhesive is a kind of larger specific epoxy adhesive of market demand, main To be applied to optical instrument, optical fiber, windshield, the solar cell such as microscope, projecting apparatus pull, jade handicraft Deng to transparency requirement is higher, hardening time requires shorter field.
The water white transparency fast-curing epoxy resin adhesive weatherability and photo and thermal stability of current domestic production are poor, general Store-through the phenomenon such as is turned white in xanthochromia.
In addition, light stabilizer also has the following disadvantages：(1) it is poor with polymer compatibility, it is impossible to uniform point in the polymer Dissipate, cause the mechanical properties decrease of polymer；(2) it is unstable to photo-thermal, failed during processing or use；(3) volatile, Migrate, ooze out and extracted by medium, is lost in during processing or use；(4) occur with polymer, other additives anti- Should, cause its ageing resistace to fail.
Therefore, the present invention provides a kind of adhesion strength height, hardening time is short, weatherability is strong, visible light transmissivity is high, comprehensive The composition epoxy resin of excellent performance.
The content of the invention
In view of the above-mentioned problems, the present invention provides a kind of transparency good composition epoxy resin, calculate by weight, including Following components：30~70 parts of bisphenol A type epoxy resin；10-35 parts of organic clay modified epoxy；0.1-2 parts of light stabilizer； 0.1-2 parts of antioxidant；10~25 parts of curing agent；0.1~15 part of diluent；20~40 parts of filler；0.5~1.5 part of coupling agent；Touch Become 0.5~3 part of agent；
Wherein, organic clay described in the organic clay modified epoxy is the 2,4 of grafting dodecyl sodium sulfate, The complex composition of 6- trihydroxybenzoic acids and acrylic acid attapulgite；The curing agent is polysulfide alcohols curing agent and modified amine Curing agent；The light stabilizer is composite polymer light stabilizer, and the composite polymer light stabilizer is grafting 2- benzene The polyvinyl chloride of base benzimidazole -5- sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and fumaric acid 2,2,6, 6- tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters copolymers.
In one embodiment, calculate by weight, including following components：35~60 parts of bisphenol A type epoxy resin；Have Clay modified epoxy resin 15-35 parts of machine；0.5-1.5 parts of light stabilizer；0.5-1.5 parts of antioxidant；10~25 parts of curing agent；It is dilute Release 2~10 parts of agent；20~30 parts of filler；0.5~1 part of coupling agent；0.5~2 part of thixotropic agent.
In one embodiment, 2-Phenylbenzimidazole -5- is grafted described in the composite polymer light stabilizer The polyvinyl chloride of sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and the tetramethyl piperazine of fumaric acid 2,2,6,6- The weight ratio of pyridine alcohol poly glycol monomethyl ether dibasic acid esters is 1：(0.1-1).
In one embodiment, 2-Phenylbenzimidazole -5- is grafted described in the composite polymer light stabilizer The polyvinyl chloride of sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and the tetramethyl piperazine of fumaric acid 2,2,6,6- The weight ratio of pyridine alcohol poly glycol monomethyl ether dibasic acid esters is 1：(0.5-1).
In one embodiment, the preparing raw material of the polysulfide alcohols curing agent include 2,6-TDI, 3- mercaptopropionic acid, Tripentaerythritol.
In one embodiment, the modified amine curing agent preparing raw material includes diethylenetriamine, thiocarbamide.
In one embodiment, the weight of the bisphenol A type epoxy resin and the organic clay modified epoxy Than for (1.5-3)：1.
In one embodiment, the weight of the bisphenol A type epoxy resin and the organic clay modified epoxy Than for 2：1.
In one embodiment, the good composition epoxy resin application of the transparency and automotive field.
Another aspect of the present invention provides a kind of preparation method of the good composition epoxy resin of transparency, including following step Suddenly：
Bisphenol A type epoxy resin, organic clay modified epoxy are added in reactor by weight, 35 are warming up to DEG C, 0.5h is stirred, filler is added, continues to stir 0.5h, then adds light stabilizer, antioxidant, curing agent, diluent, coupling Agent, thixotropic agent, stir 1-3h, obtain the photovoltaic cutting epoxide-resin glue.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to described further below.
Embodiment
The participation in the election detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention The identical implication that technical staff is generally understood that.When there is contradiction, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this Phrase will make claim be closed, it is not included the material in addition to materials of those descriptions, but relative normal Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme, It is only limited to the key element described in the clause；Other key elements are not excluded outside as the overall claim.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit During the Range Representation that choosing value is limited, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope All scopes that any pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end Value and all integers and fraction within the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " any It is a kind of " refer to that the item or event that describe thereafter may or may not occur, and the description include situation that event occurs and The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, represents that the present invention is not limited to this specific Quantity, includes the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.In some examples, approximately Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope is limited can be with Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
In addition, the indefinite article " one kind " and " one " before key element of the present invention or component are to key element or the quantitative requirement of component (i.e. occurrence number) unrestriction.Therefore " one " or " one kind " should be read as including one or at least one, and odd number The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
" polymer " means by the polymerizable compound prepared by the monomer that polymerize identical or different type.Generic term " polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " EVA ".
" EVA " means by polymerizeing polymer prepared by least two different monomers.Generic term " EVA " includes (its is general with term " terpolymer " for term " copolymer " (it is typically to refer to the polymer prepared by two kinds of different monomers) To refer to the polymer prepared by three kinds of different monomers).It also includes the polymer by polymerizeing more kinds of monomers and manufacturing. " blend " means that two or more polymer passes through polymer formed by physics or chemistry the common mixing of method.
The present invention provides a kind of transparency good composition epoxy resin, calculates by weight, including following components：Bis-phenol 30~70 parts of A types epoxy resin；10-35 parts of organic clay modified epoxy；0.1-2 parts of light stabilizer；Antioxidant 0.1-2 Part；10~25 parts of curing agent；0.1~15 part of diluent；20~40 parts of filler；0.5~1.5 part of coupling agent；Thixotropic agent 0.5~3 Part；
Wherein, organic clay described in the organic clay modified epoxy is the 2,4 of grafting dodecyl sodium sulfate, The complex composition of 6- trihydroxybenzoic acids and acrylic acid attapulgite；The curing agent is polysulfide alcohols curing agent and modified amine Curing agent；The light stabilizer is composite polymer light stabilizer, and the composite polymer light stabilizer is grafting 2- benzene The polyvinyl chloride of base benzimidazole -5- sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and fumaric acid 2,2,6, 6- tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters copolymers.
In one embodiment, calculate by weight, including following components：35~60 parts of bisphenol A type epoxy resin；Have Clay modified epoxy resin 15-35 parts of machine；0.5-1.5 parts of light stabilizer；0.5-1.5 parts of antioxidant；10~25 parts of curing agent；It is dilute Release 2~10 parts of agent；20~30 parts of filler；0.5~1 part of coupling agent；0.5~2 part of thixotropic agent.
Bisphenol A type epoxy resin
Epoxy resin refers to the resin compound at least containing two reactive epoxy groups in those molecules.Epoxy resin Have the excellent properties of many protrusions after cured, such as various materials are particularly it is very strong to the adhesion of metal, have very strong resistance to Chemical corrosivity, mechanical strength are very high, electrical insulating property is good, corrosion-resistant etc..In addition, epoxy resin can be in comparatively wide temperature model Interior solidification is enclosed, and volume contraction is small during solidification.Bisphenol A type epoxy resin be by bisphenol-A, epoxychloropropane in the basic conditions Condensation, through washing, the refined high-molecular compound of desolventizing.
Attapulgite
Attapulgite is native block structure, and color is greyish white, steel gray, pale yellow and light green.Greasy luster, light specific gravity, Mo Shi 2-3 grades of hardness, tacky when moist and plasticity is dried and shrinks small, and does not produce cracking, water imbibition by force, can reach 150% with On, PH=8.5 or so, due to internal porous road, specific surface area is big, up to 350m2/ more than g, most cation, moisture Son and a certain size organic molecule directly can be adsorbed into duct, and its stable electrochemical property.
The preparation method of the organic clay modified epoxy is as follows：
(1) organic clay, DMA are added into reactor, is warming up to 70 DEG C, stir 3h, add ring Oxygen tree fat, 10h is incubated under the conditions of 70 DEG C, adds 70 DEG C of deionized water, with extraction part DMA；It is described to have The weight ratio of machine clay and the DMA is 1：3；The weight ratio of the organic clay and the epoxy resin For (0.05-0.2)：1；
(2) mixture after extraction is steeped into 6h in 80 DEG C of vacuum degassings, adds glutaric anhydride, octadecyl trimethyl chlorine Change ammonium, continue 80 DEG C of vacuum degassing bubble 2h, then solidify 2h, 100 DEG C of solidifications 1h, 120 DEG C of solidification 5h under normal pressure at 80 DEG C, obtain institute State organic clay modified epoxy；The organic clay and the glutaric anhydride, the OTAC Weight ratio is 1：(0.2-0.5)：(0.1-0.3).
The preparation method of the organic clay is as follows：
(1) attapulgite is added into barrel temperature in 60 DEG C of high-speed mixers, acrylic acid and BPO are added by weight, Stir after 2h, discharging rises to high-speed mixer barrel temperature after 120 DEG C, above-mentioned material is refunded in high-speed mixer, at a high speed Stir and discharged after 1h, obtain acrylic acid attapulgite；The weight ratio of the attapulgite and the acrylic acid, the BPO is 100：(15-20)：(0.12-0.2)；
(2) by 2,4,6- trihydroxybenzoic acids, dodecyl sodium sulfate are dissolved in polyphosphoric acids, and 9h is reacted at 90 DEG C Afterwards, room temperature is down to, is poured into acetone, fully after washing to neutrality, filters and dries 12h at 120 DEG C in vacuum drying oven, obtain It is grafted 2,4,6- trihydroxybenzoic acids of dodecyl sodium sulfate；Described 2,4,6- trihydroxybenzoic acids and the dodecyl sulphur Sour sodium, the weight ratio of the polyphosphoric acids are 1：(0.2-1)：(10-15)；
(3) by 2,4,6- tri- hydroxyls of grafting dodecyl sodium sulfate in acrylic acid attapulgite in step (1) and step (2) Yl benzoic acid adds barrel temperature in 120 DEG C of high-speed mixers, to discharge after high-speed stirred 1h, obtain the organic clay.
Very high by acrylic acid AA reactivity in the present invention, its one end is the carboxyl of highly acid, can be with attapulgite Surface is chemically bonded, under the reaction condition of solid phase grafting, and product is combined in attapulgite's surface, is grafted dodecyl sulphur The 2 of sour sodium, 4,6- trihydroxybenzoic acids are blended with acrylic acid modified attapulgite, obtained organic clay surface covered with Machine thing contains the polar group of carboxyl, hydroxyl etc., organic clay particle is had surface lipophilic group, affine with epoxy resin Property enhancing, improve its dispersiveness in the epoxy, in addition the introducing of 2,4,6- trihydroxybenzoic acids, further increased The dispersiveness and mechanical property of machine clay particle in the epoxy.
Light stabilizer
The effect of light stabilizer is to increase the weatherability of epoxy curing compound, is especially requiring that the transparency higher application is led Domain, the application of light stabilizer is universal.Light stabilizer is called UV light stabilizing agent, can reduce visible ray or ultraviolet light to some The influence of chemical property containing the phenyl ring or heterocycle compound relatively more living dialled.
In one embodiment, 2-Phenylbenzimidazole -5- is grafted described in the composite polymer light stabilizer The polyvinyl chloride of sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and the tetramethyl piperazine of fumaric acid 2,2,6,6- The weight ratio of pyridine alcohol poly glycol monomethyl ether dibasic acid esters is 1：(0.1-1).
In one embodiment, 2-Phenylbenzimidazole -5- is grafted described in the composite polymer light stabilizer The polyvinyl chloride of sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and the tetramethyl piperazine of fumaric acid 2,2,6,6- The weight ratio of pyridine alcohol poly glycol monomethyl ether dibasic acid esters is 1：(0.5-1)；Preferably, the grafting 2-Phenylbenzimidazole -5- sulphurs The polyvinyl chloride of acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenones and the tetramethyl piperidine of fumaric acid 2,2,6,6- The weight ratio of alcohol poly glycol monomethyl ether dibasic acid esters is 1：0.63.
The preparation method of the composite polymer light stabilizer is as follows：
(1) 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID, 2,2'- dihydroxy -4,4'- dimethoxy hexichol are added into reactor Ketone, potassium carbonate, 3- propargyl bromides and acetone, flow back 24h, stops reaction, and rapid column chromatography obtains the UV Absorption of alkynyl substituted Agent；The 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone, the carbonic acid Potassium, the mol ratio of the 3- propargyl bromides are 1：0.7：3.5：1.8；The 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID and the acetone Weight ratio is 1：6；
(2) polyvinyl chloride, sodium azide, TBAB and tetrahydrofuran are added into reactor, it is anti-at 50 DEG C 20h is answered, stops after reaction, precipitates in methyl alcohol, is filtered, 50 DEG C are dried under reduced pressure 12h, obtain the polyvinyl chloride of azide substitution；It is described The weight ratio of polyvinyl chloride and the sodium azide, the TBAB, the tetrahydrofuran is 1：1.3：0.4：10；
(3) by the polyvinyl chloride of azide substitution, bromination in the UV absorbers of alkynyl substituted, step (2) in step (1) Cuprous and tetrahydrofuran is added in reactor, substitutes nitrogen three times, nitrogen protection, adds pentamethyl dimethylene triamine, room Temperature stirring 12h, stops after reaction, and with neutral alumina filtering to remove metallic catalyst, filtrate is precipitated in methyl alcohol, and 50 DEG C subtract Press dry dry 12h；Obtain being grafted 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone Polyvinyl chloride；It is the UV absorbers of the alkynyl substituted and the polyvinyl chloride of the azide substitution, the cuprous bromide, described The weight ratio of tetrahydrofuran is 1：0.2：0.6：12；
(4) monomethyl fumarate and poly glycol monomethyl ether are added in reactor, adds the toluene of 2 times of volume of mixture Solvent, is heated to 45 DEG C of stirring and dissolvings, adds 3.5% p-methyl benzenesulfonic acid of total weight of the mixture and is warming up to 105 DEG C, nitrogen Gas shielded, reacts 9h, and vacuum distillation, product is precipitated with absolute ether, and then 45 DEG C of vacuum dryings, obtain the poly- second of fumarate dimethyl Glycol monomethyl ether dibasic acid esters；Then by the fumarate dimethyl poly glycol monomethyl ether dibasic acid esters and 2,2,6,6- tetramethylpiperidinols add Enter in reactor, add the toluene solvant of 3 times of volume of mixture, be heated to 45 DEG C of stirring and dissolvings, add total weight of the mixture 4.5% tetra-n-butyl titanate, and be warming up to 105 DEG C, be passed through nitrogen protection, react 10h, absolute ether is used in vacuum distillation Precipitation, and wash for several times, 45 DEG C of vacuum dryings, obtain the tetramethylpiperidinol poly glycol monomethyl ether of fumaric acid 2,2,6,6- double Ester；The mol ratio of the monomethyl fumarate and the poly glycol monomethyl ether is 1: 1.1；The fumarate dimethyl polyethylene glycol Monomethyl ether dibasic acid esters and described 2, the mol ratio of 2,6,6- tetramethylpiperidinols is 1: 1.1；
(5) grafting 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID and 2,2'- dihydroxy -4,4'- dimethoxy are added into reactor Polyvinyl chloride, the tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters of fumaric acid 2,2,6,6-, the toluene of benzophenone, are passed through nitrogen Protection, is warming up to 90 DEG C, adds benzoyl peroxide, and insulation reaction 24h is reacted after terminating, and vacuum distillation removes toluene solvant, Then precipitated with absolute ether, filter, be dried under reduced pressure 12h in 45 DEG C, obtain composite polymer light stabilizer；The grafting 2- benzene The polyvinyl chloride of base benzimidazole -5- sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and the fumaric acid 2, 2,6,6- tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters, the weight ratio of the toluene are 1：0.8：0.07：10.
Heretofore described composite polymer light stabilizer heat decomposition temperature is high, hence it is evident that improves low molecule light stabilizer and deposits Hot procedure thermal decomposition deficiency, small molecule UV absorbers are bonded on polyvinyl chloride main chain, can be overcome The directly volatilizations of addition small molecule UV absorbers, the migration and the shortcomings of by solvent extraction in polyvinyl chloride, while can It is well dispersed within fluoropolymer resin, anti-light aging effect is played long-term effectively, effectively prevents xanthochromia, glue is influenceed The using effect of stick.
Antioxidant
Antioxidant is a class chemical substance, in the presence of it is only a small amount of in polymeric system, so that it may delay or suppresses to gather The progress of compound oxidizing process, so as to prevent the aging of polymer and extend its service life, is otherwise known as " age resistor ".
In one embodiment, the antioxidant includes one or more in BHT, DLTP；Preferably, the antioxidant For BHT.
Curing agent
At normal temperatures, epoxy resin is difficult solidification in itself, without mechanical strength, insulation with it is resistant to chemical etching etc. a series of Premium properties.The addition of curing agent can cause epoxy resin to solidify under certain condition, be formed with space network Solidfied material.Polysulfide alcohols curing agent can be used as room temperature, low temperature curing agent.There is two or more mercapto in molecule Base, by being used cooperatively with accelerator, can shorten to the hardening time under normal temperature within l0min.
In one embodiment, the preparing raw material of the polysulfide alcohols curing agent includes 2,6-TDI (Toluene-2,4-diisocyanate, 6- bis- Isocyanates), 3- mercaptopropionic acids, tripentaerythritol.
The preparation method of the polysulfide alcohols curing agent is as follows：
(1) tripentaerythritol, 3- mercaptopropionic acids, butter of tin, DMA are added into reactor, is passed through Nitrogen, 85 DEG C of preheating 30min are warming up to 110 DEG C of reaction 3h, add the concentrated sulfuric acid (water absorbing agent), continue to react 2h, stop after reaction Room temperature is cooled to, filters, isolates butter of tin, filtrate is concentrated under reduced pressure, much sulfhydryl compound；The tripentaerythritol Mol ratio with the 3- mercaptopropionic acids is 1：4.7；The weight ratio of the tripentaerythritol and the butter of tin is 1：0.02； The weight ratio of the tripentaerythritol and the DMA is 1：5；The tripentaerythritol and the concentrated sulfuric acid Weight ratio be 1：0.1；
(2) many sulfhydryl compounds, butanone are added into reactor, E-51 epoxy resin is stirring evenly and then adding into, is warming up to 95 DEG C, 3h is reacted, 70 DEG C are cooled to；3h is reacted under the conditions of being slowly added to 2,6-TDI, 70 DEG C, stops reaction, decompression is carried out dense Contracting, obtains the polysulfide alcohols curing agent；Many sulfhydryl compounds and the E-51 epoxy resin, mole of 2, the 6-TDI Than for 2.2：1：0.42；The weight ratio of many sulfhydryl compounds and the butanone is 1：5.
In one embodiment, the modified amine curing agent preparing raw material includes diethylenetriamine, thiocarbamide.
The modified amine curing agent preparation method is as follows：
Diethylenetriamine, thiocarbamide are added into reactor, 130 DEG C are warming up to, insulation reaction 3h after reaction terminating, makes temperature Degree is slowly drop down to 50 DEG C, continues to stir and constant temperature 1h, is cooled to room temperature, obtains modified amine curing agent；The diethylenetriamine with The mol ratio of the thiocarbamide is 1.6：1.
In one embodiment, the weight ratio of the Polymercaptan curing agent and the modified amine curing agent is (1-2)：1； Preferably, the weight ratio of the Polymercaptan curing agent and the modified amine curing agent is 1.4：1.
Amine curing agent enbrittles height, bad impact resistance, not good enough weatherability and toxic action, simple polymercaptan The epoxy glue of solidification is more crisp, and shear strength and fracture toughness are relatively low at room temperature；The present invention is changed by diethylenetriamine, thiocarbamide synthesis Property amine hardener, compounded by synthesizing polysulfide alcohols curing agent and modified amine curing agent, overcome amine curing agent fragility high, it is bad Impact resistance, the epoxy glue of not good enough weatherability, toxic action and the solidification of simple polymercaptan is more crisp, at room temperature shear strength and While the problems such as fracture toughness is relatively low, curing rate, shear strength and the fracture toughness of epoxide-resin glue are also improved.
In one embodiment, the weight of the bisphenol A type epoxy resin and the organic clay modified epoxy Than for (1.5-3)：1.
In one embodiment, the weight of the bisphenol A type epoxy resin and the organic clay modified epoxy Than for 2：1.
Diluent
The effect of diluent is that the viscosity for keeping epoxy-resin systems is maintained in the range of a convenient operation, typically Think that 1000mPa.s or so is proper under normal temperature.Diluent can also improve the tensile shear strength of epoxy adhesive, Raising even to the heat resistance of adhesive can also play facilitation.
Influence according to diluent to curing reaction, diluent is divided into reactive diluent and the major class of non-activated thinner two. Epoxy radicals is carried in reactive diluent molecular structure, be may participate in into the curing reaction of epoxy resin, it is solid as epoxy resin A part for compound cross-linked network structure；Non-activated thinner is not involved in curing reaction, and glue is reduced by the method for physical mixed The viscosity of stick, such as acetone, toluene, ethyl acetate equal solvent.
In one embodiment, the diluent include lauryl diglycidyl ether, tridecyl glycidol ether, It is one or more in myristyl glycidol ether；Preferably, the diluent is myristyl glycidol ether.
Filler
The effect of curing agent is the curing performance for changing adhesive, but because epoxy resin cured product crosslink density is high, is in Tridimensional network, with larger internal stress, this cured product is present matter is crisp, fatigue durability, heat resistance, shock resistance are tough Property difference the shortcomings of, it is impossible to meet some occasions to performance requirement careless quarter.Therefore, the addition of filler can then play certain delay Solution is acted on.
In one embodiment, the filler includes titanium dioxide, silicon powder, alumina powder, magnesia powder, aluminium hydroxide It is one or more in powder, calcium carbonate, modified calcium carbonate；The modified calcium carbonate is that acrylic acid calcium carbonate is grafted dodecyl sodium sulfonate Sodium；Preferably, the filler is modified calcium carbonate.
The preparation method of the modified calcium carbonate is as follows：
(1) calcium carbonate is added barrel temperature in 60 DEG C of high-speed mixers, by weight acrylic acid and BPO is added, to stir Mix after 2h, discharge, high-speed mixer barrel temperature is risen to after 120 DEG C, above-mentioned material is refunded in high-speed mixer, high-speed stirring Mix and discharged after 1h, obtain acrylic acid calcium carbonate；The weight ratio of the calcium carbonate and the acrylic acid, the BPO is 100：16： 0.15；
(2) acrylic acid calcium carbonate, dodecyl sodium sulfate are dissolved in polyphosphoric acids, react after 8h, be down at 90 DEG C Room temperature, is poured into dichloromethane, fully after washing to neutrality, is filtered and is dried 12h at 120 DEG C in vacuum drying oven, is changed Property calcium carbonate；The weight ratio of the acrylic acid calcium carbonate and the dodecyl sodium sulfate, the polyphosphoric acids is 1：0.2：12.
Coupling agent
The effect of coupling agent is the compatibility for the cohesive force and improvement inorganic filler for improving interface.Coupling agent mainly includes silicon Alkane coupling agent and the major class of titanate esters system coupling agent two.The former main function is to improve interfacial adhesion, and the latter is mainly used in Improve the compatibility of inorganic filler.
In one embodiment, the coupling agent is included in vinylsiloxane class coupling agent, polysiloxane coupling agent It is one or more；Preferably, the coupling agent is vinylsiloxane class coupling agent.
In one embodiment, the vinylsiloxane class coupling agent includes vinyl three ('beta '-methoxy ethyoxyl) Silane (XD-172), vinyltrimethoxy silane (XD-171), VTES (XD-151), vinyl three are withered It is one or more in alkenyl peroxy-silane (XD-VTCPS)；Preferably, the vinylsiloxane class coupling agent is vinyl three Ethoxysilane.
Thixotropic agent
Coating is when by shearing force, and denseness declines, and shearing force is bigger, and the amplitude of decline is also big, after shearing force is removed, Denseness slowly returns to original state again, and this phenomenon is referred to as " thixotroping ".Used in coating after thixotropic agent, the height in construction Have under shear rate compared with low-viscosity, contribute to coating to flow and be easy to construction；Under low shear rate before construction and afterwards Have compared with high viscosity, pigment sedimentation and wet film sagging can be prevented.
In one embodiment, the thixotropic agent includes organobentonite, rilanit special, Tissuemat E, gas phase two It is one or more in silica, metallic soap；Preferably, the thixotropic agent is aerosil.
In one embodiment, the weight of the bisphenol A type epoxy resin and the organic clay modified epoxy Than for (1-3)：1；Preferably, the weight ratio of the bisphenol A type epoxy resin and the organic clay modified epoxy is 2.2：1.
Epoxyn is widely used, and has excellent cementitiousness to multiple material, high, electric with adhesion strength Function admirable, shrinkage factor are low, dimensionally stable, strong weatherability the advantages of.Many sulfydryl curing agent collocation Tertiary amine accelerators and asphalt mixtures modified by epoxy resin Fat uses cooperatively and shows water white transparency and the fast advantage of curing rate.
The present invention is using the Polymercaptan curing agent synthesized by tripentaerythritol, with excellent curing rate.Aliphatic Modified amine curing agent, smell is low, also can cured epoxy resin at room temperature, it is preliminary solid but in binding agent solidification process The time of change is slower.Employ polymercaptan to be compounded with modified amine, when the curing agent is mixed with epoxy resin, room temperature can be achieved Rapid curing.
Phenyl ring in bisphenol A epoxide resin structure is rich in double bond, is easily broken off, can accelerate under air and UV environment Product aging so that bisphenol A epoxide resin haves the shortcomings that weatherability is poor, with organic modified clay to bisphenol A epoxide resin body System is modified to expect to improve its mechanical property, and the performance of clay modified composite depends primarily on organic clay in ring In scattered and compatible situation in epoxy resin system, the present invention by organic clay modified epoxy (being rich in double bond), contain The polysulfide alcohols curing agent of many sulfydryls, the effect of modified amine curing agent formulation, obtain highly cross-linked epobond epoxyn, in addition Curing agent and filler are further improved in epoxyn by attapulgite modified and filler modified calcium carbonate Dispersiveness and mechanical property, and then promote the low-temperature setting and epoxide-resin glue curing rate of epoxy resin fast, shear strength and The advantages of fracture toughness is high.The composite polymer light stabilizer heat decomposition temperature is high, hence it is evident that improve low molecule light stabilizer The deficiency of the hot procedure thermal decomposition of presence, can be well dispersed within fluoropolymer resin, play anti-light long-term effectively Aging action, effectively prevents xanthochromia, influences the using effect of adhesive.
In one embodiment, the good composition epoxy resin application of the transparency and automotive field.
Another aspect of the present invention provides a kind of preparation method of the good composition epoxy resin of transparency, including following step Suddenly：
Bisphenol A type epoxy resin, organic clay modified epoxy are added in reactor by weight, 35 are warming up to DEG C, 0.5h is stirred, filler is added, continues to stir 0.5h, then adds light stabilizer, antioxidant, curing agent, diluent, coupling Agent, thixotropic agent, stir 1-3h, obtain the photovoltaic cutting epoxide-resin glue.
The present invention is specifically described below by embodiment.It is necessarily pointed out that, following examples are only used In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
In addition, if without other explanations, raw materials used is all commercially available.
Embodiment 1
The good composition epoxy resin of the transparency, is calculated by weight, including following components：Bisphenol type epoxy tree 50 parts of fat；25 parts of organic clay modified epoxy；1 part of light stabilizer；1 part of antioxidant；20 parts of curing agent；6 parts of diluent；Fill out 25 parts of material；1 part of coupling agent；1.5 parts of thixotropic agent；
Wherein, organic clay described in the organic clay modified epoxy is the 2,4 of grafting dodecyl sodium sulfate, The complex composition of 6- trihydroxybenzoic acids and acrylic acid attapulgite；The curing agent is polysulfide alcohols curing agent and modified amine Curing agent；The light stabilizer is composite polymer light stabilizer, and the composite polymer light stabilizer is grafting 2- benzene The polyvinyl chloride of base benzimidazole -5- sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and fumaric acid 2,2,6, 6- tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters copolymers；The diluent is myristyl glycidol ether；It is described to fill out Expect for modified calcium carbonate, the modified calcium carbonate is that acrylic acid calcium carbonate is grafted dodecyl sodium sulfate；The coupling agent is second Alkenyl triethoxysilane；The thixotropic agent is aerosil；The bisphenol A type epoxy resin changes with the organic clay Property epoxy resin weight ratio be 2.2：1；The weight ratio of the Polymercaptan curing agent and the modified amine curing agent is 1.4：1；
The preparation method of the good composition epoxy resin of the transparency, comprises the following steps：
Bisphenol A type epoxy resin, organic clay modified epoxy are added in reactor by weight, 35 are warming up to DEG C, 0.5h is stirred, filler is added, continues to stir 0.5h, then adds light stabilizer, antioxidant, curing agent, diluent, coupling Agent, thixotropic agent, stir 2h, obtain the photovoltaic cutting epoxide-resin glue.
The preparation method of the organic clay modified epoxy is as follows：
(1) organic clay, DMA are added into reactor, is warming up to 70 DEG C, stir 3h, add ring Oxygen tree fat, 10h is incubated under the conditions of 70 DEG C, adds 70 DEG C of deionized water, with extraction part DMA；It is described to have The weight ratio of machine clay and the DMA is 1：3；The weight ratio of the organic clay and the epoxy resin For 0.16：1；
(2) mixture after extraction is steeped into 6h in 80 DEG C of vacuum degassings, adds glutaric anhydride, octadecyl trimethyl chlorine Change ammonium, continue 80 DEG C of vacuum degassing bubble 2h, then solidify 2h, 100 DEG C of solidifications 1h, 120 DEG C of solidification 5h under normal pressure at 80 DEG C, obtain institute State organic clay modified epoxy；The organic clay and the glutaric anhydride, the OTAC Weight ratio is 1：0.32：0.2.
The preparation method of the organic clay is as follows：
(1) attapulgite is added into barrel temperature in 60 DEG C of high-speed mixers, acrylic acid and BPO are added by weight, Stir after 2h, discharging rises to high-speed mixer barrel temperature after 120 DEG C, above-mentioned material is refunded in high-speed mixer, at a high speed Stir and discharged after 1h, obtain acrylic acid attapulgite；The weight ratio of the attapulgite and the acrylic acid, the BPO is 100：18：0.16；
(2) by 2,4,6- trihydroxybenzoic acids, dodecyl sodium sulfate are dissolved in polyphosphoric acids, and 9h is reacted at 90 DEG C Afterwards, room temperature is down to, is poured into acetone, fully after washing to neutrality, filters and dries 12h at 120 DEG C in vacuum drying oven, obtain It is grafted 2,4,6- trihydroxybenzoic acids of dodecyl sodium sulfate；Described 2,4,6- trihydroxybenzoic acids and the dodecyl sulphur Sour sodium, the weight ratio of the polyphosphoric acids are 1：0.24：12；
(3) by 2,4,6- tri- hydroxyls of grafting dodecyl sodium sulfate in acrylic acid attapulgite in step (1) and step (2) Yl benzoic acid adds barrel temperature in 120 DEG C of high-speed mixers, to discharge after high-speed stirred 1h, obtain the organic clay；Institute The weight ratio for stating acrylic acid attapulgite and 2,4,6- trihydroxybenzoic acids of the grafting dodecyl sodium sulfate is 1：0.3.
The preparation method of the polysulfide alcohols curing agent is as follows：
(1) tripentaerythritol, 3- mercaptopropionic acids, butter of tin, DMA are added into reactor, is passed through Nitrogen, 85 DEG C of preheating 30min are warming up to 110 DEG C of reaction 3h, add the concentrated sulfuric acid, continue to react 2h, room is cooled to after stopping reaction Temperature, filtering, isolates butter of tin, filtrate is concentrated under reduced pressure, much sulfhydryl compound；The tripentaerythritol and the 3- The mol ratio of mercaptopropionic acid is 1：4.7；The weight ratio of the tripentaerythritol and the butter of tin is 1：0.02；Three season The weight ratio of penta tetrol and the DMA is 1：5；The weight ratio of the tripentaerythritol and the concentrated sulfuric acid For 1：0.1；
(2) many sulfhydryl compounds, butanone are added into reactor, E-51 epoxy resin is stirring evenly and then adding into, is warming up to 95 DEG C, 3h is reacted, 70 DEG C are cooled to；3h is reacted under the conditions of being slowly added to 2,6-TDI, 70 DEG C, stops reaction, decompression is carried out dense Contracting, obtains the polysulfide alcohols curing agent；Many sulfhydryl compounds and the E-51 epoxy resin, mole of 2, the 6-TDI Than for 2.2：1：0.42；The weight ratio of many sulfhydryl compounds and the butanone is 1：5.
The modified amine curing agent preparation method is as follows：
Diethylenetriamine, thiocarbamide are added into reactor, 130 DEG C are warming up to, insulation reaction 3h after reaction terminating, makes temperature Degree is slowly drop down to 50 DEG C, continues to stir and constant temperature 1h, is cooled to room temperature, obtains modified amine curing agent；The diethylenetriamine with The mol ratio of the thiocarbamide is 1.6：1.
The preparation method of the modified calcium carbonate is as follows：
(1) calcium carbonate is added barrel temperature in 60 DEG C of high-speed mixers, by weight acrylic acid and BPO is added, to stir Mix after 2h, discharge, high-speed mixer barrel temperature is risen to after 120 DEG C, above-mentioned material is refunded in high-speed mixer, high-speed stirring Mix and discharged after 1h, obtain acrylic acid calcium carbonate；The weight ratio of the calcium carbonate and the acrylic acid, the BPO is 100：16： 0.15；
(2) acrylic acid calcium carbonate, dodecyl sodium sulfate are dissolved in polyphosphoric acids, react after 8h, be down at 90 DEG C Room temperature, is poured into dichloromethane, fully after washing to neutrality, is filtered and is dried 12h at 120 DEG C in vacuum drying oven, is changed Property calcium carbonate；The weight ratio of the acrylic acid calcium carbonate and the dodecyl sodium sulfate, the polyphosphoric acids is 1：0.2：12.
The preparation method of the composite polymer light stabilizer is as follows：
(1) 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID, 2,2'- dihydroxy -4,4'- dimethoxy hexichol are added into reactor Ketone, potassium carbonate, 3- propargyl bromides and acetone, flow back 24h, stops reaction, and rapid column chromatography obtains the UV Absorption of alkynyl substituted Agent；The 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone, the carbonic acid Potassium, the mol ratio of the 3- propargyl bromides are 1：0.7：3.5：1.8；The 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID and the acetone Weight ratio is 1：6；
(2) polyvinyl chloride, sodium azide, TBAB and tetrahydrofuran are added into reactor, it is anti-at 50 DEG C 20h is answered, stops after reaction, precipitates in methyl alcohol, is filtered, 50 DEG C are dried under reduced pressure 12h, obtain the polyvinyl chloride of azide substitution；It is described The weight ratio of polyvinyl chloride and the sodium azide, the TBAB, the tetrahydrofuran is 1：1.3：0.4：10；
(3) by the polyvinyl chloride of azide substitution, bromination in the UV absorbers of alkynyl substituted, step (2) in step (1) Cuprous and tetrahydrofuran is added in reactor, substitutes nitrogen three times, nitrogen protection, adds pentamethyl dimethylene triamine, room Temperature stirring 12h, stops after reaction, and with neutral alumina filtering to remove metallic catalyst, filtrate is precipitated in methyl alcohol, and 50 DEG C subtract Press dry dry 12h；Obtain being grafted 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone Polyvinyl chloride；It is the UV absorbers of the alkynyl substituted and the polyvinyl chloride of the azide substitution, the cuprous bromide, described The weight ratio of tetrahydrofuran is 1：0.2：0.6：12；
(4) monomethyl fumarate and poly glycol monomethyl ether are added in reactor, adds the toluene of 2 times of volume of mixture Solvent, is heated to 45 DEG C of stirring and dissolvings, adds 3.5% p-methyl benzenesulfonic acid of total weight of the mixture and is warming up to 105 DEG C, nitrogen Gas shielded, reacts 9h, and vacuum distillation, product is precipitated with absolute ether, and then 45 DEG C of vacuum dryings, obtain the poly- second of fumarate dimethyl Glycol monomethyl ether dibasic acid esters；Then by the fumarate dimethyl poly glycol monomethyl ether dibasic acid esters and 2,2,6,6- tetramethylpiperidinols add Enter in reactor, add the toluene solvant of 3 times of volume of mixture, be heated to 45 DEG C of stirring and dissolvings, add total weight of the mixture 4.5% tetra-n-butyl titanate, and be warming up to 105 DEG C, be passed through nitrogen protection, react 10h, absolute ether is used in vacuum distillation Precipitation, and wash for several times, 45 DEG C of vacuum dryings, obtain the tetramethylpiperidinol poly glycol monomethyl ether of fumaric acid 2,2,6,6- double Ester；The mol ratio of the monomethyl fumarate and the poly glycol monomethyl ether is 1: 1.1；The fumarate dimethyl polyethylene glycol Monomethyl ether dibasic acid esters and described 2, the mol ratio of 2,6,6- tetramethylpiperidinols is 1: 1.1；
(5) grafting 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID and 2,2'- dihydroxy -4,4'- dimethoxy are added into reactor Polyvinyl chloride, the tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters of fumaric acid 2,2,6,6-, the toluene of benzophenone, are passed through nitrogen Protection, is warming up to 90 DEG C, adds benzoyl peroxide, and insulation reaction 24h is reacted after terminating, and vacuum distillation removes toluene solvant, Then precipitated with absolute ether, filter, be dried under reduced pressure 12h in 45 DEG C, obtain composite polymer light stabilizer；The grafting 2- benzene The polyvinyl chloride of base benzimidazole -5- sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and the fumaric acid 2, 2,6,6- tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters, the weight ratio of the toluene are 1：0.8：0.07：10.
Embodiment 2
The good composition epoxy resin of the transparency, is calculated by weight, including following components：Bisphenol type epoxy tree 45 parts of fat；30 parts of organic clay modified epoxy；1 part of light stabilizer；1 part of antioxidant；20 parts of curing agent；6 parts of diluent；Fill out 25 parts of material；1 part of coupling agent；1.5 parts of thixotropic agent；
Wherein, organic clay described in the organic clay modified epoxy is the 2,4 of grafting dodecyl sodium sulfate, The complex composition of 6- trihydroxybenzoic acids and acrylic acid attapulgite；The curing agent is polysulfide alcohols curing agent and modified amine Curing agent；The light stabilizer is composite polymer light stabilizer, and the composite polymer light stabilizer is grafting 2- benzene The polyvinyl chloride of base benzimidazole -5- sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and fumaric acid 2,2,6, 6- tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters copolymers；The diluent is myristyl glycidol ether；It is described to fill out Expect for modified calcium carbonate, the modified calcium carbonate is that acrylic acid calcium carbonate is grafted dodecyl sodium sulfate；The coupling agent is second Alkenyl triethoxysilane；The thixotropic agent is aerosil；The bisphenol A type epoxy resin changes with the organic clay Property epoxy resin weight ratio be 2.2：1；The weight ratio of the Polymercaptan curing agent and the modified amine curing agent is 1.4：1；
The preparation method of the good composition epoxy resin of the transparency, the preparation of the organic clay modified epoxy It is prepared by method, the preparation method of the organic clay, the preparation method of the polysulfide alcohols curing agent, the modified amine curing agent Method, the preparation method of the modified calcium carbonate, the preparation method be the same as Example 1 of the composite polymer light stabilizer.
Embodiment 3
The good composition epoxy resin of the transparency, is calculated by weight, including following components：Bisphenol type epoxy tree 55 parts of fat；20 parts of organic clay modified epoxy；1 part of light stabilizer；1 part of antioxidant；20 parts of curing agent；6 parts of diluent；Fill out 25 parts of material；1 part of coupling agent；1.5 parts of thixotropic agent；
Wherein, organic clay described in the organic clay modified epoxy is the 2,4 of grafting dodecyl sodium sulfate, The complex composition of 6- trihydroxybenzoic acids and acrylic acid attapulgite；The curing agent is polysulfide alcohols curing agent and modified amine Curing agent；The light stabilizer is composite polymer light stabilizer, and the composite polymer light stabilizer is grafting 2- benzene The polyvinyl chloride of base benzimidazole -5- sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and fumaric acid 2,2,6, 6- tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters copolymers；The diluent is myristyl glycidol ether；It is described to fill out Expect for modified calcium carbonate, the modified calcium carbonate is that acrylic acid calcium carbonate is grafted dodecyl sodium sulfate；The coupling agent is second Alkenyl triethoxysilane；The thixotropic agent is aerosil；The bisphenol A type epoxy resin changes with the organic clay Property epoxy resin weight ratio be 2.2：1；The weight ratio of the Polymercaptan curing agent and the modified amine curing agent is 1.4：1；
The preparation method of the good composition epoxy resin of the transparency, the preparation of the organic clay modified epoxy It is prepared by method, the preparation method of the organic clay, the preparation method of the polysulfide alcohols curing agent, the modified amine curing agent Method, the preparation method of the modified calcium carbonate, the preparation method be the same as Example 1 of the composite polymer light stabilizer.
Embodiment 4
The good composition epoxy resin of the transparency, is calculated by weight, including following components：Bisphenol type epoxy tree 50 parts of fat；25 parts of organic clay modified epoxy；0.5 part of light stabilizer；1 part of antioxidant；20 parts of curing agent；6 parts of diluent； 25 parts of filler；1 part of coupling agent；1.5 parts of thixotropic agent；
Wherein, organic clay described in the organic clay modified epoxy is the 2,4 of grafting dodecyl sodium sulfate, The complex composition of 6- trihydroxybenzoic acids and acrylic acid attapulgite；The curing agent is polysulfide alcohols curing agent and modified amine Curing agent；The light stabilizer is composite polymer light stabilizer, and the composite polymer light stabilizer is grafting 2- benzene The polyvinyl chloride of base benzimidazole -5- sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and fumaric acid 2,2,6, 6- tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters copolymers；The diluent is myristyl glycidol ether；It is described to fill out Expect for modified calcium carbonate, the modified calcium carbonate is that acrylic acid calcium carbonate is grafted dodecyl sodium sulfate；The coupling agent is second Alkenyl triethoxysilane；The thixotropic agent is aerosil；The bisphenol A type epoxy resin changes with the organic clay Property epoxy resin weight ratio be 2.2：1；The weight ratio of the Polymercaptan curing agent and the modified amine curing agent is 1.4：1；
The preparation method of the good composition epoxy resin of the transparency, the preparation of the organic clay modified epoxy It is prepared by method, the preparation method of the organic clay, the preparation method of the polysulfide alcohols curing agent, the modified amine curing agent Method, the preparation method of the modified calcium carbonate, the preparation method be the same as Example 1 of the composite polymer light stabilizer.
Embodiment 5
The good composition epoxy resin of the transparency, is calculated by weight, including following components：Bisphenol type epoxy tree 50 parts of fat；25 parts of organic clay modified epoxy；2 parts of light stabilizer；1 part of antioxidant；20 parts of curing agent；6 parts of diluent；Fill out 25 parts of material；1 part of coupling agent；1.5 parts of thixotropic agent；
Wherein, organic clay described in the organic clay modified epoxy is the 2,4 of grafting dodecyl sodium sulfate, The complex composition of 6- trihydroxybenzoic acids and acrylic acid attapulgite；The curing agent is polysulfide alcohols curing agent and modified amine Curing agent；The light stabilizer is composite polymer light stabilizer, and the composite polymer light stabilizer is grafting 2- benzene The polyvinyl chloride of base benzimidazole -5- sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and fumaric acid 2,2,6, 6- tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters copolymers；The diluent is myristyl glycidol ether；It is described to fill out Expect for modified calcium carbonate, the modified calcium carbonate is that acrylic acid calcium carbonate is grafted dodecyl sodium sulfate；The coupling agent is second Alkenyl triethoxysilane；The thixotropic agent is aerosil；The bisphenol A type epoxy resin changes with the organic clay Property epoxy resin weight ratio be 2.2：1；The weight ratio of the Polymercaptan curing agent and the modified amine curing agent is 1.4：1；
The preparation method of the good composition epoxy resin of the transparency, the preparation of the organic clay modified epoxy It is prepared by method, the preparation method of the organic clay, the preparation method of the polysulfide alcohols curing agent, the modified amine curing agent Method, the preparation method of the modified calcium carbonate, the preparation method be the same as Example 1 of the composite polymer light stabilizer.
Embodiment 6
The good composition epoxy resin of the transparency, is calculated by weight, including following components：Bisphenol type epoxy tree 50 parts of fat；25 parts of organic clay modified epoxy；1 part of light stabilizer；1 part of antioxidant；20 parts of curing agent；6 parts of diluent；Fill out 25 parts of material；1 part of coupling agent；1.5 parts of thixotropic agent；
Wherein, organic clay described in the organic clay modified epoxy is the 2,4 of grafting dodecyl sodium sulfate, The complex composition of 6- trihydroxybenzoic acids and acrylic acid attapulgite；The curing agent is polysulfide alcohols curing agent and modified amine Curing agent；The light stabilizer is composite polymer light stabilizer, and the composite polymer light stabilizer is grafting 2- benzene The polyvinyl chloride of base benzimidazole -5- sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and fumaric acid 2,2,6, 6- tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters copolymers；The diluent is myristyl glycidol ether；It is described to fill out Expect for modified calcium carbonate, the modified calcium carbonate is that acrylic acid calcium carbonate is grafted dodecyl sodium sulfate；The coupling agent is second Alkenyl triethoxysilane；The thixotropic agent is aerosil；The bisphenol A type epoxy resin changes with the organic clay Property epoxy resin weight ratio be 2.2：1；The weight ratio of the Polymercaptan curing agent and the modified amine curing agent is 1：1；
The preparation method of the good composition epoxy resin of the transparency, the preparation of the organic clay modified epoxy It is prepared by method, the preparation method of the organic clay, the preparation method of the polysulfide alcohols curing agent, the modified amine curing agent Method, the preparation method of the modified calcium carbonate, the preparation method be the same as Example 1 of the composite polymer light stabilizer.
Embodiment 7
The good composition epoxy resin of the transparency, is calculated by weight, including following components：Bisphenol type epoxy tree 50 parts of fat；25 parts of organic clay modified epoxy；1 part of light stabilizer；1 part of antioxidant；20 parts of curing agent；6 parts of diluent；Fill out 25 parts of material；1 part of coupling agent；1.5 parts of thixotropic agent；
Wherein, organic clay described in the organic clay modified epoxy is the 2,4 of grafting dodecyl sodium sulfate, The complex composition of 6- trihydroxybenzoic acids and acrylic acid attapulgite；The curing agent is polysulfide alcohols curing agent and modified amine Curing agent；The light stabilizer is composite polymer light stabilizer, and the composite polymer light stabilizer is grafting 2- benzene The polyvinyl chloride of base benzimidazole -5- sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and fumaric acid 2,2,6, 6- tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters copolymers；The diluent is myristyl glycidol ether；It is described to fill out Expect for modified calcium carbonate, the modified calcium carbonate is that acrylic acid calcium carbonate is grafted dodecyl sodium sulfate；The coupling agent is second Alkenyl triethoxysilane；The thixotropic agent is aerosil；The bisphenol A type epoxy resin changes with the organic clay Property epoxy resin weight ratio be 2.2：1；The weight ratio of the Polymercaptan curing agent and the modified amine curing agent is 2：1；
The preparation method of the good composition epoxy resin of the transparency, the preparation of the organic clay modified epoxy It is prepared by method, the preparation method of the organic clay, the preparation method of the polysulfide alcohols curing agent, the modified amine curing agent Method, the preparation method of the modified calcium carbonate, the preparation method be the same as Example 1 of the composite polymer light stabilizer.
Comparative example 1
The good composition epoxy resin of the transparency, is calculated by weight, including following components：Bisphenol type epoxy tree 50 parts of fat；25 parts of organic clay modified epoxy；1 part of light stabilizer；1 part of antioxidant；20 parts of curing agent；6 parts of diluent；Fill out 25 parts of material；1 part of coupling agent；1.5 parts of thixotropic agent；
Wherein, organic clay described in the organic clay modified epoxy is the 2,4 of grafting dodecyl sodium sulfate, The complex composition of 6- trihydroxybenzoic acids and acrylic acid attapulgite；The curing agent is polysulfide alcohols curing agent；The light Stabilizer is composite polymer light stabilizer, and the composite polymer light stabilizer is grafting 2-Phenylbenzimidazole -5- The polyvinyl chloride of sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and the tetramethylpiperidinol of fumaric acid 2,2,6,6- Poly glycol monomethyl ether dibasic acid esters copolymer；The diluent is myristyl glycidol ether；The filler is modified calcium carbonate, The modified calcium carbonate is that acrylic acid calcium carbonate is grafted dodecyl sodium sulfate；The coupling agent is vinyl triethoxyl silicon Alkane；The thixotropic agent is aerosil；The weight of the bisphenol A type epoxy resin and the organic clay modified epoxy Amount is than being 2.2：1；
The preparation method of the good composition epoxy resin of the transparency, the preparation of the organic clay modified epoxy It is prepared by method, the preparation method of the organic clay, the preparation method of the polysulfide alcohols curing agent, the modified amine curing agent Method, the preparation method of the modified calcium carbonate, the preparation method be the same as Example 1 of the composite polymer light stabilizer.
Comparative example 2
The good composition epoxy resin of the transparency, is calculated by weight, including following components：Bisphenol type epoxy tree 50 parts of fat；25 parts of organic clay modified epoxy；1 part of light stabilizer；1 part of antioxidant；20 parts of curing agent；6 parts of diluent；Fill out 25 parts of material；1 part of coupling agent；1.5 parts of thixotropic agent；
Wherein, organic clay described in the organic clay modified epoxy is the 2,4 of grafting dodecyl sodium sulfate, The complex composition of 6- trihydroxybenzoic acids and acrylic acid attapulgite；The curing agent is modified amine curing agent；The light is steady Agent is determined for composite polymer light stabilizer, and the composite polymer light stabilizer is grafting 2-Phenylbenzimidazole -5- sulphurs The polyvinyl chloride of acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenones gathers with the tetramethylpiperidinol of fumaric acid 2,2,6,6- Glycol monoethyl ether dibasic acid esters copolymer；The diluent is myristyl glycidol ether；The filler is modified calcium carbonate, institute State modified calcium carbonate and be grafted dodecyl sodium sulfate for acrylic acid calcium carbonate；The coupling agent is VTES； The thixotropic agent is aerosil；The weight of the bisphenol A type epoxy resin and the organic clay modified epoxy Than for 2.2：1；
The preparation method of the good composition epoxy resin of the transparency, the preparation of the organic clay modified epoxy It is prepared by method, the preparation method of the organic clay, the preparation method of the polysulfide alcohols curing agent, the modified amine curing agent Method, the preparation method of the modified calcium carbonate, the preparation method be the same as Example 1 of the composite polymer light stabilizer.
Comparative example 3
The good composition epoxy resin of the transparency, is calculated by weight, including following components：Bisphenol type epoxy tree 50 parts of fat；25 parts of organic clay modified epoxy；1 part of light stabilizer；1 part of antioxidant；20 parts of curing agent；6 parts of diluent；Fill out 25 parts of material；1 part of coupling agent；1.5 parts of thixotropic agent；
Wherein, organic clay described in the organic clay modified epoxy is attapulgite；The curing agent is poly- Thio-alcohol curing agent and modified amine curing agent；The light stabilizer is composite polymer light stabilizer, the compound high score Sub-light stabilizer is poly- for grafting 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone Vinyl chloride and the tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters copolymer of fumaric acid 2,2,6,6-；The diluent is the tetradecane Base glycidol ether；The filler is modified calcium carbonate, and the modified calcium carbonate is that acrylic acid calcium carbonate is grafted dodecyl sulphur Sour sodium；The coupling agent is VTES；The thixotropic agent is aerosil；The bisphenol type epoxy The weight ratio of resin and the organic clay modified epoxy is 2.2：1；The Polymercaptan curing agent is consolidated with the modified amine The weight ratio of agent is 1.4：1；
The preparation method of the good composition epoxy resin of the transparency, the preparation of the organic clay modified epoxy Method, the preparation method of the polysulfide alcohols curing agent, the modified amine curing agent preparation method, the system of the modified calcium carbonate The preparation method be the same as Example 1 of Preparation Method, the composite polymer light stabilizer；Difference is that the organic clay is bumps Rod soil.
Comparative example 4
The good composition epoxy resin of the transparency, is calculated by weight, including following components：Bisphenol type epoxy tree 50 parts of fat；25 parts of organic clay modified epoxy；1 part of light stabilizer；1 part of antioxidant；20 parts of curing agent；6 parts of diluent；Fill out 25 parts of material；1 part of coupling agent；1.5 parts of thixotropic agent；
Wherein, organic clay described in the organic clay modified epoxy is the 2,4 of grafting dodecyl sodium sulfate, The complex composition of 6- trihydroxybenzoic acids and acrylic acid attapulgite；The curing agent is polysulfide alcohols curing agent and modified amine Curing agent；The light stabilizer is 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID and 2,2'- dihydroxy -4,4'- dimethoxy hexichol first Ketone；The diluent is myristyl glycidol ether；The filler is modified calcium carbonate, and the modified calcium carbonate is acrylic acid Calcium carbonate is grafted dodecyl sodium sulfate；The coupling agent is VTES；The thixotropic agent is gas phase dioxy SiClx；The weight ratio of the bisphenol A type epoxy resin and the organic clay modified epoxy is 2.2：1；The polymercaptan The weight ratio of curing agent and the modified amine curing agent is 1.4：1；
The preparation method of the good composition epoxy resin of the transparency, the preparation of the organic clay modified epoxy It is prepared by method, the preparation method of the organic clay, the preparation method of the polysulfide alcohols curing agent, the modified amine curing agent Method, the preparation method be the same as Example 1 of the modified calcium carbonate.
Comparative example 5
The good composition epoxy resin of the transparency, is calculated by weight, including following components：Bisphenol type epoxy tree 50 parts of fat；25 parts of organic clay modified epoxy；1 part of light stabilizer；1 part of antioxidant；20 parts of curing agent；6 parts of diluent；Fill out 25 parts of material；1 part of coupling agent；1.5 parts of thixotropic agent；
Wherein, organic clay described in the organic clay modified epoxy is the 2,4 of grafting dodecyl sodium sulfate, The complex composition of 6- trihydroxybenzoic acids and acrylic acid attapulgite；The curing agent is polysulfide alcohols curing agent and modified amine Curing agent；The light stabilizer is composite polymer light stabilizer, and the composite polymer light stabilizer is grafting 2- benzene The polyvinyl chloride of base benzimidazole -5- sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and fumaric acid 2,2,6, 6- tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters copolymers；The diluent is myristyl glycidol ether；It is described to fill out Expect for modified calcium carbonate, the modified calcium carbonate is that acrylic acid calcium carbonate is grafted dodecyl sodium sulfate；The coupling agent is second Alkenyl triethoxysilane；The thixotropic agent is aerosil；The bisphenol A type epoxy resin changes with the organic clay Property epoxy resin weight ratio be 2.2：1；The weight ratio of the Polymercaptan curing agent and the modified amine curing agent is 1.4：1； The 3380s Polymercaptan curing agents that the Polymercaptan curing agent provides for Shenzhen Jia Dida, the modified amine curing agent is Shenzhen 5408 modified amine curing agents that Jia Dida is provided；
The preparation method of the good composition epoxy resin of the transparency, the preparation of the organic clay modified epoxy Method, the preparation method of the organic clay, the preparation method of the modified calcium carbonate, the composite polymer light stabilizer Preparation method be the same as Example 1.
Performance test
1st, exemplar cold curing time 3h is carried out according to GB/T1040.2-2006 method of testings, carries out tensile strength, pulls apart Elongation and modulus of elasticity test；
2nd, carry out exemplar room temperature according to Q/Dq139-94 method of testings and strength test is cut in 200 DEG C of drop-downs.
3rd, ultraviolet-visible light transmission rate
Obtained composition epoxy resin is evenly coated on 4cmx2cm transparent book sheet glass, smearing thickness is It is fixed on after 0.7mm, solidification on framework, using air as blank reference, the UV- produced using Shanghai You Nike Instrument Ltd. 4802H types ultraviolet-uisible spectrophotometer carries out 190-1000nm full wavelength scanner.
It is seen from the above data that the composition epoxy resin that the present invention is provided has adhesion strength height, hardening time Short, weatherability is strong, visible light transmissivity is high, excellent combination property.
Above-mentioned example is merely illustrative, some features of the feature for explaining the present invention.Appended claim The scope as wide as possible for requiring to be contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention Feature example selectional restriction, and progress in science and technology by formed language performance it is inaccurate due to and not The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case Claim is covered.

Claims (10)

1. the good composition epoxy resin of a kind of transparency, it is characterised in that calculate by weight, including following components：Bisphenol-A 30~70 parts of type epoxy resin；10-35 parts of organic clay modified epoxy；0.1-2 parts of light stabilizer；0.1-2 parts of antioxidant； 10~25 parts of curing agent；0.1~15 part of diluent；20~40 parts of filler；0.5~1.5 part of coupling agent；0.5~3 part of thixotropic agent；
Wherein, organic clay described in the organic clay modified epoxy is 2, the 4,6- tri- of grafting dodecyl sodium sulfate The complex composition of hydroxybenzoic acid and acrylic acid attapulgite；The curing agent is that polysulfide alcohols curing agent and modified amine solidify Agent；The light stabilizer is composite polymer light stabilizer, and the composite polymer light stabilizer is grafting 2- phenyl benzene And the polyvinyl chloride of imidazoles -5- sulfonic acid and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone and fumaric acid 2,2,6,6- tetra- Moperone poly glycol monomethyl ether dibasic acid esters copolymer.
2. transparent good composition epoxy resin according to claim 1, it is characterised in that calculate by weight, including Following components：35~60 parts of bisphenol A type epoxy resin；15-35 parts of organic clay modified epoxy；Light stabilizer 0.5-1.5 Part；0.5-1.5 parts of antioxidant；10~25 parts of curing agent；2~10 parts of diluent；20~30 parts of filler；0.5~1 part of coupling agent； 0.5~2 part of thixotropic agent.
3. transparent good composition epoxy resin according to claim 1, it is characterised in that the composite polymer light The poly- of 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone is grafted described in stabilizer The weight ratio of vinyl chloride and the tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters of fumaric acid 2,2,6,6- is 1：(0.1-1).
4. transparent good composition epoxy resin according to claim 3, it is characterised in that the composite polymer light The poly- of 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID and 2,2'- dihydroxy -4,4'- dimethoxy-benzophenone is grafted described in stabilizer The weight ratio of vinyl chloride and the tetramethylpiperidinol poly glycol monomethyl ether dibasic acid esters of fumaric acid 2,2,6,6- is 1：(0.5-1).
5. transparent good composition epoxy resin according to claim 1, it is characterised in that the polysulfide alcohols curing agent Preparing raw material include 2,6-TDI, 3- mercaptopropionic acid, tripentaerythritol.
6. transparent good composition epoxy resin according to claim 1, it is characterised in that the modified amine curing agent system Standby raw material includes diethylenetriamine, thiocarbamide.
7. transparent good composition epoxy resin according to claim 1, it is characterised in that the bisphenol type epoxy tree The weight ratio of fat and the organic clay modified epoxy is (1.5-3)：1.
8. transparent good composition epoxy resin according to claim 7, it is characterised in that the bisphenol type epoxy tree The weight ratio of fat and the organic clay modified epoxy is 2：1.
9. the good composition epoxy resin of the transparency according to claim 1-8, it is characterised in that the good ring of the transparency Epoxy resin composition is applied and automotive field.
10. the preparation method of the good composition epoxy resin of the transparency according to claim 1-8, it is characterised in that including Following steps：
Bisphenol A type epoxy resin, organic clay modified epoxy are added in reactor by weight, 35 DEG C are warming up to, Stir 0.5h, add filler, continue stir 0.5h, then add light stabilizer, antioxidant, curing agent, diluent, coupling agent, Thixotropic agent, stirs 1-3h, obtains the photovoltaic cutting epoxide-resin glue.
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