CN110408294B - Anti-plasticizing bottom coating agent and preparation method and application thereof - Google Patents

Anti-plasticizing bottom coating agent and preparation method and application thereof Download PDF

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CN110408294B
CN110408294B CN201910827315.6A CN201910827315A CN110408294B CN 110408294 B CN110408294 B CN 110408294B CN 201910827315 A CN201910827315 A CN 201910827315A CN 110408294 B CN110408294 B CN 110408294B
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plasticizing
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ethyl acrylate
primer
epoxy resin
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CN110408294A (en
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严亮
陈文旭
徐赢斐
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Ningbo Jeeao Chuangyi New Materials Co 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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating 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
    • C09D151/02—Coating 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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  • Wood Science & Technology (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
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Abstract

The invention discloses an anti-plasticizing primer coating agent which is characterized by comprising the following components in parts by weight: 20-35 parts of 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer, 10-20 parts of fluorine modified epoxy resin, 3-6 parts of nano silicon dioxide, 0.3-0.6 part of coupling agent, 1-3 parts of boron-containing ionic liquid and 80-100 parts of solvent. The invention also provides a preparation method and application of the anti-plasticizing primer. The anti-plasticizing bottom coating agent disclosed by the invention has the advantages of high production efficiency, strong adhesive force with a base material, short curing time, obvious anti-plasticizing effect, small harm to the environment and human bodies, and good social benefit, ecological benefit and economic benefit.

Description

Anti-plasticizing bottom coating agent and preparation method and application thereof
Technical Field
The invention relates to the technical field of primers, in particular to an anti-plasticizing primer and a preparation method thereof.
Background
With the progress of science and technology and the development of society, automobiles become one of the main transportation means for people to travel, and the requirements for maintaining and beautifying the automobiles are increasingly increased. The invisible car cover is an important material for maintaining an automobile paint film, belongs to one kind of car body sticking films, is different from a color-changing sticking film which mainly aims at individual decoration, and has the main function of covering a car body by using a high-performance transparent environment-friendly film, providing all-around protection for car paint, improving the corrosion resistance, oxidation resistance and scratch resistance of a paint surface, not covering the color of the original paint, and also improving the overall glossiness of the car body. Therefore, the quality of the invisible car cover is improved, and the important effect is played on improving the oxidative beauty effect of the car.
The PVC invisible car cover is a common invisible car cover in the current market, the invisible car cover is easy to yellow due to PVC, pulverization can be generated along with volatilization of a plasticizer, and cracking caused after pulverization is fatal; in addition, the toughness of the materials is insufficient, and the materials are required to be attached to the surface of an automobile when in use, so that the surface of the materials is required to be treated, and the primer is adopted to carry out auxiliary treatment on the surface of the materials, so that the adhesion between the materials and an adhesive can be effectively enhanced, and the adhesion and the invisible effect of the invisible automobile coat can be improved.
The ideal primer performs the following functions: (1) protecting the basal plane (inhibiting the putrefaction of the basal body during the use process); (2) changing the surface chemical property of the matrix; (3) filling the pores and reinforcing surface weaknesses; (4) the base material is infiltrated into the interior of the base material, so that the strength of the base material is enhanced; (5) forming a coating film on the surface of the base material to inhibit the outward migration of water; (6) the product can be used indoors and outdoors, and has no odor; (7) can be applied to cement base, terrazzo, PVC base materials and the like; and (8) epoxy, waterborne epoxy, polyurethane, waterborne polyurethane and other materials can be used as the primer upper layer. However, the primer in the prior art generally cannot improve the plasticization resistance of the PVC invisible car cover, and further cannot effectively improve the surface performance of the PVC invisible car cover, and the adhesion performance needs to be further improved.
Chinese patent CN1303896A discloses a water-based epoxy primer and a preparation method thereof, which consists of water-based epoxy resin, acrylic emulsion, alkylphenol ethoxylates, formaldehyde and water; the product has no special requirement on the surface of the constructed wall or the humidity of the cement product which needs to be bonded, and the new wall and the old wall can be used. The primer has the advantages of no odor, no pollution, convenient construction and low cost. Although the primer uses the waterborne epoxy resin, no odor and no pollution are achieved, whether the primer is used on silicone adhesive and wood base materials or not is not described, the waterborne epoxy resin is not modified by modified silica sol, and the performance of the modified waterborne epoxy resin in the patent cannot be achieved.
Chinese patent CN103113789A discloses a primer for difficult-to-stick materials and a preparation method thereof, wherein chlorinated propylene, organic silicon polymer, acrylate copolymer, titanate coupling agent, benzene solvent, quinoline and stabilizer are mixed, and the solid content is adjusted at 77-110 ℃ to prepare the primer, which can effectively improve the bonding strength of difficult-to-stick materials such as polyethylene, polypropylene and the like, but the primer has the defects of quinoline existence, stink and high toxicity.
Therefore, a more effective method is sought, and the prepared anti-plasticizing primer has obvious anti-plasticizing effect, strong bonding capability and small harm to the environment and human body, and has very important significance.
Disclosure of Invention
The invention mainly aims to provide the anti-plasticization primer which has the advantages of high production efficiency, strong adhesion with a base material, short curing time, remarkable anti-plasticization effect, small harm to the environment and human bodies, and good social benefit, ecological benefit and economic benefit. Meanwhile, the invention also provides a preparation method and application of the anti-plasticizing primer.
In order to achieve the aim, the invention provides an anti-plasticizing primer which comprises the following components in parts by weight: 20-35 parts of 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer, 10-20 parts of fluorine modified epoxy resin, 3-6 parts of nano silicon dioxide, 0.3-0.6 part of coupling agent, 1-3 parts of boron-containing ionic liquid and 80-100 parts of solvent.
Further, the coupling agent is at least one selected from a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570; the solvent is at least one of acetone, butanone, ethyl acetate or butyl acetate.
Further, the preparation method of the copolymer of ethyl 2-cyano-3- (2-furyl) acrylate/ethyl 3-benzoylacrylate/1-vinylimidazole/allyl cyclodextrin comprises the following steps: adding 2-cyano-3- (2-furyl) ethyl acrylate, 3-benzoyl ethyl acrylate, 1-vinyl imidazole, allyl cyclodextrin and an initiator into a high-boiling-point solvent, carrying out polymerization reaction for 3-5 hours at 70-80 ℃ in the atmosphere of nitrogen or inert gas, cooling to room temperature after the reaction is finished, precipitating a polymer in water, washing with ethanol, and drying to obtain the 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer.
Preferably, the mass ratio of the ethyl 2-cyano-3- (2-furyl) acrylate, the ethyl 3-benzoylacrylate, the 1-vinyl imidazole, the allyl cyclodextrin, the initiator and the high boiling point solvent is 1:1:0.3 (0.1-0.2) to (0.02-0.03) to (8-12).
Preferably, the high boiling point solvent is at least one selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide.
Preferably, the initiator is selected from at least one of azobisisobutyronitrile and azobisisoheptonitrile; the inert gas is selected from helium, neon and argon.
Further, the preparation method of the fluorine modified epoxy resin comprises the following steps: dissolving epoxy resin in N-methyl pyrrolidone to form a solution, then adding 2-fluorobenzylamine and an alkaline catalyst into the solution, stirring and reacting for 4-6 hours at 70-80 ℃, then separating out in water, taking out and drying to obtain the fluorine modified epoxy resin.
Preferably, the mass ratio of the epoxy resin, the N-methylpyrrolidone, the 2-fluorobenzylamine and the alkaline catalyst is 1 (3-5): 0.2-0.4): 0.1.
Preferably, the alkaline catalyst is at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Further, the preparation method of the anti-plasticizing primer comprises the following steps: the components are mixed and stirred for 1 to 2 hours, and then the solid content is adjusted to 40 to 50 weight percent by an evaporation reflux method at the temperature of between 80 and 110 ℃ to prepare the anti-plasticizing primer.
The invention also aims to provide an application of the anti-plasticizing primer on the invisible car cover.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) the anti-plasticizing bottom coating agent disclosed by the invention has the advantages of simple preparation method and process, convenience in operation and high preparation efficiency, and meets the requirement of large-scale production.
(2) The anti-plasticizing bottom coating agent disclosed by the invention overcomes the defects that the bottom coating agent in the prior art can not improve the anti-plasticizing performance of a PVC invisible car cover generally, can not effectively improve the surface performance of the PVC invisible car cover, and the bonding performance needs to be further improved, and has the advantages of high production efficiency, strong adhesion with a base material, short curing time, remarkable anti-plasticizing effect, small harm to the environment and human body, and good social benefit, ecological benefit and economic benefit.
(3) The anti-plasticizing bottom coating agent disclosed by the invention can effectively adjust the interaction force between the plasticizer and PVC through the synergistic effect of the components, and balance the migration and plasticization of the plasticizer; the 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer is prepared by copolymerizing monomers such as 2-cyano-3- (2-furyl) ethyl acrylate, 3-benzoyl ethyl acrylate, 1-vinyl imidazole, allyl cyclodextrin copolymer and the like, and the introduced furan group and imidazole group can effectively enhance the adhesive force due to containing more active groups, and can also play a role in eliminating free radicals and improving the anti-aging performance of a coating; the introduction of cyano and benzoyl can improve the weather resistance of the paint; the other components also contain more active groups, so that the adhesive property of the material can be improved, and the invisible effect of the invisible car cover can be improved; an imidazole structure is introduced into the copolymer, so that the copolymer is easy to generate a crosslinking reaction with chlorine on the surface of PVC, and further the migration of a plasticizer in the PVC is hindered; the cyclodextrin can be beneficial to improving the bonding performance on one hand and can resist plasticization on the other hand due to the cavity structure of the cyclodextrin; by adding the boron-containing ionic liquid, the flame retardant property and the bonding property of the primer can be effectively improved, and the primer can play a role in plasticization, so that the migration of the conventional plasticizer in PVC can be effectively prevented; the epoxy resin modified by fluorine can effectively endow the epoxy resin with excellent performances such as weather resistance, yellowing resistance, temperature resistance and the like.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
The allyl cyclodextrin is prepared in advance, and the preparation method refers to the following steps: synthesis and first resolution of an all-methyl-moiety allylcyclodextrin as a gas chromatography stationary phase, chemical reagent, 2002,24 (3); the boron-containing ionic liquid is prepared in advance, and the preparation method refers to the following steps: the synthesis and standard of the boron-containing ionic liquid and the application thereof in the synthesis of borophosphate, namely Lixinjie, university of northeast, 2012; other raw materials were all purchased commercially.
Example 1
An anti-plasticizing primer coating comprises the following components in parts by weight: 20 parts of 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer, 10 parts of fluorine modified epoxy resin, 3 parts of nano silicon dioxide, KH 5500.3 parts of silane coupling agent, 1 part of boron-containing ionic liquid and 80 parts of acetone.
The preparation method of the 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer comprises the following steps: adding 10g of 2-cyano-3- (2-furyl) ethyl acrylate, 10g of 3-benzoyl ethyl acrylate, 3g of 1-vinyl imidazole, 1g of allyl cyclodextrin and 0.2g of azobisisobutyronitrile into 80g of N, N-dimethylformamide, carrying out polymerization reaction for 3 hours at 70 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, precipitating a polymer in water, washing with ethanol, and drying to obtain the 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer.
The preparation method of the fluorine modified epoxy resin comprises the following steps: 10g of epoxy resin is dissolved in 30g of N-methyl pyrrolidone to form a solution, then 2g of 2-fluorobenzylamine and 1g of sodium hydroxide are added into the solution, the mixture is stirred and reacted for 4 hours at 70 ℃, and then the mixture is separated out in water, taken out and dried to obtain the fluorine modified epoxy resin.
The preparation method of the anti-plasticizing primer comprises the following steps: the components are mixed and stirred for 1 hour, and then the solid content is adjusted to 40 weight percent by an evaporation reflux method at 80 ℃ to prepare the anti-plasticizing primer.
The anti-plasticizing bottom coating agent is applied to invisible car coats.
Example 2
An anti-plasticizing primer coating comprises the following components in parts by weight: 23 parts of 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer, 13 parts of fluorine modified epoxy resin, 4 parts of nano silicon dioxide, KH 5600.4 parts of silane coupling agent, 1.5 parts of boron-containing ionic liquid and 85 parts of butanone.
The preparation method of the 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer comprises the following steps: adding 10g of 2-cyano-3- (2-furyl) ethyl acrylate, 10g of 3-benzoyl ethyl acrylate, 3g of 1-vinyl imidazole, 1.2g of allyl cyclodextrin and 0.22g of azobisisoheptonitrile into 90g of N, N-dimethylacetamide, carrying out polymerization reaction for 3.5 hours at 73 ℃ in a helium atmosphere, cooling to room temperature after the reaction is finished, precipitating a polymer in water, washing with ethanol, and drying to obtain the 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer.
The preparation method of the fluorine modified epoxy resin comprises the following steps: 10g of epoxy resin is dissolved in 35g of N-methyl pyrrolidone to form a solution, then 2.5g of 2-fluorobenzylamine and 1g of potassium hydroxide are added into the solution, the mixture is stirred and reacted for 4.5 hours at 73 ℃, then the mixture is separated out in water, and the mixture is taken out and dried to obtain the fluorine modified epoxy resin.
The preparation method of the anti-plasticizing primer comprises the following steps: the components are mixed and stirred for 1.2 hours, and then the solid content is adjusted to 43 weight percent by an evaporation reflux method at 90 ℃ to prepare the anti-plasticizing primer.
The anti-plasticizing bottom coating agent is applied to invisible car coats.
Example 3
An anti-plasticizing primer coating comprises the following components in parts by weight: 27 parts of 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer, 15 parts of fluorine modified epoxy resin, 4.5 parts of nano silicon dioxide, KH 5700.45 parts of silane coupling agent, 2 parts of boron-containing ionic liquid and 90 parts of ethyl acetate.
The preparation method of the 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer comprises the following steps: adding 10g of 2-cyano-3- (2-furyl) ethyl acrylate, 10g of 3-benzoyl ethyl acrylate, 3g of 1-vinyl imidazole, 1.5g of allyl cyclodextrin and 0.25g of azobisisobutyronitrile into 100g of N-methyl pyrrolidone, carrying out polymerization reaction for 4 hours at 75 ℃ in neon atmosphere, cooling to room temperature after the reaction is finished, precipitating a polymer in water, washing with ethanol, and drying to obtain the 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer.
The preparation method of the fluorine modified epoxy resin comprises the following steps: dissolving 10g of epoxy resin in 40g of N-methylpyrrolidone to form a solution, then adding 3g of 2-fluorobenzylamine and 1g of sodium carbonate into the solution, stirring and reacting for 5 hours at 75 ℃, then precipitating in water, taking out and drying to obtain the fluorine modified epoxy resin.
The preparation method of the anti-plasticizing primer comprises the following steps: the components are mixed and stirred for 1.5 hours, and then the solid content is adjusted to 45 weight percent by an evaporation reflux method at 100 ℃ to prepare the anti-plasticizing primer.
The anti-plasticizing bottom coating agent is applied to invisible car coats.
Example 4
An anti-plasticizing primer coating comprises the following components in parts by weight: 32 parts of 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer, 18 parts of fluorine modified epoxy resin, 5.5 parts of nano silicon dioxide, 0.55 part of coupling agent, 2.8 parts of boron-containing ionic liquid and 95 parts of solvent.
The coupling agent is formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to the mass ratio of 1:3: 1; the solvent is formed by mixing acetone, butanone, ethyl acetate and butyl acetate according to the mass ratio of 1:1:3: 2.
The preparation method of the 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer comprises the following steps: adding 10g of 2-cyano-3- (2-furyl) ethyl acrylate, 10g of 3-benzoyl ethyl acrylate, 3g of 1-vinyl imidazole, 1.8g of allyl cyclodextrin and 0.28g of initiator into 115g of a high-boiling-point solvent, carrying out polymerization reaction for 4.5 hours at 78 ℃ in an argon atmosphere, cooling to room temperature after the reaction is finished, precipitating a polymer in water, washing with ethanol, and drying to obtain a 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer; the high boiling point solvent is formed by mixing N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide according to the mass ratio of 1:3:2: 2; the initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5.
The preparation method of the fluorine modified epoxy resin comprises the following steps: dissolving 10g of epoxy resin in 45g of N-methylpyrrolidone to form a solution, then adding 3.8g of 2-fluorobenzylamine and 1g of alkaline catalyst into the solution, stirring and reacting at 78 ℃ for 5.8 hours, then separating out in water, taking out and drying to obtain fluorine modified epoxy resin; the alkaline catalyst is prepared by mixing sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate according to the mass ratio of 1:3:5: 2.
The preparation method of the anti-plasticizing primer comprises the following steps: the components are mixed and stirred for 1.8 hours, and then the solid content is adjusted to 48 weight percent by an evaporation reflux method at 105 ℃ to prepare the anti-plasticizing primer.
The anti-plasticizing bottom coating agent is applied to invisible car coats.
Example 5
An anti-plasticizing primer coating comprises the following components in parts by weight: 35 parts of 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer, 20 parts of fluorine modified epoxy resin, 6 parts of nano silicon dioxide, KH 5500.6 parts of silane coupling agent, 3 parts of boron-containing ionic liquid and 100 parts of butyl acetate.
The preparation method of the 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer comprises the following steps: adding 10g of 2-cyano-3- (2-furyl) ethyl acrylate, 10g of 3-benzoyl ethyl acrylate, 3g of 1-vinyl imidazole, 2g of allyl cyclodextrin and 0.3g of azobisisobutyronitrile into 120g of dimethyl sulfoxide, carrying out polymerization reaction for 5 hours at 80 ℃ in a nitrogen atmosphere, cooling to room temperature after the reaction is finished, precipitating a polymer in water, washing with ethanol, and drying to obtain the 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer.
The preparation method of the fluorine modified epoxy resin comprises the following steps: dissolving 10g of epoxy resin in 50g of N-methylpyrrolidone to form a solution, then adding 4g of 2-fluorobenzylamine and 1g of potassium carbonate into the solution, stirring and reacting at 80 ℃ for 6 hours, then precipitating in water, taking out and drying to obtain the fluorine modified epoxy resin.
The preparation method of the anti-plasticizing primer comprises the following steps: the components are mixed and stirred for 2 hours, and then the solid content is adjusted to 50 weight percent by an evaporation reflux method at 110 ℃ to prepare the anti-plasticizing primer.
The anti-plasticizing bottom coating agent is applied to invisible car coats.
Comparative example 1
The invention provides an anti-plasticizing primer, and the formula and the preparation method are similar to those of the primer in the example 1, except that the fluorine modified epoxy resin is not added.
Comparative example 2
The invention provides an anti-plasticizing primer, and the formula and the preparation method are similar to those of the primer in the embodiment 1, except that no nano silicon dioxide is added.
Comparative example 3
The invention provides an anti-plasticization primer, the formula and the preparation method are similar to those of the example 1, except that no boron-containing ionic liquid is added.
Comparative example 4
The invention provides an anti-plasticization primer, the formula and the preparation method are similar to those of the example 1, except that no comonomer allyl cyclodextrin is added in the preparation process of the copolymer.
Comparative example 5
A commercially available primer.
The primer prepared in the above examples 1-5 and comparative examples 1-5 is used for priming PVC, and then the performance of the PVC primer is tested, the test results are shown in Table 1, and the test method refers to YFCS-SY 001-2011.
TABLE 1
Item Thermal stability Adhesion Property Tensile strength at 160 DEG C Precipitation of plasticizer
Unit of — — MPa ml/100g
Example 1 No cracking and no bubbles Qualified 1.5 0.2
Example 2 No cracking and no bubbles Qualified 1.6 0.1
Example 3 No cracking and no bubbles Qualified 1.6 0.1
Example 4 No cracking and no bubbles Qualified 1.7 0
Example 5 No cracking and no bubbles Qualified 1.8 0
Comparative example 1 Micro cracking Fail to be qualified 1.0 1
Comparative example 2 Micro cracking Qualified 0.9 0.8
Comparative example 3 Micro-bubbles Qualified 1.2 0.7
Comparative example 4 Micro-bubbles Qualified 1.1 1.1
Comparative example 5 With cracks and blisters Fail to be qualified 0.7 1.6
As can be seen from table 1, the anti-plasticization primer disclosed in the embodiments of the present invention has more excellent thermal stability, adhesion, mechanical properties, and anti-plasticization performance compared to the commercially available products.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (9)

1. The anti-plasticizing primer is characterized by comprising the following components in parts by weight: 20-35 parts of 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer, 10-20 parts of fluorine modified epoxy resin, 3-6 parts of nano silicon dioxide, 0.3-0.6 part of coupling agent, 1-3 parts of boron-containing ionic liquid and 80-100 parts of solvent;
the preparation method of the 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer comprises the following steps: adding 2-cyano-3- (2-furyl) ethyl acrylate, 3-benzoyl ethyl acrylate, 1-vinyl imidazole, allyl cyclodextrin and an initiator into a high-boiling-point solvent, carrying out polymerization reaction for 3-5 hours at 70-80 ℃ in the atmosphere of nitrogen or inert gas, cooling to room temperature after the reaction is finished, precipitating a polymer in water, washing with ethanol, and drying to obtain the 2-cyano-3- (2-furyl) ethyl acrylate/3-benzoyl ethyl acrylate/1-vinyl imidazole/allyl cyclodextrin copolymer.
2. The anti-plasticizing primer according to claim 1 wherein the coupling agent is selected from at least one of silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH 570; the solvent is at least one of acetone, butanone, ethyl acetate or butyl acetate.
3. The anti-plasticizing primer according to claim 1 wherein the mass ratio of ethyl 2-cyano-3- (2-furyl) acrylate, ethyl 3-benzoylacrylate, 1-vinylimidazole, allylcyclodextrin, initiator, high boiling point solvent is 1:1:0.3 (0.1-0.2): 0.02-0.03): 8-12.
4. The anti-plasticizing primer according to claim 1 wherein the high boiling point solvent is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide.
5. The anti-plasticising primer according to claim 1, characterised in that the initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptonitrile; the inert gas is selected from helium, neon and argon.
6. The anti-plasticising primer coating according to claim 1, characterised in that the process for the preparation of the fluorine-modified epoxy resin comprises the following steps: dissolving epoxy resin in N-methyl pyrrolidone to form a solution, then adding 2-fluorobenzylamine and an alkaline catalyst into the solution, stirring and reacting for 4-6 hours at 70-80 ℃, then separating out in water, taking out and drying to obtain the fluorine modified epoxy resin.
7. The anti-plasticization primer according to claim 6, wherein the mass ratio of the epoxy resin, the N-methylpyrrolidone, the 2-fluorobenzylamine and the alkaline catalyst is 1 (3-5): 0.2-0.4): 0.1; the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
8. The anti-plasticizing primer according to any one of claims 1 to 7, characterized in that the process for preparing the anti-plasticizing primer comprises the following steps: the components are mixed and stirred for 1 to 2 hours, and then the solid content is adjusted to 40 to 50 weight percent by an evaporation reflux method at the temperature of between 80 and 110 ℃ to prepare the anti-plasticizing primer.
9. Use of an anti-plasticising primer according to any one of claims 1 to 7 on a contact car cover.
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