CN110408294A - Anti- plasticising silane coupling agent of one kind and its preparation method and application - Google Patents

Anti- plasticising silane coupling agent of one kind and its preparation method and application Download PDF

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Publication number
CN110408294A
CN110408294A CN201910827315.6A CN201910827315A CN110408294A CN 110408294 A CN110408294 A CN 110408294A CN 201910827315 A CN201910827315 A CN 201910827315A CN 110408294 A CN110408294 A CN 110408294A
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coupling agent
silane coupling
parts
plasticising
furyl
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CN110408294B (en
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严亮
陈文旭
徐赢斐
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Ningbo Czechoslovakia New Materials Co Ltd
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Ningbo Czechoslovakia New Materials Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D151/00Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/02Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to polysaccharides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18Fireproof paints including high temperature resistant paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention discloses a kind of anti-plasticising silane coupling agents; it is characterised in that it includes each component of following parts by weight: 2- cyano -3- (2- furyl) ethyl acrylate/3- benzoylacrylate/1- vinyl imidazole/20-35 parts of allyl cyclodextrin copolymers, 10-20 parts of fluorine richness epoxy resin, 3-6 parts of nano silica, 0.3-0.6 parts of coupling agent, 1-3 parts of boracic ionic liquid, 80-100 parts of solvent.The present invention also provides the preparation method and applications of the anti-plasticising silane coupling agent.Anti- plasticising silane coupling agent high production efficiency disclosed by the invention, strong with the adhesive force of substrate, curing time is short, and anti-plasticization effect is significant, small to the harm of environment and human body, has good social benefit, ecological benefits and economic benefit.

Description

Anti- plasticising silane coupling agent of one kind and its preparation method and application
Technical field
The present invention relates to silane coupling agent technical fields, more particularly to a kind of anti-plasticising silane coupling agent and preparation method thereof.
Background technique
With advances in technology and society development, automobile have become people's traffic trip main means of transport it One, it is increasing to automobile maintenance beauty demand.Invisible vehicle cover is a kind of important materials of Automotive Paint Film Properties maintenance, belongs to vehicle body One kind of pad pasting, different from the color tuning foil with individual character decoration as the main purpose, the main function of invisible vehicle cover is exactly using high The environmentally-friendly transparent film of performance covers vehicle body, and comprehensive protection is provided to vehicle paint, improves the anti-corruption of lacquer painting, antioxygen, anti-scratch rubs Ability, it will not both cover former Qi Yanse, moreover it is possible to improve the whole glossiness of vehicle body.Therefore, the quality pair of invisible vehicle cover is improved The effect of improvement automobile oxidation beauty plays the role of vital.
PVC invisible vehicle cover is a kind of invisible vehicle cover common currently on the market, and due to PVC Huang easily occurs for this kind of invisible vehicle cover Become, with " plasticizer " volatilization can generate dusting, and after dusting caused by cracking be fatal, in addition, PVC contact clothing construct In the process, the plasticizer volatilization that will lead to is heated, carcinogen is generated, is the direct inducement of carcinoma of testis;In addition this kind of material is tough Property it is insufficient, need to be bonded with car surface when in use, therefore, it is necessary to handle its surface, using silane coupling agent to its table Face, which carries out aid in treatment, can effectively enhance the attachment between adhesive, improve the stealthy effect of adhesive force and invisible vehicle cover.
Ideal silane coupling agent can realize following function: (1) basal plane being protected (to inhibit the turbid work of corruption of matrix in use With);(2) change matrix surface chemistry physical property;(3) filling matrix surface hole and enhancing surface weak area;(4) it penetrates into substrate Portion, enhancing base materials intensity;(5) film is formed in substrate surface, inhibits moisture to external migration;(6) can outdoor application indoors, nothing Smell;(7) cement base, terrazzo, PVC base etc. be can be applied to;(8) epoxy, water-base epoxy, poly- ammonia can be used in priming paint upper layer The materials such as ester and aqueous polyurethane.However, silane coupling agent in the prior art cannot generally improve the anti-plasticising of PVC invisible vehicle cover Property, in turn, it not can effectively improve the surface property of PVC contact clothing, adhesive property needs to be further increased.
Chinese patent CN1303896A discloses a kind of water epoxy priming coating agent and preparation method, by aqueous epoxy resins, Acrylic emulsion, alkyl phenol polyoxyethylene ether, formaldehyde and water composition;The product is to constructed surface of wall or need to bond cement system The humidity of product can be used without particular/special requirement, new and old wall.The silane coupling agent odorlessness, it is pollution-free, it is easy for construction, it is at low cost.It should Although silane coupling agent uses aqueous epoxy resins, accomplish odorlessness, pollution-free, but do not illustrate its whether be used for silicone adhesive with it is wooden On substrate, also aqueous epoxy resins are not modified with modified silicasol, modified waterborne epoxy in this patent cannot be reached The performance of resin.
Chinese patent CN103113789A discloses the silane coupling agent and preparation method of a kind of difficult viscous material, by chlorination third Alkene, organosilicon polymer, acrylic acid esters co-polymer, titanate coupling agent, benzene kind solvent, quinoline and stabilizer mixing, in 77- Solid content is adjusted at 110 DEG C, silane coupling agent is made, can effectively improve the adhesive strength of the difficult viscous material such as polyethylene, polypropylene, but should Silane coupling agent component is with the presence of quinoline, foul smelling and the big disadvantage of toxicity.
Therefore, seek more efficient way, prepare that anti-plasticization effect is significant, and cementitiousness is strong, to environment and human body The small anti-plasticising silane coupling agent of harm have very important significance.
Summary of the invention
The main purpose of the present invention is to provide a kind of anti-plasticising silane coupling agent, the anti-plasticising silane coupling agent high production efficiency, with The adhesive force of substrate is strong, and curing time is short, and anti-plasticization effect is significant, small to the harm of environment and human body, has good society Benefit, ecological benefits and economic benefit.Meanwhile the present invention also provides the preparation method and application of the anti-plasticising silane coupling agent.
To achieve the above objectives, the present invention provides a kind of anti-plasticising silane coupling agent, each component including following parts by weight: 2- cyanogen Base -3- (2- furyl) ethyl acrylate/3- benzoylacrylate/1- vinyl imidazole/allyl cyclodextrin copolymerization 20-35 parts of object, 10-20 parts of fluorine richness epoxy resin, 3-6 parts of nano silica, 0.3-0.6 parts of coupling agent, boracic ionic liquid 1-3 parts of body, 80-100 parts of solvent.
Further, the coupling agent is selected from Silane coupling agent KH550, silane coupling agent KH560, silane coupling agent At least one of KH570;The solvent is at least one of acetone, butanone, ethyl acetate or butyl acetate.
Further, 2- cyano -3- (2- furyl) ethyl acrylate/3- benzoylacrylate/1- second Alkenyl imidazoles/allyl cyclodextrin copolymers preparation method includes the following steps: 2- cyano -3- (2- furyl) propylene Acetoacetic ester, 3- benzoylacrylate, 1- vinyl imidazole, allyl cyclodextrin, initiator are added to high boiling solvent In, it carries out polymerization reaction 3-5 hours, is cooled to room temperature after reaction, in water at nitrogen or 70-80 DEG C of atmosphere of inert gases In settle out polymer, then through ethanol washing, drying, obtain 2- cyano -3- (2- furyl) ethyl acrylate/3- benzoyl third Olefin(e) acid ethyl ester/1- vinyl imidazole/allyl cyclodextrin copolymers.
Preferably, 2- cyano -3- (2- furyl) ethyl acrylate, 3- benzoylacrylate, 1- ethylene Base imidazoles, allyl cyclodextrin, initiator, high boiling solvent mass ratio be 1:1:0.3:(0.1-0.2): (0.02-0.03): (8-12)。
Preferably, the high boiling solvent is selected from n,N-Dimethylformamide, n,N-dimethylacetamide, N- methylpyrrole At least one of alkanone, dimethyl sulfoxide.
Preferably, the initiator is selected from least one of azodiisobutyronitrile, azobisisoheptonitrile;The indifferent gas Body is selected from one of helium, neon, argon gas.
Further, the preparation method of the fluorine richness epoxy resin includes the following steps: for epoxy resin to be dissolved in N- first Solution is formed in base pyrrolidones, 2- fluorin benzyl amine and basic catalyst is then added into solution again, is stirred at 70-80 DEG C anti- Answer 4-6 hours, after be precipitated in water, it is dry after taking-up, obtain fluorine richness epoxy resin.
Preferably, the mass ratio of the epoxy resin, N-Methyl pyrrolidone, 2- fluorin benzyl amine, basic catalyst is 1:(3- 5):(0.2-0.4):0.1。
Preferably, the basic catalyst is at least one in sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate.
Further, the preparation method of the anti-plasticising silane coupling agent, includes the following steps: to mix each component, stirs 1-2 Hour, then adjusting solid content with the method for evaporation reflux at 80-110 DEG C is 40-50wt%, and anti-plasticising silane coupling agent is made.
It is application on invisible vehicle cover it is another object of the present invention to provide a kind of above-mentioned anti-plasticising silane coupling agent.
Due to the application of the above technical scheme, the invention has the following advantages:
(1) anti-plasticising silane coupling agent disclosed by the invention, preparation method simple process is easy to operate, and preparation efficiency is high, meets big rule Mould production requirement.
(2) anti-plasticising silane coupling agent disclosed by the invention, overcoming silane coupling agent in the prior art, cannot generally to improve PVC hidden The anti-plasticity of shape car clothing, not can effectively improve the surface property of PVC contact clothing, and what adhesive property needed to be further increased lacks It falls into, there is high production efficiency, strong with the adhesive force of substrate, curing time is short, and anti-plasticization effect is significant, to the danger of environment and human body Evil is small, has the advantages that good social benefit, ecological benefits and economic benefit.
(3) anti-plasticising silane coupling agent disclosed by the invention can effectively adjust plasticizer by the synergistic effect between each component Interaction force between PVC balances Plasticizer migration and plasticity;2- cyano -3- (2- furyl) ethyl acrylate/ 3- benzoylacrylate/1- vinyl imidazole/allyl cyclodextrin copolymers are by 2- cyano -3- (2- furyl) third The copolymerization of the monomers such as olefin(e) acid ethyl ester, 3- benzoylacrylate, 1- vinyl imidazole, allyl cyclodextrin copolymers is made, The furan group and imidazole group of introducing can effectively increase adherence, and can also play elimination due to containing more active group Free radical improves coating anti-aging property, and the introducing of acrylate structural is so that paint has conventional polypropylene esters of gallic acid paint The advantages of, improve the comprehensive performance of paint;The introducing of cyano, benzoyl can improve the weatherability of paint;In other each components Due to also containing more active group, it can also improve the adhesive property of material, improve the stealthy effect of invisible vehicle cover;In copolymer Glyoxaline structure is introduced, easily crosslinks and reacts with the chlorine of PVC surface, further hinders migration of plasticizer in PVC;Cyclodextrin by In its void structure, on the one hand can be conducive to improve adhesive property, another invention is also resistant to be plasticized;Pass through boracic ionic liquid It is added, can effectively improve the flame retardant property and adhesive property of silane coupling agent, while can also play plasticization, effectively prevent in PVC The migration of Conventional plasticizers;By fluorine richness epoxy resin, the superiority such as its weatherability, color inhibition, temperature tolerance can be effectively assigned Energy.
Specific embodiment
It is described below for disclosing the present invention so that those skilled in the art can be realized the present invention.It is excellent in being described below Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.
Allyl cyclodextrin described in the embodiment of the present invention is previously prepared, preparation method reference: full methyl moiety allyl Cyclodextrin as GC stationary phase synthesis and first split, chemical reagent, 2002,24(3);The boracic ionic liquid Body is previously prepared, preparation method reference: synthesis, standard and its application in borophosphate synthesis of boracic ionic liquid, Li Xinjie, Northeastern University, 2012;Other raw materials are commercially available.
Embodiment 1
A kind of anti-plasticising silane coupling agent, each component including following parts by weight: 2- cyano -3- (2- furyl) ethyl acrylate/3- Benzoylacrylate/1- vinyl imidazole/20 parts of allyl cyclodextrin copolymers, is received 10 parts of fluorine richness epoxy resin Rice 3 parts of silica, 0.3 part of Silane coupling agent KH550,1 part of boracic ionic liquid, 80 parts of acetone.
2- cyano -3- (2- furyl) ethyl acrylate/3- benzoylacrylate/1- vinyl imidazole/ The preparation method of allyl cyclodextrin copolymers, include the following steps: by 2- cyano -3- (2- furyl) ethyl acrylate 10g, 3- benzoylacrylate 10g, 1- vinyl imidazole 3g, allyl cyclodextrin 1g, azodiisobutyronitrile 0.2g are added to In n,N-Dimethylformamide 80g, carries out polymerization reaction 3 hours at 70 DEG C of nitrogen atmosphere, is cooled to room temperature after reaction, Settle out polymer in water, then through ethanol washing, drying, obtains 2- cyano -3- (2- furyl) ethyl acrylate/3- benzoyl Base ethyl acrylate/1- vinyl imidazole/allyl cyclodextrin copolymers.
The preparation method of the fluorine richness epoxy resin includes the following steps: epoxy resin 10g being dissolved in N- methylpyrrole Solution is formed in alkanone 30g, and 2- fluorin benzyl amine 2g and sodium hydroxide 1g is then added into solution again, is stirred to react 4 at 70 DEG C Hour, after be precipitated in water, it is dry after taking-up, obtain fluorine richness epoxy resin.
The preparation method of the anti-plasticising silane coupling agent, includes the following steps: to mix each component, stirs 1 hour, then exist Adjusting solid content with the method for evaporation reflux at 80 DEG C is 40wt%, and anti-plasticising silane coupling agent is made.
The above-mentioned anti-plasticising silane coupling agent of one kind is application on invisible vehicle cover.
Embodiment 2
A kind of anti-plasticising silane coupling agent, each component including following parts by weight: 2- cyano -3- (2- furyl) ethyl acrylate/3- Benzoylacrylate/1- vinyl imidazole/23 parts of allyl cyclodextrin copolymers, is received 13 parts of fluorine richness epoxy resin Rice 4 parts of silica, 0.4 part of silane coupling agent KH560,1.5 parts of boracic ionic liquid, 85 parts of butanone.
2- cyano -3- (2- furyl) ethyl acrylate/3- benzoylacrylate/1- vinyl imidazole/ The preparation method of allyl cyclodextrin copolymers, include the following steps: by 2- cyano -3- (2- furyl) ethyl acrylate 10g, 3- benzoylacrylate 10g, 1- vinyl imidazole 3g, allyl cyclodextrin 1.2g, azobisisoheptonitrile 0.22g are added Into n,N-dimethylacetamide 90g, carries out polymerization reaction 3.5 hours at 73 DEG C of helium atmosphere, be cooled to after reaction Room temperature, settle out polymer in water, then through ethanol washing, drying, obtains 2- cyano -3- (2- furyl) ethyl acrylate/3- Benzoylacrylate/1- vinyl imidazole/allyl cyclodextrin copolymers.
The preparation method of the fluorine richness epoxy resin includes the following steps: epoxy resin 10g being dissolved in N- methylpyrrole Solution is formed in alkanone 35g, and 2- fluorin benzyl amine 2.5g and potassium hydroxide 1g is then added into solution again, is stirred to react at 73 DEG C 4.5 hours, after be precipitated in water, it is dry after taking-up, obtain fluorine richness epoxy resin.
The preparation method of the anti-plasticising silane coupling agent, includes the following steps: to mix each component, stirring 1.2 hours, then Adjusting solid content with the method for evaporation reflux at 90 DEG C is 43wt%, and anti-plasticising silane coupling agent is made.
The above-mentioned anti-plasticising silane coupling agent of one kind is application on invisible vehicle cover.
Embodiment 3
A kind of anti-plasticising silane coupling agent, each component including following parts by weight: 2- cyano -3- (2- furyl) ethyl acrylate/3- Benzoylacrylate/1- vinyl imidazole/27 parts of allyl cyclodextrin copolymers, is received 15 parts of fluorine richness epoxy resin Rice 4.5 parts of silica, 0.45 part of silane coupling agent KH570,2 parts of boracic ionic liquid, 90 parts of ethyl acetate.
2- cyano -3- (2- furyl) ethyl acrylate/3- benzoylacrylate/1- vinyl imidazole/ The preparation method of allyl cyclodextrin copolymers, include the following steps: by 2- cyano -3- (2- furyl) ethyl acrylate 10g, 3- benzoylacrylate 10g, 1- vinyl imidazole 3g, allyl cyclodextrin 1.5g, azodiisobutyronitrile 0.25g are added Into N-Methyl pyrrolidone 100g, is carried out polymerization reaction 4 hours at 75 DEG C of neon atmosphere, be cooled to room after reaction Temperature, settle out polymer in water, then through ethanol washing, drying, obtains 2- cyano -3- (2- furyl) ethyl acrylate/3- benzene Formoxyl ethyl acrylate/1- vinyl imidazole/allyl cyclodextrin copolymers.
The preparation method of the fluorine richness epoxy resin includes the following steps: epoxy resin 10g being dissolved in N- methylpyrrole Solution is formed in alkanone 40g, 2- fluorin benzyl amine 3g and sodium carbonate 1g is then added into solution again, and it is small to be stirred to react 5 at 75 DEG C When, after be precipitated in water, it is dry after taking-up, obtain fluorine richness epoxy resin.
The preparation method of the anti-plasticising silane coupling agent, includes the following steps: to mix each component, stirring 1.5 hours, then Adjusting solid content with the method for evaporation reflux at 100 DEG C is 45wt%, and anti-plasticising silane coupling agent is made.
The above-mentioned anti-plasticising silane coupling agent of one kind is application on invisible vehicle cover.
Embodiment 4
A kind of anti-plasticising silane coupling agent, each component including following parts by weight: 2- cyano -3- (2- furyl) ethyl acrylate/3- Benzoylacrylate/1- vinyl imidazole/32 parts of allyl cyclodextrin copolymers, is received 18 parts of fluorine richness epoxy resin Rice 5.5 parts of silica, 0.55 part of coupling agent, 2.8 parts of boracic ionic liquid, 95 parts of solvent.
The coupling agent is Silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570 in mass ratio 1: 3:1 is mixed;The solvent is acetone, butanone, ethyl acetate, butyl acetate 1:1:3:2 in mass ratio are mixed.
2- cyano -3- (2- furyl) ethyl acrylate/3- benzoylacrylate/1- vinyl imidazole/ The preparation method of allyl cyclodextrin copolymers, include the following steps: by 2- cyano -3- (2- furyl) ethyl acrylate 10g, 3- benzoylacrylate 10g, 1- vinyl imidazole 3g, allyl cyclodextrin 1.8g, initiator 0.28g are added to high boiling In point solvent 115g, carries out polymerization reaction 4.5 hours at 78 DEG C of argon atmosphere, be cooled to room temperature after reaction, in water Settle out polymer, then through ethanol washing, drying, obtains 2- cyano -3- (2- furyl) ethyl acrylate/3- benzoyl propylene Acetoacetic ester/1- vinyl imidazole/allyl cyclodextrin copolymers;High boiling solvent is N,N-dimethylformamide, N, N- diformazan Yl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide 1:3:2:2 in mass ratio are mixed;The initiator is that azo two is different Butyronitrile, azobisisoheptonitrile 3:5 in mass ratio are mixed.
The preparation method of the fluorine richness epoxy resin includes the following steps: epoxy resin 10g being dissolved in N- methylpyrrole Solution is formed in alkanone 45g, 2- fluorin benzyl amine 3.8g and basic catalyst 1g is then added into solution again, is stirred at 78 DEG C anti- Answer 5.8 hours, after be precipitated in water, it is dry after taking-up, obtain fluorine richness epoxy resin;The basic catalyst is hydroxide Sodium, potassium hydroxide, sodium carbonate, potassium carbonate 1:3:5:2 in mass ratio are mixed.
The preparation method of the anti-plasticising silane coupling agent, includes the following steps: to mix each component, stirring 1.8 hours, then Adjusting solid content with the method for evaporation reflux at 105 DEG C is 48wt%, and anti-plasticising silane coupling agent is made.
The above-mentioned anti-plasticising silane coupling agent of one kind is application on invisible vehicle cover.
Embodiment 5
A kind of anti-plasticising silane coupling agent, each component including following parts by weight: 2- cyano -3- (2- furyl) ethyl acrylate/3- Benzoylacrylate/1- vinyl imidazole/35 parts of allyl cyclodextrin copolymers, is received 20 parts of fluorine richness epoxy resin Rice 6 parts of silica, 0.6 part of Silane coupling agent KH550,3 parts of boracic ionic liquid, 100 parts of butyl acetate.
2- cyano -3- (2- furyl) ethyl acrylate/3- benzoylacrylate/1- vinyl imidazole/ The preparation method of allyl cyclodextrin copolymers, include the following steps: by 2- cyano -3- (2- furyl) ethyl acrylate 10g, 3- benzoylacrylate 10g, 1- vinyl imidazole 3g, allyl cyclodextrin 2g, azodiisobutyronitrile 0.3g are added to In dimethyl sulfoxide 120g, carries out polymerization reaction 5 hours, be cooled to room temperature after reaction, in water at 80 DEG C of nitrogen atmosphere Settle out polymer, then through ethanol washing, drying, obtains 2- cyano -3- (2- furyl) ethyl acrylate/3- benzoyl propylene Acetoacetic ester/1- vinyl imidazole/allyl cyclodextrin copolymers.
The preparation method of the fluorine richness epoxy resin includes the following steps: epoxy resin 10g being dissolved in N- methylpyrrole Solution is formed in alkanone 50g, 2- fluorin benzyl amine 4g and potassium carbonate 1g is then added into solution again, and it is small to be stirred to react 6 at 80 DEG C When, after be precipitated in water, it is dry after taking-up, obtain fluorine richness epoxy resin.
The preparation method of the anti-plasticising silane coupling agent, includes the following steps: to mix each component, stirs 2 hours, then exist Adjusting solid content with the method for evaporation reflux at 110 DEG C is 50wt%, and anti-plasticising silane coupling agent is made.
The above-mentioned anti-plasticising silane coupling agent of one kind is application on invisible vehicle cover.
Comparative example 1
The present invention provides a kind of anti-plasticising silane coupling agent, and formula and preparation method are similar to Example 1, the difference is that not adding Fluorine richness epoxy resin.
Comparative example 2
The present invention provides a kind of anti-plasticising silane coupling agent, and formula and preparation method are similar to Example 1, the difference is that not adding Nano silica.
Comparative example 3
The present invention provides a kind of anti-plasticising silane coupling agent, and formula and preparation method are similar to Example 1, the difference is that not adding Boracic ionic liquid.
Comparative example 4
The present invention provides a kind of anti-plasticising silane coupling agent, and formula and preparation method are similar to Example 1, the difference is that copolymer Without addition comonomer allyl cyclodextrin in preparation process.
Comparative example 5
Commercially available silane coupling agent.
Then silane coupling agent prepared by above embodiments 1-5 and comparative example 1-5 carries out PVC primary coat to PVC primary coat performance Test, test result are shown in Table 1, and test method refers to YFCS-SY001-2011.
Table 1
Project Thermal stability Adhesion 160 DEG C of tensile strengths Plasticizer
Unit MPa ml/100g
Embodiment 1 Without cracking and bubble It is qualified 1.5 0.2
Embodiment 2 Without cracking and bubble It is qualified 1.6 0.1
Embodiment 3 Without cracking and bubble It is qualified 1.6 0.1
Embodiment 4 Without cracking and bubble It is qualified 1.7 0
Embodiment 5 Without cracking and bubble It is qualified 1.8 0
Comparative example 1 Small cracking It is unqualified 1.0 1
Comparative example 2 Small cracking It is qualified 0.9 0.8
Comparative example 3 Micro-bubble It is qualified 1.2 0.7
Comparative example 4 Micro-bubble It is qualified 1.1 1.1
Comparative example 5 There are cracking and bubble It is unqualified 0.7 1.6
As seen from Table 1, anti-plasticising silane coupling agent disclosed by the embodiments of the present invention has more excellent heat compared with commercial product Stability, adhesion, mechanical mechanics property, and anti-plasticising performance is more preferably.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its Equivalent defines.

Claims (10)

1. a kind of anti-plasticising silane coupling agent, which is characterized in that each component including following parts by weight: 2- cyano -3- (2- furyl) Ethyl acrylate/3- benzoylacrylate/1- vinyl imidazole/20-35 parts of allyl cyclodextrin copolymers, fluorine richness 10-20 parts of epoxy resin, 3-6 parts of nano silica, 0.3-0.6 parts of coupling agent, 1-3 parts of boracic ionic liquid, solvent 80- 100 parts.
2. anti-plasticising silane coupling agent according to claim 1, which is characterized in that the coupling agent is selected from silane coupling agent At least one of KH550, silane coupling agent KH560, silane coupling agent KH570;The solvent is acetone, butanone, acetic acid second At least one of ester or butyl acetate.
3. anti-plasticising silane coupling agent according to claim 1, which is characterized in that 2- cyano -3- (2- furyl) propylene Acetoacetic ester/3- benzoylacrylate/1- vinyl imidazole/allyl cyclodextrin copolymers preparation method, including such as Lower step: by 2- cyano -3- (2- furyl) ethyl acrylate, 3- benzoylacrylate, 1- vinyl imidazole, allyl Cyclodextrin, initiator are added in high boiling solvent, and polymerization reaction 3- is carried out at nitrogen or 70-80 DEG C of atmosphere of inert gases It 5 hours, is cooled to room temperature after reaction, settle out polymer in water, then through ethanol washing, drying, obtains 2- cyano -3- (2- furyl) ethyl acrylate/3- benzoylacrylate/1- vinyl imidazole/allyl cyclodextrin copolymers.
4. anti-plasticising silane coupling agent according to claim 3, which is characterized in that 2- cyano -3- (2- furyl) propylene The quality of acetoacetic ester, 3- benzoylacrylate, 1- vinyl imidazole, allyl cyclodextrin, initiator, high boiling solvent Than for 1:1:0.3:(0.1-0.2): (0.02-0.03): (8-12).
5. anti-plasticising silane coupling agent according to claim 3, which is characterized in that the high boiling solvent is selected from N, N- dimethyl At least one of formamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide.
6. anti-plasticising silane coupling agent according to claim 3, which is characterized in that the initiator be selected from azodiisobutyronitrile, At least one of azobisisoheptonitrile;The inert gas is selected from one of helium, neon, argon gas.
7. anti-plasticising silane coupling agent according to claim 1, which is characterized in that the preparation side of the fluorine richness epoxy resin Method, includes the following steps: for epoxy resin to be dissolved in N-Methyl pyrrolidone and forms solution, and 2- fluorine is then added into solution again Benzylamine and basic catalyst are stirred to react 4-6 hours at 70-80 DEG C, after be precipitated in water, it is dry after taking-up, obtain fluorine and change Property epoxy resin.
8. anti-plasticising silane coupling agent according to claim 7, which is characterized in that the epoxy resin, N-Methyl pyrrolidone, 2- fluorin benzyl amine, basic catalyst mass ratio be 1:(3-5): (0.2-0.4): 0.1;The basic catalyst is selected from hydroxide Sodium, sodium carbonate, in potassium carbonate is at least one at potassium hydroxide.
9. anti-plasticising silane coupling agent according to claim 1-8, which is characterized in that the system of the anti-plasticising silane coupling agent Preparation Method includes the following steps: to mix each component, stirs 1-2 hours, then with the method for evaporation reflux at 80-110 DEG C Adjusting solid content is 40-50wt%, and anti-plasticising silane coupling agent is made.
10. a kind of application of anti-plasticising silane coupling agent according to claim 1-8 on invisible vehicle cover.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001131469A (en) * 1999-11-09 2001-05-15 Jsr Corp Film-forming composition, method for forming film and film
US20030035748A1 (en) * 1998-04-27 2003-02-20 Toan Trinh Uncomplexed cyclodextrin compositions for odor and wrinkle control
EP1499667A1 (en) * 2002-04-30 2005-01-26 Hydromer, Inc. Coating composition for multiple hydrophilic applications
WO2005047354A1 (en) * 2003-11-13 2005-05-26 ETH Zürich Process for producing homo-and co-polymers by raft emulsion polymerization
CN104746382A (en) * 2015-03-11 2015-07-01 山东鲁南新材料股份有限公司 Wallpaper base paper capable of adsorbing formaldehyde and production method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030035748A1 (en) * 1998-04-27 2003-02-20 Toan Trinh Uncomplexed cyclodextrin compositions for odor and wrinkle control
JP2001131469A (en) * 1999-11-09 2001-05-15 Jsr Corp Film-forming composition, method for forming film and film
EP1499667A1 (en) * 2002-04-30 2005-01-26 Hydromer, Inc. Coating composition for multiple hydrophilic applications
WO2005047354A1 (en) * 2003-11-13 2005-05-26 ETH Zürich Process for producing homo-and co-polymers by raft emulsion polymerization
CN104746382A (en) * 2015-03-11 2015-07-01 山东鲁南新材料股份有限公司 Wallpaper base paper capable of adsorbing formaldehyde and production method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
北京市油漆厂编: "《涂料工业》", 31 October 1971, 燃料化学工业出版社 *

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