CN103396558A - Vinyl-terminated fluorosilicone graft polymer, and preparation method and applications thereof - Google Patents
Vinyl-terminated fluorosilicone graft polymer, and preparation method and applications thereof Download PDFInfo
- Publication number
- CN103396558A CN103396558A CN2013102720303A CN201310272030A CN103396558A CN 103396558 A CN103396558 A CN 103396558A CN 2013102720303 A CN2013102720303 A CN 2013102720303A CN 201310272030 A CN201310272030 A CN 201310272030A CN 103396558 A CN103396558 A CN 103396558A
- Authority
- CN
- China
- Prior art keywords
- mass parts
- graftomer
- fluorine silicon
- vinyl
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to a fluorosilicone graft polymer field, and discloses a vinyl-terminated fluorosilicone graft polymer, and a modified epoxy acrylic resin paint thereof. The vinyl-terminated fluorosilicone graft polymer can be prepared by the following method: adding 100 parts by weight of hydroxyl-terminated fluorosilicone graft polymer 0.05-1 part by weight of catalyst and 10-20 parts by weight of isocyanate monomer into 100-500 parts by weight of solvent, uniformly mixing, reacting at 60-100 DEG C for 4-24h, adding 1-20 parts by weight of (methyl) hydroxyalkyl acrylate, and reacting at 60-100 DEG C for 2-12h, to obtain the vinyl-terminated fluorosilicone graft polymer. The vinyl-terminated fluorosilicone graft polymer contains functional carbon-carbon double bonds, can performs ultraviolet cure and free radical polymerization. The paint prepared by the vinyl-terminated fluorosilicone graft polymer has excellent hydrophobic performance, chemical resistance, pollution resistance (3%), and aging resistance.
Description
Technical field
The invention belongs to fluorine silicon graftomer preparing technical field, particularly a kind of end-vinyl fluorine silicon graftomer and its preparation method and application.
Background technology
Ultraviolet-curing paint is short owing to having a set time, and the characteristics such as energy consumption is low, solvent-free, be widely used in the novel building base material, the fields such as binding agent, printing ink, metal electron component package.Wherein, the bisphenol-A epoxy acrylic resin paint is cheap because of it, source is abundant, hardness is high, advantages such as transparency is good and being widely used, but also exist weathering resistance, the problem such as anti-corrosion-resistant, particularly due to the higher surface tension of epoxy acrylic resin, the epoxypaint surface of preparation has higher surface energy, limits its use in high-end fields such as anti-fouling ship paint, electronic products.
The fluorine carbon bond can be large, arranges closely, can effectively prevent the exposure of carbon atom and carbochain, so fluoropolymer shows excellent chemical stability, water tolerance, high thermal resistance, corrosion resistance nature.Silica bond energy in organosilicon material is large, and segment is soft, has the performance of organic inorganics concurrently, therefore has remarkable high-low temperature resistant, UV resistant, anti-oxidant degradation property.Fluorine silicon contained polymer has excellent heatproof, waterproof, the performance such as antifouling, weather-proof, ageing-resistant, therefore the organic silicon-fluorine polymkeric substance is widely used in the industrial circles such as automobile, electronics, aviation, application, weaving, and wherein the organic silicon-fluorine polymer application demonstrates the ageing-resistant energy of excellent water proof anti-soil performance in coatings industry.Present fluorine-containing epoxy acrylic resin is mainly to add fluorine atom single or that lacked in the main chain section, although such monomer can improve the performance such as heat-resisting, corrosion-resistant of coating, but, because its fluorine content is not high, need a large amount of interpolation fluorochemical monomers, but improved widely use cost; Although the fluorine silicon contained polymer of blend can reach hydrophobic performance that a small amount of silicon-fluorine polymer thing improves coating, anti-pollution characteristic etc. in addition, easily occurs being separated, and affects the mechanical and physical performance of coating.
Summary of the invention
For the shortcoming and deficiency that overcome above-mentioned prior art, primary and foremost purpose of the present invention is to provide a kind of end-vinyl fluorine silicon graftomer.
Another purpose of the present invention is to provide a kind of preparation method of above-mentioned end-vinyl fluorine silicon graftomer.
Still a further object of the present invention is to provide the application of above-mentioned end-vinyl fluorine silicon graftomer in preparation modified epoxy acrylate resin coating.
Purpose of the present invention realizes by following proposal:
A kind of end-vinyl fluorine silicon graftomer has following structure:
N is the integer in 5～100;
R, R
3For hydrogen or methyl;
R
1For dimethylene, trimethylene or tetramethylene;
R
2For tolyl, hexa-methylene, 4,4 '-ditan, 1,3,3-trimethyl-cyclohexane, phenyl or tri-methyl hexamethylene;
R
fFor the Polyfluoroalkyl of C atomicity 1～8, namely the hydrogen atom in alkyl is by the some or all of displacement of fluorine atom.
The preparation method of above-mentioned end-vinyl fluorine silicon graftomer comprises following concrete steps:
Fluorine silicon graftomer with the terminal hydroxy group end-blocking of 100 mass parts, 0.05～1 mass parts of catalyst, 1～20 mass parts isocyanate-monomer joins in 100～500 mass parts solvents, mix, 60～100 ℃ of reaction 4～24h, add 1～20 mass parts (methyl) acrylic acid hydroxy alkyl ester, 60～100 ℃ of reaction 2～12h, obtain end-vinyl fluorine silicon graftomer.
Described solvent refers at least a in tetrahydrofuran (THF) (THF), DMF (DMF) and N,N-dimethylacetamide (DMAC), and being preferably volume ratio is the THF/DMAC mixed solvent of 1:3.
Described catalyzer refers at least a in dibutyl tin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tin and dibutyltin diacetate, preferred dibutyl tin dilaurate.
Described isocyanate-monomer nail phenylene diisocyanate (TDI), isophorone diisocyanate (IPDI), PPDI, trimethylammonium hexamethylene diisocyanate, 4, at least a in 4 '-diphenylmethanediisocyanate (MDI) and hexamethylene diisocyanate (HDI), at least a in preferred tolylene diisocyanate (TDI) and isophorone diisocyanate (IPDI).
At least a in described (methyl) acrylic acid hydroxy alkyl ester nail base Hydroxyethyl acrylate, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate and methacrylic acid hydroxy butyl ester.
The fluorine silicon graftomer of described terminal hydroxy group end-blocking is prepared by following methods: get end hydroxyl silicone oil 100 mass parts, end carboxy acrylic fluoroalkyl ester polymer 10～100 mass parts, dewatering agent 0～5 mass parts, catalyzer 0.01～3 mass parts, DMF (DMF) or N,N-dimethylacetamide (DMAC) 0～500 mass parts, 100～180 ℃ are reacted 8～36h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
At least a in described end hydroxyl silicone oil finger tip hydroxyl dimethyl silicone oil, end hydroxypropyl dimethyl silicone oil and terminal hydroxy group methyl phenyl silicone oil.
Described dewatering agent refers to 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and N, at least a in N '-dicyclohexylcarbodiimide (DCC).
Described catalyzer refers at least a in DMAP (DMAP), 1-hydroxyl-7-azo benzotriazole (HOAT), 6-chloro-1-hydroxy benzo triazole (HOBT), Mono-n-butyltin (MBTO) and Dibutyltin oxide (DBTO).
described end carboxy acrylic fluoroalkyl ester polymer is prepared by following methods: with 2 mass parts butyl ethyl malonates, 50 mass parts toluene and 3 mass parts concentration are that the TBAH aqueous solution of 25wt% is even, react 3h under 30 ℃, toluene is removed in decompression, then add 80 mass parts tetrahydrofuran (THF)s and 5～50 mass parts fluorochemical monomers, reaction 0.5h, after tetrahydrofuran (THF) is removed in decompression, the 5 mass parts trifluoroacetic acids and the 60 mass parts dioxane mixing solutionss that the product that obtains are placed in 60 ℃ are hydrolyzed 12h, obtain holding carboxy acrylic fluoroalkyl ester polymer.
Described fluorochemical monomer refers to vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl esters, methacrylic acid-1H, at least a in 1H-perfluoro monooctyl ester and methacrylic acid 17 fluorine certain herbaceous plants with big flowers esters.
The application of above-mentioned end-vinyl fluorine silicon graftomer in preparation modified epoxy acrylate resin coating, comprise following steps: 2～100 mass parts end-vinyl fluorine silicon graftomer are joined in the solvent of 100～500 mass parts, add 80～100 mass parts epoxy (methyl) acrylic resins, the light trigger of 1～5 mass parts, mix, obtain modified epoxy acrylate resin coating.
Described solvent refers at least a in tetrahydrofuran (THF) (THF), DMF (DMF) and N,N-dimethylacetamide (DMAC), and preferred volume ratio is the THF/DMAC mixing solutions of 1:3.
Described light trigger refers to 2-hydroxy-2-methyl-1-phenyl-acetone (1173), 1-hydroxy-cyclohexyl phenyl ketone (184), 2; 4,6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-at least a in 1-acetone (659) and EDMAB (EDB).
Described modified epoxy acrylate resin coating is ultraviolet-curing paint.
Mechanism of the present invention is:
End-vinyl fluorine silicon graftomer provided by the present invention is functional carbon-carbon double bond because end contains, and can carry out ultraviolet light polymerization and Raolical polymerizable.This functional graftomer separately UV-light reaction or with the epoxy acrylic resin copolyreaction, general UV-light radical initiator polymerization is applicable to the polymerization of body series.Because end-vinyl fluorine silicon graftomer contains high molecular weight and fluorine silicon content, make this functional fluorine silicon graftomer more easily move to coating surface, a small amount of functional fluorine silicon graftomer can reach excellent hydrophobic performance, chemically-resistant, anti-pollution and the performance such as ageing-resistant.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) end-vinyl fluorine silicon graftomer end of the present invention contains functional carbon-carbon double bond, can carry out ultraviolet light polymerization and Raolical polymerizable.
(2) coating that utilizes end-vinyl fluorine silicon graftomer of the present invention to prepare has excellent hydrophobic performance (water contact angle is up to 130 °), chemically-resistant, anti-pollution (3%) and performances such as ageing-resistant (1000h non-foaming, do not come off).
Description of drawings
Fig. 1 is the IR spectrogram of the end-vinyl fluorine silicon graftomer for preparing of embodiment 1.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) preparation of end carboxy acrylic trifluoro ethyl ester polymkeric substance: with 2 mass parts butyl ethyl malonates, 50 mass parts toluene and 3 mass parts concentration are that the TBAH aqueous solution of 25wt% is even, react 3h under 30 ℃, toluene is removed in decompression, then add 80 mass parts tetrahydrofuran (THF)s and 5 mass parts vinylformic acid trifluoro ethyl esters, mix reaction 0.5h, after tetrahydrofuran (THF) is removed in decompression, be to be hydrolyzed 12h in the 18 mass parts trifluoroacetic acids of 60 ℃ and 60 mass parts dioxane mixing solutionss with the product that obtains in temperature, obtain holding carboxy acrylic trifluoro ethyl ester polymkeric substance, it is 15000 that number-average molecular weight obtains by gel permeation chromatography.
(2) preparation of the fluorine silicon graftomer of terminal hydroxy group end-blocking: end hydroxypropyl silicone oil 100 mass parts (molecular weight 20000, four li, Shanghai industry and trade company limited), end carboxy acrylic trifluoro ethyl ester polymkeric substance 75 mass parts that step (1) prepares, catalyzer Dibutyltin oxide (DBTO) 0.01 mass parts,, at 180 ℃ of reaction 36h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
(3) preparation of end-vinyl fluorine silicon graftomer: the fluorine silicon graftomer of the terminal hydroxy group end-blocking that 100 mass parts steps (2) are prepared, 0.05 mass parts dibutyl tin dilaurate, 3 mass parts isophorone diisocyanates (IPDI) join the THF/DMAC mixed solvent that 500 mass parts volume ratios are 1:3, mix, 60 ℃ of reactions at 24h, then add 5 mass parts hydroxyethyl methylacrylates at 60 ℃ of reaction 12h, obtain end-vinyl fluorine silicon graftomer, it is carried out the IR spectroscopic analysis, see Fig. 1.
As seen from Figure 1,1638cm
-1And 1741cm
-1Belong to respectively carbon-carbon double bond stretching vibration peak and carbonylic stretching vibration peak, 1300cm
-1, 1190cm
-1Belong to respectively CF
3And CF
2The CF asymmetrical stretching vibration, 3297cm
-1For the NH stretching vibration peak.
(4) preparation of modified epoxy acrylate resin coating: fluorine silicon graftomer 1 mass parts of getting the end-vinyl in step (3) is dissolved in the THF/DMAC mixed solvent that 200 mass parts volume ratios are 1:4, add 99 mass parts epoxy methacrylic resins, 1 mass parts light trigger EDMAB (EDB), stir, obtain modified epoxy acrylate resin coating.
Embodiment 2
(1) preparation of end carboxyl trifluoroethyl methacrylate polymkeric substance: with 2 mass parts butyl ethyl malonates, 50 mass parts toluene and 3 mass parts concentration are that the TBAH aqueous solution of 25wt% is even, react 3h under 30 ℃, toluene is removed in decompression, then add 80 mass parts tetrahydrofuran (THF)s and 15 trifluoroethyl methacrylates, mix reaction 0.5h, after tetrahydrofuran (THF) is removed in decompression, be to be hydrolyzed 12h in the 5 mass parts trifluoroacetic acids of 60 ℃ and 60 mass parts dioxane mixing solutionss with the product that obtains in temperature, obtain holding carboxyl trifluoroethyl methacrylate polymkeric substance, it is 1000 that number-average molecular weight obtains by gel permeation chromatography.
(2) preparation of the fluorine silicon graftomer of terminal hydroxy group end-blocking: end hydroxypropyl silicone oil 100 mass parts (molecular weight 2000, four li, Shanghai industry and trade company limited), end carboxyl trifluoroethyl methacrylate polymkeric substance 50 mass parts that step (1) prepares, catalyzer Mono-n-butyltin (MBTO) 0.03 mass parts,, at 160 ℃ of reaction 18h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
The fluorine silicon graftomer of the terminal hydroxy group end-blocking that (3) step of 100 mass parts (2) is prepared, 0.8 mass parts two (dodecyl sulphur) dibutyl tin, tolylene diisocyanate (TDI) 20 mass parts add 350 mass parts N, in dinethylformamide (DMF) solvent, mix,, at 14h, then add hydroxyethyl methylacrylate 10 mass parts at 80 ℃ of reaction 8h 80 ℃ of reactions, obtain end-vinyl fluorine silicon graftomer.
(4) preparation of modified epoxy acrylate resin coating: get end-vinyl fluorine silicon graftomer in 3 mass parts steps (3) and be dissolved in the DMAC solvent of 400 mass parts, add 97 mass parts epoxy acrylic resins, 5 mass parts light trigger 1-hydroxy-cyclohexyl phenyl ketones (184), stir, obtain modified epoxy acrylate resin coating.
Embodiment 3
(1) preparation of end carboxyl Hexafluorobutyl mathacrylate polymkeric substance: with 2 mass parts butyl ethyl malonates, 50 mass parts toluene and 3 mass parts concentration are that the TBAH aqueous solution of 25wt% is even, react 3h under 30 ℃, toluene is removed in decompression, then the Hexafluorobutyl mathacrylate that adds 80 mass parts tetrahydrofuran (THF)s and 10 mass parts, mix reaction 0.5h, after tetrahydrofuran (THF) is removed in decompression, it is that 5 mass parts trifluoroacetic acids and the 60 mass parts dioxane mixing solutionss of 60 ℃ are hydrolyzed 12h that the product that obtains is placed in temperature, obtain holding carboxyl Hexafluorobutyl mathacrylate polymkeric substance, it is 5580 that number-average molecular weight obtains by gel permeation chromatography.
(2) preparation of the fluorine silicon graftomer of terminal hydroxy group end-blocking: (molecular weight is 4000 to 100 mass parts end hydroxyl silicone oils, four li, Shanghai industry and trade company limited), end carboxyl Hexafluorobutyl mathacrylate polymkeric substance 40 mass parts that step (1) prepares, dewatering agent EDC5 mass parts, catalyzer DMAP (DMAP) 1 mass parts, DMF (DMF) 100 mass parts,, at 100 ℃ of reaction 36h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
(3) preparation of end-vinyl fluorine silicon graftomer: the fluorine silicon graftomer of the terminal hydroxy group end-blocking that 100 mass parts steps (2) are prepared, 0.2 mass parts stannous octoate, 15 mass parts isophorone diisocyanates (IPDI) add 150 mass parts N, in dinethylformamide (DMF), mix,, at 10h, then add 18 mass parts Hydroxyethyl acrylates at 90 ℃ of reaction 4h 90 ℃ of reactions, obtain end-vinyl fluorine silicon graftomer.
(4) preparation of modified epoxy acrylate resin coating: fluorine silicon graftomer 10 mass parts of getting the end-vinyl in step (3) are dissolved in the THF/DMAC mixed solvent that 300 mass parts volume ratios are 1:2, add epoxy acrylic resin 90 mass parts, 3 mass parts light trigger 2-hydroxy-2-methyl-1-phenyl-acetones (1173), stir, obtain modified epoxy acrylate resin coating.
Embodiment 4
(1) preparation of end carboxyl methacrylic acid 17 fluorine certain herbaceous plants with big flowers ester polymers: with 2 mass parts butyl ethyl malonates, 50 mass parts toluene and 3 mass parts concentration are that the TBAH aqueous solution of 25wt% is even, react 3h under 30 ℃, toluene is removed in decompression, then add 80 mass parts tetrahydrofuran (THF)s and 50 mass parts methacrylic acid 17 fluorine certain herbaceous plants with big flowers esters, mix reaction 0.5h, after tetrahydrofuran (THF) is removed in decompression, be to be hydrolyzed 12h in the 5 mass parts trifluoroacetic acids of 60 ℃ and 60 mass parts dioxane mixing solutionss with the product that obtains in temperature, obtain holding carboxyl methacrylic acid 17 fluorine certain herbaceous plants with big flowers ester polymers, it is 8000 that number-average molecular weight obtains by gel permeation chromatography.
(2) preparation of the fluorine silicon graftomer of terminal hydroxy group end-blocking: (molecular weight is 10000 to end hydroxyl silicone oil 100 mass parts, four li, Shanghai industry and trade company limited), end carboxyl methacrylic acid 17 fluorine certain herbaceous plants with big flowers ester polymer 35 mass parts that step (1) prepares, dewatering agent N, N '-dicyclohexylcarbodiimide (DCC) 4 mass parts, catalyzer nitrogen azoles (HOAT) 3 mass parts, N, dinethylformamide (DMF) 300 mass parts,, at 110 ℃ of reaction 8h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
(3) preparation of end-vinyl fluorine silicon graftomer: the fluorine silicon graftomer of the terminal hydroxy group end-blocking that 100 mass parts steps (2) are prepared, 0.08 mass parts stannous octoate, 4,4 '-diphenylmethanediisocyanate (MDI), 1 mass parts joins 300 mass parts N, in N-N,N-DIMETHYLACETAMIDE (DMAC), mix, 100 ℃ of reactions at 4h, then add hydroxyethyl methylacrylate 1 mass parts at 100 ℃ of reaction 2h, obtain end-vinyl fluorine silicon graftomer.
(4) preparation of modified epoxy acrylate resin coating: end-vinyl fluorine silicon graftomer 2 mass parts of getting in step (3) are dissolved in the THF/DMAC mixed solvent that 100 mass parts volume ratios are 1:4; add epoxy acrylic resin 98 mass parts; light trigger 2; 4; 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO) 4 mass parts; stir, obtain modified epoxy acrylate resin coating.
Embodiment 5
(1) preparation of end carboxyl dodecafluoroheptyl methacrylate polymkeric substance: with 2 mass parts butyl ethyl malonates, 50 mass parts toluene and 3 mass parts concentration are that the TBAH aqueous solution of 25wt% is even, react 3h under 30 ℃, toluene is removed in decompression, then add 80 mass parts tetrahydrofuran (THF)s and 30 mass parts dodecafluoroheptyl methacrylates, mix reaction 0.5h, after tetrahydrofuran (THF) is removed in decompression, be to be hydrolyzed 12h in the 5 mass parts trifluoroacetic acids of 60 ℃ and 60 mass parts dioxane mixing solutionss with the product that obtains in temperature, obtain holding carboxyl dodecafluoroheptyl methacrylate polymkeric substance, it is 3000 that number-average molecular weight obtains by gel permeation chromatography.
(2) preparation of the fluorine silicon graftomer of terminal hydroxy group end-blocking: end hydroxyl silicone oil 100 mass parts (molecular weight 10000, four li, Shanghai industry and trade company limited), end carboxyl dodecafluoroheptyl methacrylate polymkeric substance 10 mass parts that step (1) prepares, 4 mass parts dewatering agent N, N '-dicyclohexylcarbodiimide (DCC), catalyzer 6-chloro-1-hydroxy benzo triazole (HOBT) 0.08 mass parts, N, N-N,N-DIMETHYLACETAMIDE (DMAC) 500 mass parts,, at 130 ℃ of reaction 10h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
(3) preparation of end-vinyl fluorine silicon graftomer: the fluorine silicon graftomer of the terminal hydroxy group end-blocking that 100 mass parts steps (2) are prepared, 0.5 mass parts dibutyltin diacetate, hexamethylene diisocyanate (HDI) 10 mass parts join THF/DMAC mixed solvent 300 mass parts that volume ratio is 1:3, mix, 65 ℃ of reactions at 20h, then add Propylene glycol monoacrylate 8 mass parts at 65 ℃ of reaction 10h, obtain end-vinyl fluorine silicon graftomer.
(4) preparation of modified epoxy acrylate resin coating: end-vinyl fluorine silicon graftomer 20 mass parts of getting in step (3) are dissolved in the THF/DMAC mixed solvent that 300 mass parts volume ratios are 1:4, add epoxy acrylic resin 80 mass parts, light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (1173) 3 mass parts, stir, obtain modified epoxy acrylate resin coating.
Embodiment 6
(1) end carboxyl methacrylic acid-1H, the preparation of-1H-perfluoro monooctyl ester polymkeric substance: with 2 mass parts butyl ethyl malonates, 50 mass parts toluene and 3 mass parts concentration are that the TBAH aqueous solution of 25wt% is even, react 3h under 30 ℃, toluene is removed in decompression, then add 80 mass parts tetrahydrofuran (THF)s and 20 mass parts methacrylic acid-1H,-1H-perfluoro monooctyl ester, mix reaction 0.5h, after tetrahydrofuran (THF) is removed in decompression, be to be hydrolyzed 12h in the 5 mass parts trifluoroacetic acids of 60 ℃ and 60 mass parts dioxane mixing solutionss with the product that obtains in temperature, obtain holding carboxyl methacrylic acid-1H,-1H-perfluoro monooctyl ester polymkeric substance, it is 4000 that number-average molecular weight obtains by gel permeation chromatography.
(2) preparation of the fluorine silicon graftomer of terminal hydroxy group end-blocking: (molecular weight is 2000 to end hydroxypropyl silicone oil 100 mass parts, four li, Shanghai industry and trade company limited), end carboxyl methacrylic acid-1H that step (1) prepares,-1H-perfluoro monooctyl ester polymkeric substance 100 mass parts, catalyzer Dibutyltin oxide (DBTO) 0.05 mass parts, DMF (DMF) 400 mass parts,, at 100 ℃ of reaction 20h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
(3) preparation of end-vinyl fluorine silicon graftomer: the fluorine silicon graftomer of the terminal hydroxy group end-blocking that 100 mass parts steps (2) are prepared, 1 mass parts two (dodecyl sulphur) dibutyl tin, 20 mass parts tolylene diisocyanates (TDI) join N, in N-N,N-DIMETHYLACETAMIDE (DMAC) 500 mass parts solvents, mix,, at 8h, then add methacrylic acid hydroxy butyl ester 20 mass parts at 85 ℃ of reaction 6h 85 ℃ of reactions, obtain end-vinyl fluorine silicon graftomer.
(4) preparation of modified epoxy acrylate resin coating: end-vinyl fluorine silicon graftomer 7.5 mass parts of getting in step (3) are dissolved in the THF/DMAC mixed solvent that 200 mass parts volume ratios are 1:4, add epoxy acrylic resin 92.5 mass parts, light trigger 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-1-acetone (659) 2.5 mass parts, stir, obtain modified epoxy acrylate resin coating.
Embodiment 7: the performance measurement of modified epoxy acrylate resin coating
The performance of the modified epoxy acrylate resin coating that embodiment 1～6 is prepared is measured.Do not add end-vinyl fluorine silicon graftomer and carry out modification, directly 100 mass parts epoxy acrylic resins and light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (1173) 3 mass parts are stirred, obtain contrasting coating.Do not add epoxy acrylic resin, 100 mass parts end-vinyl fluorine silicon graftomer and 3 mass parts light trigger 2-hydroxy-2-methyl-1-phenyl-acetones (1173) are stirred, obtain blank contrast.Coating is placed under UV-light after irradiation is solidified and measured performance.
Wherein, with water contact angle: adopt contact angle measurement to measure the contact angle of distilled water on film coated surface, all measurements are all carried out under room temperature (25 ℃); The test of acid resistance and salt resistant character is sample to be put into 40wt% vitriol oil water and 5wt%NaCl solution soaks 24h, surveys its contact angle; Stain resistance: press GB/9780-1988 and measure; Artificial ageing resistance: press GB/T1865-88 and measure.The results are shown in Table 1.
Can find out that by table 1 the pure epoxy acrylic resin that compares adds the hydrophobic properties of the surface, chemically-resistant of the coating of fluorine silicon graftomer and the performance such as ageing-resistant all obviously to improve; Along with the increase of the content of fluorine silicon graftomer, the over-all properties of coating also obviously improves thereupon; In addition,, by the comparative example, can find out when the increase of fluorochemical monomer side chain fluorine atom, the corresponding raising of coating property of fluorine silicon graftomer modification.
The performance index of table 1 modified epoxy acrylate resin coating
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. end-vinyl fluorine silicon graftomer is characterized in that having following structure:
N is the integer in 5～100;
R, R
3For hydrogen or methyl;
R
1For dimethylene, trimethylene or tetramethylene;
R
2For tolyl, hexa-methylene, 4,4 '-ditan, 1,3,3-trimethyl-cyclohexane, phenyl or tri-methyl hexamethylene;
R
fFor the Polyfluoroalkyl of C atomicity 1～8, namely the hydrogen atom in alkyl is by the some or all of displacement of fluorine atom.
2. the preparation method of an end-vinyl fluorine silicon graftomer claimed in claim 1, it is characterized in that comprising following concrete steps: with the fluorine silicon graftomer of the terminal hydroxy group end-blocking of 100 mass parts, 0.05～1 mass parts of catalyst, 1～20 mass parts isocyanate-monomer joins in 100～500 mass parts solvents, mix, 60～100 ℃ of reaction 4～24h, add 1～20 mass parts (methyl) acrylic acid hydroxy alkyl ester, 60～100 ℃ of reaction 2～12h, obtain end-vinyl fluorine silicon graftomer.
3. the preparation method of end-vinyl fluorine silicon graftomer according to claim 2 is characterized in that: described solvent refers at least a in tetrahydrofuran (THF), DMF and N,N-dimethylacetamide; Described catalyzer refers at least a in dibutyl tin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tin and dibutyltin diacetate; Described isocyanate-monomer nail phenylene diisocyanate, isophorone diisocyanate, PPDI, trimethylammonium hexamethylene diisocyanate, 4, at least a in 4 '-diphenylmethanediisocyanate and hexamethylene diisocyanate; At least a in described (methyl) acrylic acid hydroxy alkyl ester nail base Hydroxyethyl acrylate, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate and methacrylic acid hydroxy butyl ester.
4. the preparation method of end-vinyl fluorine silicon graftomer according to claim 2 is characterized in that: described solvent refers to that volume ratio is the tetrahydrofuran (THF)/N,N-dimethylacetamide mixed solvent of 1:3; Described catalyzer refers to dibutyl tin dilaurate; At least a in described isocyanate-monomer nail phenylene diisocyanate and isophorone diisocyanate.
5. the preparation method of end-vinyl fluorine silicon graftomer according to claim 2, it is characterized in that: the fluorine silicon graftomer of described terminal hydroxy group end-blocking is prepared by following methods: get end hydroxyl silicone oil 100 mass parts, end carboxy acrylic fluoroalkyl ester polymer 10～100 mass parts, dewatering agent 0～5 mass parts, catalyzer 0.01～3 mass parts, N, dinethylformamide or N, N-N,N-DIMETHYLACETAMIDE 0～500 mass parts, 100～180 ℃ are reacted 8～36h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
6. the preparation method of end-vinyl fluorine silicon graftomer according to claim 5 is characterized in that: at least a in described end hydroxyl silicone oil finger tip hydroxyl dimethyl silicone oil, end hydroxypropyl dimethyl silicone oil and terminal hydroxy group methyl phenyl silicone oil; Described dewatering agent refers to 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride and N, at least a in N '-dicyclohexylcarbodiimide; Described catalyzer refers at least a in DMAP, 1-hydroxyl-7-azo benzotriazole, 6-chloro-1-hydroxy benzo triazole, Mono-n-butyltin and Dibutyltin oxide.
7. the preparation method of end-vinyl fluorine silicon graftomer according to claim 5, it is characterized in that: described end carboxy acrylic fluoroalkyl ester polymer is prepared by following methods: with 2 mass parts butyl ethyl malonates, 50 mass parts toluene and 3 mass parts concentration are that the TBAH aqueous solution of 25wt% is even, react 3h under 30 ℃, toluene is removed in decompression, then add 80 mass parts tetrahydrofuran (THF)s and 5～50 mass parts fluorochemical monomers, reaction 0.5h, after tetrahydrofuran (THF) is removed in decompression, the 5 mass parts trifluoroacetic acids and the 60 mass parts dioxane mixing solutionss that the product that obtains are placed in 60 ℃ are hydrolyzed 12h, obtain holding carboxy acrylic fluoroalkyl ester polymer.
8. the preparation method of end-vinyl fluorine silicon graftomer according to claim 7, it is characterized in that: described fluorochemical monomer refers to vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl esters, methacrylic acid-1H, at least a in 1H-perfluoro monooctyl ester and methacrylic acid 17 fluorine certain herbaceous plants with big flowers esters.
9. the application of end-vinyl fluorine silicon graftomer claimed in claim 1 in preparation modified epoxy acrylate resin coating, it is characterized in that comprising following steps: 2～100 mass parts end-vinyl fluorine silicon graftomer are joined, in the solvent of 100～500 mass parts, add 80～100 mass parts epoxy (methyl) acrylic resins, the light trigger of 1～5 mass parts, mix, obtain modified epoxy acrylate resin coating.
10. the application of end-vinyl fluorine silicon graftomer according to claim 9 in preparation modified epoxy acrylate resin coating, it is characterized in that: described solvent refers to tetrahydrofuran (THF), N, at least a in dinethylformamide and N,N-dimethylacetamide; Described light trigger refers to 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxy-cyclohexyl phenyl ketone, 2; 4,6-trimethylbenzoyl-diphenyl phosphine oxide, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-at least a in 1-acetone and EDMAB.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310272030.3A CN103396558B (en) | 2013-07-01 | 2013-07-01 | End-vinyl fluorine silicon graftomer and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310272030.3A CN103396558B (en) | 2013-07-01 | 2013-07-01 | End-vinyl fluorine silicon graftomer and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103396558A true CN103396558A (en) | 2013-11-20 |
| CN103396558B CN103396558B (en) | 2015-11-18 |
Family
ID=49560308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310272030.3A Active CN103396558B (en) | 2013-07-01 | 2013-07-01 | End-vinyl fluorine silicon graftomer and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103396558B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061770A (en) * | 2015-08-10 | 2015-11-18 | 广东博兴新材料科技有限公司 | Organic fluorine-silicon light-cured resin and preparation method therefor and application thereof |
| CN106674450A (en) * | 2016-12-06 | 2017-05-17 | 哈尔滨工业大学无锡新材料研究院 | Triblock hybrid fluorosilicone polymer and preparation method thereof |
| CN107522865A (en) * | 2017-08-29 | 2017-12-29 | 无锡龙驰氟硅新材料有限公司 | A kind of silicon-fluorine polymer thing and its preparation method and application |
| CN110003441A (en) * | 2019-04-22 | 2019-07-12 | 广州大学 | A kind of preparation method of UV curable water-borne isocyanates grafting fluorosilicone modified epoxy acrylate resin |
| CN113150283A (en) * | 2021-05-10 | 2021-07-23 | 哈尔滨工业大学无锡新材料研究院 | Fluorosilicone polymer capable of being subjected to UV light and thermal curing, preparation method thereof and coating |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63182379A (en) * | 1987-01-22 | 1988-07-27 | Yokohama Rubber Co Ltd:The | Coating material for glass run of automobile |
| CN1718656A (en) * | 2005-07-28 | 2006-01-11 | 同济大学 | A kind of ultraviolet-curing paint that contains POSS and preparation method thereof |
| CN102344516A (en) * | 2011-07-13 | 2012-02-08 | 中科院广州化学有限公司 | (Alkyl)fluoroalkyl acrylate polymer containing terminal alkyl ester or terminal carboxylic acid, its preparation and application |
| CN102898932A (en) * | 2012-09-21 | 2013-01-30 | 中科院广州化学有限公司 | Composite ultraviolet-curing coating containing vinyl-terminated fluorinated alkyl ester polymer, its preparation and application |
-
2013
- 2013-07-01 CN CN201310272030.3A patent/CN103396558B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63182379A (en) * | 1987-01-22 | 1988-07-27 | Yokohama Rubber Co Ltd:The | Coating material for glass run of automobile |
| CN1718656A (en) * | 2005-07-28 | 2006-01-11 | 同济大学 | A kind of ultraviolet-curing paint that contains POSS and preparation method thereof |
| CN102344516A (en) * | 2011-07-13 | 2012-02-08 | 中科院广州化学有限公司 | (Alkyl)fluoroalkyl acrylate polymer containing terminal alkyl ester or terminal carboxylic acid, its preparation and application |
| CN102898932A (en) * | 2012-09-21 | 2013-01-30 | 中科院广州化学有限公司 | Composite ultraviolet-curing coating containing vinyl-terminated fluorinated alkyl ester polymer, its preparation and application |
Non-Patent Citations (3)
| Title |
|---|
| 刘长利等: "光固化有机硅材料研究进展", 《材料导报》 * |
| 肖文清等: "国内硅氟树脂涂料的研究新进展", 《广州化工》 * |
| 陶永红等: "有机硅/丙烯酸酯/聚氨酯光固化树脂的合成及应用", 《有机硅材料》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061770A (en) * | 2015-08-10 | 2015-11-18 | 广东博兴新材料科技有限公司 | Organic fluorine-silicon light-cured resin and preparation method therefor and application thereof |
| CN105061770B (en) * | 2015-08-10 | 2017-08-04 | 广东博兴新材料科技有限公司 | A kind of organic fluorinated silicone light-cured resin and its preparation method and application |
| CN106674450A (en) * | 2016-12-06 | 2017-05-17 | 哈尔滨工业大学无锡新材料研究院 | Triblock hybrid fluorosilicone polymer and preparation method thereof |
| CN106674450B (en) * | 2016-12-06 | 2019-07-05 | 无锡龙驰氟硅新材料有限公司 | Three block heterozygosis silicon-fluorine polymer object and preparation method thereof |
| CN107522865A (en) * | 2017-08-29 | 2017-12-29 | 无锡龙驰氟硅新材料有限公司 | A kind of silicon-fluorine polymer thing and its preparation method and application |
| CN110003441A (en) * | 2019-04-22 | 2019-07-12 | 广州大学 | A kind of preparation method of UV curable water-borne isocyanates grafting fluorosilicone modified epoxy acrylate resin |
| CN110003441B (en) * | 2019-04-22 | 2021-06-22 | 广州大学 | Preparation method of UV-cured waterborne isocyanate-grafted fluorosilicone modified epoxy acrylic resin |
| CN113150283A (en) * | 2021-05-10 | 2021-07-23 | 哈尔滨工业大学无锡新材料研究院 | Fluorosilicone polymer capable of being subjected to UV light and thermal curing, preparation method thereof and coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103396558B (en) | 2015-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103396558B (en) | End-vinyl fluorine silicon graftomer and its preparation method and application | |
| CN108587271B (en) | Water-based UV polyurethane coating and preparation method thereof | |
| CN103589298B (en) | One is coating material solidified and preparation method containing end-vinyl amphipathic fluoride graftomer complex light | |
| Ghosal et al. | High-performance soya polyurethane networked silica hybrid nanocomposite coatings | |
| CN103627003B (en) | A kind of fluorine silicon graftomer Graft Epoxy Resin and preparation method thereof | |
| CN111826075B (en) | Self-repairing organic fluorine-silicon modified polyurethane waterproof coating and preparation method thereof | |
| CN104830222B (en) | Dual-curable polyurethane paint with low surface energy and preparation method thereof | |
| JP5704188B2 (en) | Waterproof / moisture-proof coating composition | |
| Liang et al. | Bio-based omniphobic polyurethane coating providing anti-smudge and anti-corrosion protection | |
| CN101775144B (en) | Fluorine silicon resin, preparation method thereof and antifouling paint | |
| JP2012251035A (en) | Curable resin composition | |
| CN103588950B (en) | A kind of end-vinyl amphipathic fluoride graftomer and preparation method thereof and application | |
| Srivastava et al. | UV curable polyurethane acrylate coatings for metal surfaces | |
| CN112079983A (en) | Synthetic method of organic fluorine and silicon modified waterborne polyurethane | |
| Narute et al. | Study of the performance of polyurethane coatings derived from cottonseed oil polyol | |
| CN108300292A (en) | It is a kind of containing acrylate modified organic siliconresin high-weatherability photocureable coating | |
| Cui et al. | Fabrication of UV/moisture dual curing coatings based on fluorinated polyoxetanes for anti-fouling applications | |
| CN104693408A (en) | Organic fluorine-modified polyurethane photocuring prepolymer, preparation method thereof and ultraviolet light curing film prepared from organic fluorine-modified polyurethane photocuring prepolymer | |
| CN103589297B (en) | A kind of containing end-vinyl fluorine silicon graft copolymer photocuring composite coating and preparation method | |
| CN104650314A (en) | Dual-curing organic fluorine modified polyurethane pre-polymer and preparation method thereof as well as ultraviolet photo-cured membrane manufactured by polyurethane pre-polymer | |
| Popa et al. | Copolymerization of butyl acrylate with methyl methacrylate in a bubble column reactor and the use of copolymer in corrosion protection | |
| CN113683934B (en) | High-transparency washable acrylate anti-corrosion coating and preparation method thereof | |
| CN113387898B (en) | Ten-functionality fluorine-containing photocuring anti-fouling additive and application thereof | |
| JP5338809B2 (en) | Polyfunctional fluorine-containing compound and method for producing the compound | |
| Chen et al. | High solid and low viscosity waterborne polyurethane acrylate with excellent anti-corrosion and anti-bacterial performances |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |