CN102898932B - Composite ultraviolet-curing coating containing vinyl-terminated fluorinated alkyl ester polymer, its preparation and application - Google Patents
Composite ultraviolet-curing coating containing vinyl-terminated fluorinated alkyl ester polymer, its preparation and application Download PDFInfo
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Abstract
The invention discloses a composite ultraviolet-curing coating containing a vinyl-terminated fluorinated alkyl ester polymer, its preparation and application. The composite ultraviolet-curing coating contains the following components by weight: 100 parts of epoxy (meth) acrylic resin, 0.01-50 parts of the vinyl-terminated fluorinated alkyl ester polymer as shown in formula I, 2-20 parts of an active diluent monomer, 0.5-8 parts of a photoinitiator, 2-30 parts of an inorganic salt filler, 0.5-5 parts of a dispersing agent and 0.1-4 parts of a defoaming agent. The vinyl-terminated fluorinated alkyl ester polymer and the epoxy (meth) acrylic resin in the composite ultraviolet-curing coating have good compatibility. The composite ultraviolet-curing coating provided in the invention has the advantages of excellent hydrophobicity, chemical and pollution resistance, as well as wide application range. (formula I).
Description
Technical field
The present invention relates to chemistry painting industry, the particularly coating material solidified and preparation and application of a kind of complex light containing end-vinyl fluorinated alkyl ester polymer.
Background technology
The features such as ultraviolet-curing paint is short owing to having set time, and energy consumption is low, solvent-free, are widely used in novel building base material, the fields such as binding agent, ink, metal electron component package.Wherein, epoxy (methyl) acrylic resin paint is cheap because of it, abundance, hardness is high, advantages such as transparency is good and being widely used, but also there is weathering resistance, the problem such as wear no resistance, particularly due to surface tension that epoxy acrylic resin is higher, the epoxypaint surface of preparation has and has higher surface energy, thus limits its use at the hydrophobic speciality coating of height.Although add by physics mode surface property and the chemical resistance that organic fluorine can improve coating, because organic fluorine is with the poor compatibility of epoxy coating, easily occurs being separated, reduce the bulk properties of coating; Add micromolecular reactive fluorochemical monomer in addition, although can increase its consistency, usage quantity is large, and has certain volatility, contaminate environment.Moreover from technique effect, short fluorine-containing chain is difficult to the surface moving to coating, weakens the effect of fluoro-containing group modification, thus causes cost relatively high, thus strongly limit the range of application of organic fluorine coating.
Summary of the invention
Primary and foremost purpose of the present invention is to overcome the shortcoming and defect of existing epoxy (methyl) acrylic resin paint at hydrophobic performance, anti-pollution characteristic, weather resistance, and overcome existing organic fluorine add coating be easily separated, the shortcomings such as the how low sticking power of addition, provide a kind of high water-fast, corrosion-resistant, high adhesive force, Environmental Safety complex light containing end-vinyl fluorinated alkyl ester polymer coating material solidified.
Another object of the present invention is to provide the described preparation method coating material solidified containing the complex light of end-vinyl fluorinated alkyl ester polymer.
Another object of the present invention is to provide the described application coating material solidified containing the complex light of end-vinyl fluorinated alkyl ester polymer.
Object of the present invention is achieved through the following technical solutions: a kind of complex light containing end-vinyl fluorinated alkyl ester polymer is coating material solidified, comprises the following component by mass parts:
Epoxy (methyl) acrylic resin 100 parts, end-vinyl fluorinated alkyl ester polymer 0.01 ~ 50 part, activity diluting monomer 2 ~ 20 parts, light trigger 0.5 ~ 8 part, inorganic salt filler 2 ~ 30 parts, dispersion agent 0.5 ~ 5 part and defoamer 0.1 ~ 4 part;
Described epoxy (methyl) acrylic resin refers to epoxy methacrylic resin or epoxy acrylic resin; It is that diglycidyl ether type epoxy resin and (methyl) vinylformic acid (i.e. acrylic or methacrylic acid) reaction are obtained, prepared by the method comprising following steps: by 100 mass parts diglycidyl ether type epoxy resin heated and stirred to 60 ~ 90 DEG C, then 0.1 ~ 100 mass parts (methyl) vinylformic acid is added, 0.05 ~ 3 mass parts of catalyst and 0.05 ~ 3 mass parts stopper, then 95 ~ 130 DEG C are warmed up to, react 1 ~ 7 hour, obtained epoxy (methyl) acrylic resin;
The oxirane value of described diglycidyl ether type epoxy resin is 0.01 ~ 0.87, is at least one in bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, epoxidation linear phenolic resin, Resorcinol bisglycidyl ether type epoxy resin, Phloroglucinol monomethyl ether three-glycidyl ether type epoxy resin or two Resorcinol formal four diglycidyl ether type epoxy resin;
Described catalyzer is preferably quaternary ammonium salt, is more preferably Tetrabutyl amonium bromide;
Described stopper is preferably Resorcinol;
The structural formula of described end-vinyl fluorinated alkyl ester polymer is such as formula shown in I:
(formula I);
Wherein: R ' is-H or-CH
3; R " represent that carbon chain lengths is C
1~ C
4alkyl; R " ' be-H or-CH
3; R
fexpression carbon chain lengths is C
1~ C
16fluorine-containing ester group, fluorine-containing ester group refers to hydrogen atom wherein by the some or all of displacement of fluorine atom; N is the integer between 3 ~ 50;
Described end-vinyl fluorinated alkyl ester polymer is obtained by the preparation method comprising following steps:
(1) be that the TBAH aqueous solution of mass percent 10% is even by 0.5 ~ 10 mass parts butyl ethyl malonate, 20 ~ 200 mass parts toluene and 0.2 ~ 20 mass parts concentration, reaction 1 ~ 20h; Then 40 ~ 200 mass parts tetrahydrofuran (THF)s and 10 ~ 100 mass parts fluorochemical monomers are added, mix reaction 0.2 ~ 3h, after removing tetrahydrofuran (THF), be hydrolyzed 0.5 ~ 6h in the mixing solutions of 20 ~ 80 DEG C in temperature by the product obtained, obtain the fluoropolymer of end carboxyl; Wherein, described mixing solutions is that 5 ~ 60 mass parts trifluoroacetic acids and 30 ~ 100 mass parts dioxane are mixed to get;
(2) mix in the fluoropolymer of 2 ~ 20 mass parts end carboxylic acids and 30 ~ 300 mass parts solvents, then 5 ~ 40 mass parts (methyl) acrylic acid hydroxy alkyl ester, 0.2 ~ 5 mass parts dewatering agent and 0.01 ~ 2 mass parts of catalyst is added, in 0 ~ 60 DEG C of reaction 4 ~ 48 hours, obtained end-vinyl fluorinated alkyl ester polymer;
Fluorochemical monomer described in step (1) is preferably at least one in vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester or methacrylic acid-1H ,-1H-perfluoro monooctyl ester;
Solvent described in step (2) is at least one in tetrahydrofuran (THF), pyridine, methylene dichloride, trichloromethane or dimethyl formamide;
(methyl) acrylic acid hydroxy alkyl ester described in step (2) is at least one in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410 or hy-droxybutyl;
Dewatering agent described in step (2) is preferably 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) or N, N ' one or both in-dicyclohexylcarbodiimide (DCC);
Catalyzer described in step (2) is preferably at least one in DMAP (DMAP), the chloro-1-hydroxy benzo triazole (HOBT) of 1-hydroxyl-7-azo benzotriazole (HOAT) or 6-;
Described activity diluting monomer is preferably at least one in tripropylene glycol dimethacrylate, tri (propylene glycol) diacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, ethoxyquin Glycerin triacrylate or ethoxyquin Glycerin methyl triacrylate;
Described light trigger is preferably benzophenone, Benzoin ethyl ether, benzoin dimethylether, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyciohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide or two 2, at least one in 4,6-trimethylbenzoyl phenyl phosphine oxide;
Described inorganic salt filler is preferably at least one in titanium dioxide, talcum powder, light calcium carbonate or water-ground limestone;
Described defoamer is preferably mineral oil defoaming agent or polysiloxane defoamers;
The defoamer that described mineral oil defoaming agent is preferably Shanghai this promise chemistry Science and Technology Ltd., model is SN-919 or Guangzhou Guan Zhi Chemical Co., Ltd., model are one or both in the defoamer of BEK-750;
Described polysiloxane defoamers is preferably Guangzhou Fu Yuan Science and Technology Ltd., model is at least one in the defoamer of FY2309, FY2311H or FY-3300;
Described dispersion agent is preferably vinylformic acid sodium salt, polyacrylic acid sodium salt or polycarboxylate sodium;
The described preparation method coating material solidified containing the complex light of end-vinyl fluorinated alkyl ester polymer, comprises following steps:
(1) preparation of epoxy (methyl) acrylic resin: by 100 mass parts diglycidyl ether type epoxy resin heated and stirred to 60 ~ 90 DEG C, then 0.1 ~ 100 mass parts (methyl) vinylformic acid is added, 0.05 ~ 3 mass parts of catalyst and 0.05 ~ 3 mass parts stopper, then 95 ~ 130 DEG C are warmed up to, react 1 ~ 7 hour, obtained epoxy (methyl) acrylic resin;
(2) preparation of the fluoropolymer of end carboxyl: the TBAH aqueous solution by 0.5 ~ 10 mass parts butyl ethyl malonate, 20 ~ 200 mass parts toluene and 0.2 ~ 20 mass parts concentration being mass percent 10% is even, reaction 1 ~ 20h; Then 40 ~ 200 mass parts tetrahydrofuran (THF)s and 10 ~ 100 mass parts fluorochemical monomers are added, mix reaction 0.2 ~ 3h, after removing tetrahydrofuran (THF), be hydrolyzed 0.5 ~ 6h in the mixing solutions of 20 ~ 80 DEG C in temperature by the product obtained, obtain the fluoropolymer of end carboxyl; Wherein, described mixing solutions is that 5 ~ 60 mass parts trifluoroacetic acids and 30 ~ 100 mass parts dioxane are mixed to get;
(3) preparation of end-vinyl fluorinated alkyl ester polymer: mix in the fluoropolymer of end carboxylic acid prepared by 2 ~ 20 mass parts steps (2) and 30 ~ 300 mass parts solvents, then 5 ~ 40 mass parts (methyl) acrylic acid hydroxy alkyl ester, 0.2 ~ 5 mass parts dewatering agent and 0.01 ~ 2 mass parts of catalyst is added, in 0 ~ 60 DEG C of reaction 4 ~ 48 hours, obtained end-vinyl fluorinated alkyl ester polymer;
(4) containing the preparation that the complex light of end-vinyl fluorinated alkyl ester polymer is coating material solidified: end-vinyl fluorinated alkyl ester polymer, 2 ~ 20 mass parts activity diluting monomers, 0.5 ~ 8 mass parts light trigger, 2 ~ 30 mass parts inorganic salt filler, 0.5 ~ 5 mass parts dispersion agent and 0.1 ~ 4 mass parts defoamer prepared by epoxy (methyl) acrylic resin 100 mass parts steps (1) prepared, 0.01 ~ 50 mass parts step (3) mix, the complex light obtained containing end-vinyl fluorinated alkyl ester polymer is coating material solidified.
The oxirane value of the diglycidyl ether type epoxy resin described in step (1) is 0.01 ~ 0.87, is at least one in bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, epoxidation linear phenolic resin, Resorcinol bisglycidyl ether type epoxy resin, Phloroglucinol monomethyl ether three-glycidyl ether type epoxy resin or two Resorcinol formal four diglycidyl ether type epoxy resin;
Catalyzer described in step (1) is preferably quaternary ammonium salt, is more preferably Tetrabutyl amonium bromide;
Stopper described in step (1) is preferably Resorcinol;
Fluorochemical monomer described in step (2) is preferably at least one in vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester or methacrylic acid-1H ,-1H-perfluoro monooctyl ester;
Solvent described in step (3) is at least one in tetrahydrofuran (THF), pyridine, methylene dichloride, trichloromethane or dimethyl formamide;
(methyl) acrylic acid hydroxy alkyl ester described in step (3) is at least one in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, hy-droxybutyl;
Dewatering agent described in step (3) is preferably 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) or N, N ' one or both in-dicyclohexylcarbodiimide (DCC);
Catalyzer described in step (3) is preferably at least one in DMAP (DMAP), the chloro-1-hydroxy benzo triazole (HOBT) of 1-hydroxyl-7-azo benzotriazole (HOAT), 6-;
Described coating material solidified can the applying in building field, electronic applications of complex light containing end-vinyl fluorinated alkyl ester polymer.
The present invention has following advantage and effect relative to prior art:
Complex light containing end-vinyl fluorinated alkyl ester polymer provided by the present invention is coating material solidified is the carbon-carbon double bond fluoropolymer (i.e. end-vinyl fluorinated alkyl ester polymer) added in epoxy (methyl) acrylic resin containing photoactivatable groups.Because fluoropolymer has high molecular weight and fluorine content, fluoropolymer is made more easily to move to the coating material solidified air-coating surface of complex light, thus cause the fluorine content on surface to be greatly greater than body fluorine content, thus, a small amount of end (methyl) alkyl acrylate fluoropolymer can make composite coating have excellent hydrophobic performance, chemically-resistant and anti-pollution characteristic; In addition, owing to introducing photosensitive group in fluoropolymer, chemical bonding can be carried out with (methyl) acrylic acid epoxy resin, improve the consistency containing end-vinyl fluorinated alkyl ester polymer and epoxy (methyl) acrylic acid epoxy resin.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) preparation of epoxy methacrylic resin: 100 mass parts bisphenol A epoxide resins (oxirane value 0.01) are added in the reactor that reflux condensing tube, dropping funnel, thermometer and agitator are housed, heated and stirred to 60 DEG C, then 2.5 mass parts Tetrabutyl amonium bromides, 0.5 mass parts Resorcinol and 20 mass parts methacrylic acids are added, be warmed up to 130 DEG C, react 2 hours, obtained epoxy methacrylic resin.
(2) preparation of the fluoropolymer of end carboxyl: the TBAH aqueous solution by 10 quality butyl ethyl malonates, 30 mass parts toluene and 0.2 mass parts concentration being mass percent 10% is even, reaction 10h; Then 40 mass parts tetrahydrofuran (THF)s and 10 mass parts vinylformic acid trifluoro ethyl ester monomers are added, mix reaction 0.3h, after removing tetrahydrofuran (THF), by the product obtained hydrolysis 6h in the mixing solutions (10 mass parts trifluoroacetic acids and 60 mass parts dioxane are mixed to get) of 80 DEG C, obtain the fluoropolymer of end carboxyl.
(3) preparation of end-vinyl fluorinated alkyl ester polymer: the fluoropolymer of the end carboxylic acid 2 mass parts steps (2) prepared joins in 100 mass parts tetrahydrofuran solutions and mixes, then 5 mass parts hydroxyethyl methylacrylates, 1 mass parts N is added, N '-dicyclohexylcarbodiimide and 0.05 mass parts 1-hydroxyl-7 azo benzotriazole, 20 DEG C of reactions 15 hours, obtained end-vinyl fluorinated alkyl ester polymer.By FT-IR(1635 and 1608cm
-1the charateristic avsorption band of C=O and C=C respectively) and
1h-NMR(4.2 ~ 4.4ppm is-CH
2cH
2the charateristic avsorption band of-middle Hydrogen Proton; 5.6 ~ 5.7 and 6.0 ~ 6.1ppm be CH
2the absorption peak of Hydrogen Proton in=C-double bond) to determine, its structure is such as formula shown in II:
(formula II);
(4) containing the preparation that the complex light of end-vinyl fluorinated alkyl ester polymer is coating material solidified: epoxy methacrylic resin 100 mass parts prepared by step (1), join in container, end-vinyl fluorinated alkyl ester polymer 20 mass parts prepared by step (3) is added again successively under strong stirring, tripropylene glycol dimethacrylate 15 mass parts, light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone 0.5 mass parts, titanium dioxide 20 mass parts, dispersion agent (vinylformic acid sodium salt, DC40, Weifang Heng Hai Chemical Co., Ltd.) 0.5 mass parts, defoamer organic silicone oil (FY-3300, Guangzhou Fu Yuan Science and Technology Ltd.) 0.5 mass parts, often add a kind of reaction raw materials all to stir, add another kind of reaction raw materials again.After mixing, the complex light obtained containing end-vinyl fluorinated alkyl ester polymer is coating material solidified.
After curing of coating, performance is as follows: film adhesive (measures by GB/T 1720-1979 (1989), following examples are same) be 1 grade, (contact angle measurement is adopted to measure the contact angle of distilled water in film coated surface with the contact angle of water, all measurements are all carried out under room temperature (25 DEG C), following examples with) 105 °, pencil hardness (measures by GB/6739-1996, following examples are same) 4H, artificial weathering ageing resistance (measures by GB/T1865-88, following examples are same) 550h, water tolerance (measures by GB/1733-1993, following examples with) 270h is unchanged, acid resistance (measures by GB/T9274-1988, following examples with) the unchanged and alkali resistance of 72h (measures by GB/T9274-1988, following examples with) 72h is unchanged.
Embodiment 2
(1) preparation of epoxy methacrylic resin: get bisphenol-s epoxy resin (oxirane value 0.51) 100 mass parts and add in the reactor that reflux condensing tube, dropping funnel, thermometer and agitator are housed, heated and stirred to 85 DEG C, then Tetrabutyl amonium bromide 3 mass parts is added, Resorcinol 0.05 mass parts, vinylformic acid 100 mass parts, be warmed up to 125 DEG C, react 6.5 hours, obtained epoxy acrylic resin.
(2) preparation of the fluoropolymer of end carboxyl: the TBAH aqueous solution by 7 mass parts butyl ethyl malonates, 120 mass parts toluene and 12 mass parts concentration being mass percent 10% is even, reaction 20h; Then 180 mass parts tetrahydrofuran (THF)s and 100 mass parts trifluoroethyl methacrylate monomers are added, mix reaction 0.2h, after removing tetrahydrofuran (THF), by the product obtained hydrolysis 2h in the mixing solutions (5 mass parts trifluoroacetic acids and 100 mass parts dioxane are mixed to get) of 20 DEG C, obtain the fluoropolymer of end carboxyl.
(3) preparation of end-vinyl fluorinated alkyl ester polymer: the fluoropolymer of the end carboxyl 5 mass parts steps (2) prepared joins in 280 parts by mass Methylene chloride solution and mixes, then 20 mass parts Hydroxyethyl acrylates, 3 mass parts N are added, N '-dicyclohexylcarbodiimide and 1.5 mass parts DMAPs, 0 DEG C of reaction 48 hours, obtained end-vinyl fluorinated alkyl ester polymer.By FT-IR(1638 and 1606cm
-1the charateristic avsorption band of C=O and C=C respectively) and
1h-NMR(5.7 ~ 5.8 and 6.3 ~ 6.4ppm are CH
2=C-, 6.0 ~ 6.2ppm are the absorption peak of C=CH-C=O Hydrogen Proton in double bond) to determine, its structure is as shown in formula III:
(formula III);
(4) containing the preparation that the complex light of end-vinyl fluorinated alkyl ester polymer is coating material solidified: epoxy acrylic resin 100 mass parts prepared by step (1), join in container, end-vinyl fluorinated alkyl ester polymer 35 mass parts prepared by step (3) is added again successively under strong stirring, tri (propylene glycol) diacrylate 2 mass parts, light trigger Benzoin ethyl ether 1.5 mass parts, talcum powder 25 mass parts, polycarboxylate sodium (SN-5040, Guangzhou Guan Zhi Chemical Co., Ltd.) 2 mass parts and mineral oil defoaming agent (SN-919, this promise chemistry Science and Technology Ltd. of Shanghai) 3.5 mass parts, often add a kind of reaction raw materials all to stir, add another kind of reaction raw materials again.After mixing, the complex light obtained containing end-vinyl fluorinated alkyl ester polymer is coating material solidified.
After curing of coating, performance is as follows: adhesion 1 grade, unchanged with the contact angle 125 ° of water, pencil hardness 4H, artificial weathering ageing resistance 600h, water tolerance 300h, and acid resistance 72h is unchanged and alkali resistance 72h is unchanged.
Embodiment 3
(1) preparation of epoxy methacrylic resin: get epoxidation linear phenolic resin (oxirane value 0.50, Wuxi resin processing plant, model F51) 100 mass parts add in the reactor that reflux condensing tube, dropping funnel, thermometer and agitator are housed, heated and stirred to 90 DEG C, then adds Tetrabutyl amonium bromide 0.05 mass parts, Resorcinol 3 mass parts, methacrylic acid 0.1 mass parts, be warmed up to 110 DEG C, react 1 hour, obtained epoxy methacrylic resin.
(2) preparation of the fluoropolymer of end carboxyl: 4 mass parts butyl ethyl malonates, 200 mass parts toluene and 3 mass parts concentration are that the TBAH aqueous solution of mass percent 10% is even, reaction 1h; Then 60 mass parts tetrahydrofuran (THF)s and 50 mass parts Hexafluorobutyl mathacrylate monomers are added, mix reaction 1.5h, after removing tetrahydrofuran (THF), by the product obtained hydrolysis 3h in the mixing solutions (20 mass parts trifluoroacetic acids and 30 mass parts dioxane are mixed to get) of 40 DEG C, obtain the fluoropolymer of end carboxyl.
(3) preparation of end-vinyl fluorinated alkyl ester polymer: the fluoropolymer of the end carboxylic acid 10 mass parts steps (2) prepared joins in 300 mass parts chloroform solns and mixes, then 30 mass parts hy-droxybutyl, 3.5 mass parts 1-ethyls-(3-dimethylaminopropyl) carbodiimide hydrochloride and the chloro-1-hydroxy benzo triazole of 0.01 mass parts 6-is added, 40 DEG C of reactions 35 hours, obtained end-vinyl fluorinated alkyl ester polymer.By FT-IR(1633 and 1611cm
-1the charateristic avsorption band of C=O and C=C respectively) and
1h-NMR(5.7 ~ 5.8 and 6.3 ~ 6.4ppm are CH
2=C-, 6.0 ~ 6.2ppm are the absorption peak of C=CH-C=O Hydrogen Proton in double bond) to determine, its structure is such as formula shown in IV:
(formula IV);
(4) containing the preparation that the complex light of end-vinyl fluorinated alkyl ester polymer is coating material solidified: epoxy methacrylic resin 100 mass parts prepared by step (1), join in container, add terminal methyl vinylformic acid prepared by step (3) under strong stirring more successively and fluoridize butyl ester polymkeric substance thing 2.8 mass parts, pentaerythritol triacrylate 20 mass parts, light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone 6.5 mass parts, talcum powder 30 mass parts, defoamer mineral oils (BEK-750, Guangzhou Guan Zhi Chemical Co., Ltd.) 0.1 mass parts and dispersion agent polyacrylic acid sodium salt (TH-1100, Shandong Taihe Water Treatment Co., Ltd.) 0.5 mass parts, often add a kind of reaction raw materials all to stir, add another kind of reaction raw materials again.After mixing, the complex light obtained containing end-vinyl fluorinated alkyl ester polymer is coating material solidified.
After curing of coating, performance is as follows: sticking power 2 grades, with contact angle 115 °, the pencil hardness 5H of water, artificial weathering ageing resistance 600h is unchanged, water tolerance 260h is unchanged, acid resistance 72h is unchanged and alkali resistance 72h is unchanged.
Embodiment 4
(1) preparation of epoxy acrylic resin: get Phloroglucinol monomethyl ether three-glycidyl ether type epoxy resin (oxirane value 0.87) 100 mass parts and add in the reactor that reflux condensing tube, dropping funnel, thermometer and agitator are housed, heated and stirred to 90 DEG C, then Tetrabutyl amonium bromide 1.8 mass parts is added, Resorcinol 2.1 mass parts, vinylformic acid 38 mass parts, be warmed up to 95 DEG C, react 4 hours, obtained epoxy acrylic resin.
(2) preparation of the fluoropolymer of end carboxyl: the TBAH aqueous solution by 10 mass parts butyl ethyl malonates, 200 mass parts toluene and 20 mass parts concentration being mass percent 10% is even, reaction 15h; Then 200 mass parts tetrahydrofuran (THF)s and 100 mass parts dodecafluoroheptyl methacrylates are added, mix reaction 3h, after removing tetrahydrofuran (THF), by the product obtained hydrolysis 0.5h in the mixing solutions (60 mass parts trifluoroacetic acids and 100 mass parts dioxane close and obtain very much) of 50 DEG C, obtain the fluoropolymer of end carboxyl.
(3) preparation of end-vinyl fluorinated alkyl ester polymer: the fluoropolymer of the end carboxylic acid 20 mass parts steps (2) prepared joins in 180 mass parts pyridine solutions and mixes, then 40 mass parts hy-droxybutyl, 5 mass parts N are added, N-dicyclohexylcarbodiimide and 2 mass parts N-hydroxyl tetrazoles, in 50 DEG C of reactions 4 hours, obtained end-vinyl fluorinated alkyl ester polymer.By FT-IR(1642 and 1608cm
-1the charateristic avsorption band of C=O and C=C respectively) and
1h-NMR(5.7 ~ 5.8 and 6.3 ~ 6.4ppm are CH
2=C-, 6.0 ~ 6.2ppm are the absorption peak of C=CH-C=O Hydrogen Proton in double bond) to determine, its structure is such as formula shown in V:
(formula V);
(4) containing the preparation that the complex light of end-vinyl fluorinated alkyl ester polymer is coating material solidified: epoxy acrylic resin 100 mass parts prepared by step (1), join in container, end-vinyl fluorinated alkyl ester polymer 50 mass parts prepared by step (3) is added again successively under strong stirring, pentaerythritol acrylate trimethyl 8 mass parts, light trigger 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide 8 mass parts, light calcium carbonate 30 mass parts, polycarboxylate sodium (SN-5040, Guangzhou Guan Zhi Chemical Co., Ltd.)) 5 mass parts, defoamer organic silicone oil (FY2309, Guangzhou Fu Yuan Science and Technology Ltd.) 4 mass parts, often add a kind of reaction raw materials all to stir, add another kind of reaction raw materials again.After mixing, the complex light obtained containing end-vinyl fluorinated alkyl ester polymer is coating material solidified.
After curing of coating, performance is as follows: adhesion 1 grade, with contact angle 127 °, the pencil hardness 5H of water, artificial weathering ageing resistance 600h is unchanged, water tolerance 270h is unchanged, acid resistance 72h is unchanged and alkali resistance 72h is unchanged.
Embodiment 5
(1) preparation of epoxy methacrylic resin: get bisphenol f type epoxy resin (oxirane value 0.63) 100 mass parts and add in the reactor that reflux condensing tube, dropping funnel, thermometer and agitator are housed, heated and stirred to 68 DEG C, then Tetrabutyl amonium bromide 0.08 mass parts is added, Resorcinol 1.5 mass parts and methacrylic acid 38 mass parts, be warmed up to 100 DEG C, react 7 hours, obtained epoxy methacrylic resin.
(2) preparation of the fluoropolymer of end carboxyl: the TBAH aqueous solution by 0.5 mass parts butyl ethyl malonate, 20 mass parts toluene and 0.2 mass parts concentration being mass percent 10% is even, reaction 8h; Then 60 mass parts tetrahydrofuran (THF)s and 10 mass parts Hexafluorobutyl mathacrylates are added, mix reaction 2.5h, after removing tetrahydrofuran (THF), by the product obtained hydrolysis 4h in the mixing solutions (40 mass parts trifluoroacetic acids and 80 mass parts dioxane are mixed to get) of 30 DEG C, obtain the fluoropolymer of end carboxyl.
(3) preparation of end-vinyl fluorinated alkyl ester polymer: the fluoropolymer of the end carboxylic acid 2 mass parts steps (2) prepared joins in 30 mass parts dimethyl formamides and mixes, then 8 mass parts Rocryl 410s, 0.2 mass parts N is added, N '-dicyclohexylcarbodiimide and 1.8 mass parts DMAPs, 60 DEG C of reactions 48 hours, obtained end-vinyl fluorinated alkyl ester polymer.By FT-IR(1640 and 1607cm
-1the charateristic avsorption band of C=O and C=C respectively) and
1h-NMR(5.6 ~ 5.7 and 6.0 ~ 6.1ppm are CH
2the absorption peak of Hydrogen Proton in=C-double bond) to determine, its structure is such as formula shown in VI:
(formula VI);
(4) containing the preparation that the complex light of end-vinyl fluorinated alkyl ester polymer is coating material solidified: epoxy methacrylic resin 100 mass parts prepared by step (1), join in container, end-vinyl fluorinated alkyl ester polymer 0.01 mass parts prepared by step (3) is added again successively under strong stirring, ethoxyquin Glycerin triacrylate 10 mass parts, light trigger 2, 4, 6-trimethylbenzoyl phenyl phosphine oxide 3.5 mass parts, water-ground limestone 8 mass parts, vinylformic acid sodium salt (DC40, Weifang Heng Hai Chemical Co., Ltd.) 2 mass parts and defoamer mineral oils (BEK-750, Guangzhou Guan Zhi Chemical Co., Ltd.) 0.5 mass parts, often add a kind of reaction raw materials all to stir, add another kind of reaction raw materials again.After mixing, the complex light obtained containing end-vinyl fluorinated alkyl ester polymer is coating material solidified.
After curing of coating, performance is as follows: adhesion 1 grade, with the contact angle 113 ° of water, pencil hardness 5H, the 600h of resistance to artificial weathering are unchanged, water tolerance 250h is unchanged, acid resistance 72h is unchanged and alkali resistance 72h is unchanged.
Embodiment 6
(1) preparation of epoxy acrylic resin: get Resorcinol bisglycidyl ether type epoxy resin (oxirane value 0.85) 100 mass parts and add in the reactor that reflux condensing tube, dropping funnel, thermometer and agitator are housed, heated and stirred to 78 DEG C, then Tetrabutyl amonium bromide 0.08 mass parts, Resorcinol 1.5 mass parts and vinylformic acid 50 mass parts is added, be warmed up to 108 DEG C, react 2.5 hours, obtained epoxy acrylic resin.
(2) preparation of the fluoropolymer of end carboxyl: be that mass percent 10% TBAH aqueous solution is even by 2 mass parts butyl ethyl malonates, 120 mass parts toluene and 1 mass parts concentration, reaction 5h; Then 120 mass parts tetrahydrofuran (THF)s and 50 mass parts dodecafluoroheptyl methacrylates are added, mix reaction 1.5h, after removing tetrahydrofuran (THF), by the product obtained hydrolysis 3h in the mixing solutions (30 mass parts trifluoroacetic acids and 60 mass parts dioxane are mixed to get) of 70 DEG C, obtain the fluoropolymer of end carboxyl.
(3) preparation of end-vinyl fluorinated alkyl ester polymer: the fluoropolymer of the end carboxylic acid 12 mass parts steps (2) prepared joins in 150 mass parts tetrahydrofuran solutions and mixes, then 18 mass parts Propylene glycol monoacrylates, 0.5 mass parts 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and 0.85 mass parts DMAP is added, 35 DEG C of reactions 42 hours, obtained end-vinyl fluorinated alkyl ester polymer.By FT-IR(1638 and 1610cm
-1the charateristic avsorption band of C=O and C=C respectively) and
1h-NMR(5.7 ~ 5.8 and 6.3 ~ 6.4ppm are CH
2the absorption peak of Hydrogen Proton in=C-double bond, 6.0 ~ 6.2 is the absorption peak of Hydrogen Proton in-C=CH-C=O double bond) determine, its structure is such as formula shown in VII:
(formula VII);
(4) containing the preparation that the complex light of end-vinyl fluorinated alkyl ester polymer is coating material solidified: epoxy acrylic resin 100 mass parts prepared by step (1), join in container, end-vinyl fluorinated alkyl ester polymer 2 mass parts prepared by step (3) is added again successively under strong stirring, ethoxyquin Glycerin methyl triacrylate 12 mass parts, light trigger benzoin dimethylether 3.2 mass parts, titanium dioxide 2 mass parts, polyacrylic acid sodium salt (TH-1100, Shandong Taihe Water Treatment Co., Ltd.) 2 mass parts and the polysiloxane-based (FY2311H of defoamer, Guangzhou Fu Yuan Science and Technology Ltd.) 0.5 mass parts, often add a kind of reaction raw materials all to stir, add another kind of reaction raw materials again.After mixing, the complex light obtained containing end-vinyl fluorinated alkyl ester polymer is coating material solidified.
After curing of coating, performance is as follows: adhesion 1 grade, with contact angle 118 °, the pencil hardness 4H of water, artificial weathering ageing resistance 600h is unchanged, water tolerance 260h is unchanged, acid resistance 72h is unchanged and alkali resistance 72h is unchanged.
In embodiment 1 ~ 6, along with adding of end-vinyl fluorinated alkyl ester polymer, coating weather-proof, water-fast, anti-pollution characteristic, shock resistance is greatly improved, and there are good sticking power and hardness, particularly hydrophobic performance is greatly improved, and describes the performance that (methyl) alkyl acrylate fluoropolymer can be good at improving coating, reaches the technology of the present invention and improve effect.
Comparing embodiment 1
(1) synthesis of component A (glycidyl resin): oxirane value be 0.35 bisphenol type epoxy 100 mass parts add in the reactor that reflux condensing tube, dropping funnel, thermometer and agitator are housed, heated and stirred to 70 DEG C, then Tetrabutyl amonium bromide 0.5 mass parts, Resorcinol 1 mass parts and methacrylic acid 25 mass parts is dripped, be warmed up to 110 DEG C, react 3 hours.
(2) synthesis of B component (end-vinyl fluorinated alkyl ester polymer):
1. the TBAH aqueous solution of 3 mass parts butyl ethyl malonates, 100 mass parts toluene and 8 mass parts concentration mass percents 10% is even, reaction 9h; Then 40 mass parts tetrahydrofuran (THF)s and 20 mass parts vinylformic acid hexafluoro butyl esters are added, mix reaction 1h, after removing tetrahydrofuran (THF), by the product obtained hydrolysis 4.5h in the mixing solutions (50 mass parts trifluoroacetic acids and 100 mass parts dioxane are mixed to get) of 40 DEG C, obtain the fluoropolymer of end carboxyl;
2. the fluoropolymer of 5 mass parts end carboxyl is joined in 100 parts by mass Methylene chloride solution and mix, then 10 mass parts Rocryl 410s, 1 mass parts N is added, N '-dicyclohexylcarbodiimide (DCC) and 0.01 mass parts of catalyst DMAP (DMAP), 40 DEG C of reactions 30 hours, obtain end-vinyl fluorinated alkyl ester polymer.
(3) component C is other components: be activity diluting monomer (tri (propylene glycol) diacrylate 10 mass parts, light trigger (2-hydroxy-2-methyl-1-phenyl-1-acetone) 5 parts, inorganic salt filler (titanium dioxide) 15 mass parts, dispersion agent (polycarboxylate sodium SN-5040) 3 mass parts, defoamer (type siloxane defoamer FY-3300) 2 mass parts.
Component A, B component and component C are mixed, stir, obtain coating, its performance is as shown in table 1:
Table 1
As can be seen from Table 1, under same materials conditions of mixture ratios, add the performance such as hydrophobic that a small amount of end-vinyl fluorinated alkyl ester polymer significantly can improve coating in formula, along with the increase of end-vinyl fluorinated alkyl esters polymer content, the over-all properties of coating is greatly improved.
Comparing embodiment 2
(1) synthesis of component A (acrylic acid epoxy resin): oxirane value is epoxidation linear phenolic resin (the Wuxi resin processing plant of 0.57, model F51) 100 mass parts, add in the reactor that reflux condensing tube, dropping funnel, thermometer and agitator are housed, heated and stirred to 80 DEG C, then TBAH 1 mass parts, Resorcinol 0.05 mass parts and vinylformic acid 40 mass parts is added, be warmed up to 90 DEG C, react 7 hours, obtain acrylic acid epoxy resin.
(2) synthesis of B component (end-vinyl fluorinated alkyl ester polymer):
1. the TBAH aqueous solution by 8 mass parts butyl ethyl malonates, 200 mass parts toluene and 15 mass parts concentration being mass percent 10% is even, reaction 12h; Then 100 mass parts tetrahydrofuran (THF)s are added, 20 mass parts Hexafluorobutyl mathacrylates, mix reaction 1.5h, after removing tetrahydrofuran (THF), by the product obtained hydrolysis 8h in the mixing solutions (20 mass parts trifluoroacetic acids and 80 mass parts dioxane are mixed to get) of 55 DEG C, obtain the fluoropolymer of end carboxyl;
2. the TBAH aqueous solution by 3 mass parts butyl ethyl malonates, 80 mass parts toluene and 20 mass parts concentration being mass percent 10% is even, reaction 12h; Then the dodecafluoroheptyl methacrylate monomer of 100 mass parts tetrahydrofuran (THF)s and 40 mass parts is added, mix reaction 1.5h, after removing tetrahydrofuran (THF), by the product obtained hydrolysis 8h in the mixing solutions (80 mass parts trifluoroacetic acids and 100 mass parts dioxane are mixed to get) of 55 DEG C, obtain the fluoropolymer of end carboxyl;
3. the fluoropolymer of 10 mass parts end carboxyl is joined 50 mass parts pyridines, then 10 mass parts methacrylate, 2 mass parts 1-ethyls-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and 1 mass parts of catalyst N-hydroxyl tetrazole is added 25 DEG C of reactions 35 hours, end-vinyl fluorinated alkyl ester polymer.Wherein, end-vinyl fluorinated alkyl ester polymer prepared by the fluoropolymer of end carboxyl step 1. obtained is used in the formula 6,8 and 10 in table 2; End-vinyl fluorinated alkyl ester polymer prepared by the fluoropolymer of end carboxyl step 2. obtained is used in the formula 7,9 and 11 in table 2.
(3) component C is other components: be activity diluting monomer (pentaerythritol triacrylate) 20 mass parts, light trigger (1-hydroxy-cyciohexyl phenyl ketone) 6 parts, inorganic salt filler (light calcium carbonate) 20 mass parts, dispersion agent (polyacrylic acid sodium salt, TH-1100) 2 mass parts, defoamer (asking mineral oil defoaming agent to be SN-919) 2 mass parts.
Component A, B component and component C are mixed, stir, obtain coating, its performance is as shown in table 2:
Table 2
Fill a prescription 6 and 7,8 and 9,10 and 11 relatively from table 2, under identical material conditions of mixture ratios, the fluorine-containing end of the chain is longer, and the hydrophobic performance of coating is better.
Comparing embodiment 3:
The preparation that the complex light of trifluoroethyl methacrylate is coating material solidified: epoxy acrylic resin 100 mass parts prepared by step (1) in embodiment 2, join in container, trifluoroethyl methacrylate 35 mass parts is added again successively under strong stirring, tri (propylene glycol) diacrylate 2 mass parts, light trigger Benzoin ethyl ether 1.5 mass parts, talcum powder 25 mass parts, polycarboxylate sodium (SN-5040, Guangzhou Guan Zhi Chemical Co., Ltd.) 2 mass parts and mineral oil defoaming agent (SN-919, this promise chemistry Science and Technology Ltd. of Shanghai) 3.5 mass parts, often add a kind of reaction raw materials all to stir, add another kind of reaction raw materials again.After mixing, the complex light obtained containing trifluoroethyl methacrylate is coating material solidified.
After curing of coating, performance is as follows: adhesion 1 grade, unchanged with the contact angle 78 ° of water, pencil hardness 4H, artificial weathering ageing resistance 600h, water tolerance 220h, and acid resistance 72h is unchanged and alkali resistance 72h is unchanged.
Comparing embodiment 4
Containing the preparation that the complex light of Hexafluorobutyl mathacrylate is coating material solidified: epoxy methacrylic resin 100 mass parts prepared by step (1) in embodiment 3, join in container, step Hexafluorobutyl mathacrylate 2.8 mass parts is added again successively under strong stirring, pentaerythritol triacrylate 20 mass parts, light trigger 2-hydroxy-2-methyl-1-phenyl-1-acetone 6.5 mass parts, talcum powder 30 mass parts, defoamer mineral oils (BEK-750, Guangzhou Guan Zhi Chemical Co., Ltd.) 0.1 mass parts and dispersion agent polyacrylic acid sodium salt (TH-1100, Shandong Taihe Water Treatment Co., Ltd.) 0.5 mass parts, often add a kind of reaction raw materials all to stir, add another kind of reaction raw materials again.After mixing, the complex light obtained containing Hexafluorobutyl mathacrylate is coating material solidified.
After curing of coating, performance is as follows: sticking power 2 grades, with contact angle 85 °, the pencil hardness 4H of water, artificial weathering ageing resistance 600h is unchanged, water tolerance 240h is unchanged, acid resistance 72h is unchanged and alkali resistance 72h is unchanged.
The difference of comparing embodiment 3 and embodiment 2 is only the end-vinyl fluorinated alkyl ester polymer replacing embodiment 2 to prepare with trifluoroethyl methacrylate.The difference of comparing embodiment 4 and embodiment 3 is only the end-vinyl fluorinated alkyl ester polymer replacing embodiment 3 to prepare with Hexafluorobutyl mathacrylate.Can be obtained by comparing embodiment 3 and comparing embodiment 4, the end-vinyl fluorinated alkyl ester polymer obtained by the present invention than add merely film that fluorochemical monomer obtains surface property and antifouling water resistance better.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. the complex light containing end-vinyl fluorinated alkyl ester polymer is coating material solidified, it is characterized in that comprising the following component by mass parts:
Epoxy (methyl) acrylic resin 100 parts, end-vinyl fluorinated alkyl ester polymer 0.01 ~ 50 part, activity diluting monomer 2 ~ 20 parts, light trigger 0.5 ~ 8 part, inorganic salt filler 2 ~ 30 parts, dispersion agent 0.5 ~ 5 part and defoamer 0.1 ~ 4 part;
Described epoxy (methyl) acrylic resin is prepared by the method comprising following steps: by 100 mass parts diglycidyl ether type epoxy resin heated and stirred to 60 ~ 90 DEG C, then 0.1 ~ 100 mass parts (methyl) vinylformic acid is added, 0.05 ~ 3 mass parts of catalyst and 0.05 ~ 3 mass parts stopper, then 95 ~ 130 DEG C are warmed up to, react 1 ~ 7 hour, obtained epoxy (methyl) acrylic resin;
The structural formula of described end-vinyl fluorinated alkyl ester polymer is such as formula shown in I:
(formula I);
Wherein: R ' is-H or-CH
3; R " represent that carbon chain lengths is C
1~ C
4alkyl; R " ' be-H or-CH
3; R
fexpression carbon chain lengths is C
1~ C
16fluorine-containing ester group, fluorine-containing ester group refers to hydrogen atom wherein by the some or all of displacement of fluorine atom; N is the integer between 3 ~ 50.
2. the complex light containing end-vinyl fluorinated alkyl ester polymer according to claim 1 is coating material solidified, it is characterized in that: the oxirane value of described diglycidyl ether type epoxy resin is 0.01 ~ 0.87, is at least one in bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, epoxidation linear phenolic resin, Resorcinol bisglycidyl ether type epoxy resin, Phloroglucinol monomethyl ether three-glycidyl ether type epoxy resin or two Resorcinol formal four diglycidyl ether type epoxy resin;
Described catalyzer is quaternary ammonium salt;
Described stopper is Resorcinol.
3. the complex light containing end-vinyl fluorinated alkyl ester polymer according to claim 1 is coating material solidified, it is characterized in that: described end-vinyl fluorinated alkyl ester polymer is obtained by the preparation method comprising following steps:
(1) be that the TBAH aqueous solution of mass percent 10% is even by 0.5 ~ 10 mass parts butyl ethyl malonate, 20 ~ 200 mass parts toluene and 0.2 ~ 20 mass parts concentration, reaction 1 ~ 20h; Then 40 ~ 200 mass parts tetrahydrofuran (THF)s and 10 ~ 100 mass parts fluorochemical monomers are added, mix reaction 0.2 ~ 3h, remove after tetrahydrofuran (THF) changes, be hydrolyzed 0.5 ~ 6h in the mixing solutions of 20 ~ 80 DEG C in temperature by the product obtained, obtain the fluoropolymer of end carboxyl; Wherein, described mixing solutions is that 5 ~ 60 mass parts trifluoroacetic acids and 30 ~ 100 mass parts dioxane are mixed to get;
(2) mix in the fluoropolymer of 2 ~ 20 mass parts end carboxylic acids and 30 ~ 300 mass parts solvents, then 5 ~ 40 mass parts (methyl) acrylic acid hydroxy alkyl ester, 0.2 ~ 5 mass parts dewatering agent and 0.01 ~ 2 mass parts of catalyst is added, in 0 ~ 60 DEG C of reaction 4 ~ 48 hours, obtained end-vinyl fluorinated alkyl ester polymer.
4. the complex light containing end-vinyl fluorinated alkyl ester polymer according to claim 3 is coating material solidified, it is characterized in that:
Fluorochemical monomer described in step (1) is at least one in vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester or methacrylic acid-1H ,-1H-perfluoro monooctyl ester;
Solvent described in step (2) is at least one in tetrahydrofuran (THF), pyridine, methylene dichloride, trichloromethane or dimethyl formamide;
(methyl) acrylic acid hydroxy alkyl ester described in step (2) is at least one in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410 or hy-droxybutyl;
Dewatering agent described in step (2) is 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride or N, N ' one or both in-dicyclohexylcarbodiimide;
Catalyzer described in step (2) is at least one in DMAP, 1-hydroxyl-7-azo benzotriazole or the chloro-1-hydroxy benzo triazole of 6-.
5. the complex light containing end-vinyl fluorinated alkyl ester polymer according to claim 1 is coating material solidified, it is characterized in that: described activity diluting monomer is at least one in tripropylene glycol dimethacrylate, tri (propylene glycol) diacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, ethoxyquin Glycerin triacrylate or ethoxyquin Glycerin methyl triacrylate;
Described light trigger is benzophenone, Benzoin ethyl ether, benzoin dimethylether, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyciohexyl phenyl ketone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide or two 2, at least one in 4,6-trimethylbenzoyl phenyl phosphine oxide;
Described inorganic salt filler is at least one in titanium dioxide, talcum powder, light calcium carbonate or water-ground limestone;
Described defoamer is mineral oil defoaming agent or polysiloxane defoamers;
Described dispersion agent is vinylformic acid sodium salt, polyacrylic acid sodium salt or polycarboxylate sodium.
6. the complex light containing end-vinyl fluorinated alkyl ester polymer according to claim 5 is coating material solidified, it is characterized in that:
The defoamer of described mineral oil defoaming agent to be model be SN-919 or model are one or both in the defoamer of BEK-750;
The described polysiloxane defoamers at least one that to be model be in the defoamer of FY2309 or FY-3300.
7. the preparation method coating material solidified containing the complex light of end-vinyl fluorinated alkyl ester polymer described in any one of claim 1 ~ 6, is characterized in that comprising following steps:
(1) preparation of epoxy (methyl) acrylic resin: by 100 mass parts diglycidyl ether type epoxy resin heated and stirred to 60 ~ 90 DEG C, then 0.1 ~ 100 mass parts (methyl) vinylformic acid is added, 0.05 ~ 3 mass parts of catalyst and 0.05 ~ 3 mass parts stopper, then 95 ~ 130 DEG C are warmed up to, react 1 ~ 7 hour, obtained epoxy (methyl) acrylic resin;
(2) preparation of the fluoropolymer of end carboxyl: the TBAH aqueous solution by 0.5 ~ 10 mass parts butyl ethyl malonate, 20 ~ 200 mass parts toluene and 0.2 ~ 20 mass parts concentration being mass percent 10% is even, reaction 1 ~ 20h; Then 40 ~ 200 mass parts tetrahydrofuran (THF)s and 10 ~ 100 mass parts fluorochemical monomers are added, mix reaction 0.2 ~ 3h, after removing tetrahydrofuran (THF), be hydrolyzed 0.5 ~ 6h in the mixing solutions of 20 ~ 80 DEG C in temperature by the product obtained, obtain the fluoropolymer of end carboxyl; Wherein, described mixing solutions is that 5 ~ 60 mass parts trifluoroacetic acids and 30 ~ 100 mass parts dioxane are mixed to get;
(3) preparation of end-vinyl fluorinated alkyl ester polymer: mix in the fluoropolymer of end carboxylic acid prepared by 2 ~ 20 mass parts steps (2) and 30 ~ 300 mass parts solvents, then 5 ~ 40 mass parts (methyl) acrylic acid hydroxy alkyl ester, 0.2 ~ 5 mass parts dewatering agent and 0.01 ~ 2 mass parts of catalyst is added, in 0 ~ 60 DEG C of reaction 4 ~ 48 hours, obtained end-vinyl fluorinated alkyl ester polymer;
(4) containing the preparation that the complex light of end-vinyl fluorinated alkyl ester polymer is coating material solidified: end-vinyl fluorinated alkyl ester polymer, 2 ~ 20 mass parts activity diluting monomers, 0.5 ~ 8 mass parts light trigger, 2 ~ 30 mass parts inorganic salt filler, 0.5 ~ 5 mass parts dispersion agent and 0.1 ~ 4 mass parts defoamer prepared by epoxy (methyl) acrylic resin 100 mass parts steps (1) prepared, 0.01 ~ 50 mass parts step (3) mix, the complex light obtained containing end-vinyl fluorinated alkyl ester polymer is coating material solidified.
8. the preparation method coating material solidified containing the complex light of end-vinyl fluorinated alkyl ester polymer according to claim 7, is characterized in that:
The oxirane value of the diglycidyl ether type epoxy resin described in step (1) is 0.01 ~ 0.87, is at least one in bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin, epoxidation linear phenolic resin, Resorcinol bisglycidyl ether type epoxy resin, Phloroglucinol monomethyl ether three-glycidyl ether type epoxy resin or two Resorcinol formal four diglycidyl ether type epoxy resin;
Catalyzer described in step (1) is quaternary ammonium salt;
Stopper described in step (1) is Resorcinol;
Fluorochemical monomer described in step (2) is at least one in vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester or methacrylic acid-1H ,-1H-perfluoro monooctyl ester;
Solvent described in step (3) is at least one in tetrahydrofuran (THF), pyridine, methylene dichloride, trichloromethane or dimethyl formamide;
(methyl) acrylic acid hydroxy alkyl ester described in step (3) is at least one in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, hy-droxybutyl;
Dewatering agent described in step (3) is 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride or N, N ' one or both in-dicyclohexylcarbodiimide;
Catalyzer described in step (3) is at least one in DMAP, 1-hydroxyl-7-azo benzotriazole or the chloro-1-hydroxy benzo triazole of 6-.
9. the application coating material solidified containing the complex light of end-vinyl fluorinated alkyl ester polymer described in any one of claim 1 ~ 6: it is characterized in that: the described complex light containing end-vinyl fluorinated alkyl ester polymer is coating material solidified to be applied in building field, electronic applications.
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| CN103289058B (en) * | 2013-06-06 | 2017-12-01 | 京东方科技集团股份有限公司 | The epoxy acrylic resin of fluorine richness, ultraviolet curing varnish and preparation method thereof, the method that the gloss oil is coated on to base material |
| CN103396558B (en) * | 2013-07-01 | 2015-11-18 | 中科院广州化学有限公司 | End-vinyl fluorine silicon graftomer and its preparation method and application |
| CN103589297B (en) * | 2013-10-24 | 2016-10-05 | 中科院广州化学有限公司 | A kind of containing end-vinyl fluorine silicon graft copolymer photocuring composite coating and preparation method |
| CN103627003B (en) * | 2013-10-24 | 2016-03-16 | 中科院广州化学有限公司 | A kind of fluorine silicon graftomer Graft Epoxy Resin and preparation method thereof |
| CN103589298B (en) * | 2013-10-24 | 2015-11-18 | 中科院广州化学有限公司 | One is coating material solidified and preparation method containing end-vinyl amphipathic fluoride graftomer complex light |
| TWI662020B (en) * | 2014-10-03 | 2019-06-11 | 日商迪愛生股份有限公司 | Epoxy ester compound, cellulose ester resin composition, optical film and liquid crystal display device |
| CN104830191B (en) * | 2015-04-28 | 2017-02-01 | 中科院广州化学有限公司南雄材料生产基地 | Monovinyl-terminated fluorine-containing prepolymer/epoxy (methyl) acrylate composite UV-cured paint, preparation and applications thereof |
| CN104789094B (en) * | 2015-04-28 | 2017-01-18 | 中科院广州化学有限公司南雄材料生产基地 | Carboxyl-terminated fluorine-containing prepolymer modified epoxy coating and preparation method and application thereof |
| CN106010065A (en) * | 2016-05-17 | 2016-10-12 | 江苏博开达工业化住宅制造有限公司 | Surface treatment method for connecting device for modular buildings |
| CN106632795B (en) * | 2016-12-06 | 2019-02-19 | 哈尔滨工业大学无锡新材料研究院 | UV self-cross linking type fluorubber and preparation method thereof |
| CN108587416B (en) * | 2018-05-08 | 2020-04-17 | 中科广化（重庆）新材料研究院有限公司 | Fluorine-containing prepolymer modified waterborne epoxy (methyl) acrylate composite UV (ultraviolet) curing coating and preparation and application thereof |
| CN108822264B (en) * | 2018-07-12 | 2019-04-02 | 东营亿鑫化工有限公司 | A kind of carboxylate polymer's dispersing agent with defoaming function |
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