CN103396558B - End-vinyl fluorine silicon graftomer and its preparation method and application - Google Patents
End-vinyl fluorine silicon graftomer and its preparation method and application Download PDFInfo
- Publication number
- CN103396558B CN103396558B CN201310272030.3A CN201310272030A CN103396558B CN 103396558 B CN103396558 B CN 103396558B CN 201310272030 A CN201310272030 A CN 201310272030A CN 103396558 B CN103396558 B CN 103396558B
- Authority
- CN
- China
- Prior art keywords
- mass parts
- graftomer
- fluorine silicon
- preparation
- vinyl
- 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.)
- Active
Links
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to fluorine silicon graftomer preparing technical field, disclose a kind of end-vinyl fluorine silicon graftomer and modified epoxy acrylate resin coating thereof.This end-vinyl fluorine silicon graftomer is prepared by following methods: by 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 DEG C of reaction 4 ~ 24h, add 1 ~ 20 mass parts (methyl) acrylic acid hydroxy alkyl ester, 60 ~ 100 DEG C of reaction 2 ~ 12h, obtain end-vinyl fluorine silicon graftomer.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, the coating utilizing it to prepare has excellent hydrophobic performance, chemically-resistant, anti-pollution (3%) and the performance such as ageing-resistant.
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
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, bisphenol-A epoxy 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 the problem such as weathering resistance, resistance to corrosion-resistant, particularly due to surface tension that epoxy acrylic resin is higher, the epoxypaint surface of preparation has and has higher surface energy, limits its use in the high-end field such as anti-fouling ship paint, electronic product.
Fluorine carbon bond can be large, and arrangement closely, effectively can 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, oxidative degradation performance.Fluorine silicon contained polymer has excellent heatproof, waterproof, the performance such as antifouling, weather-proof, ageing-resistant, therefore organic silicon-fluorine polymkeric substance is widely used in the industrial circles such as automobile, electronics, aviation, application, weaving, and wherein organic silicon-fluorine polymer application demonstrates excellent water proof anti-soil ageing-resistant energy performance in coatings industry.Current fluorine-containing epoxy acrylic resin mainly adds fluorine atom that is single or that lacked in 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 to add fluorochemical monomer in a large number, but greatly increase use cost; Although fluorine silicon contained polymer blended in addition can reach hydrophobic performance, anti-pollution characteristic etc. that a small amount of silicon-fluorine polymer thing improves coating, easily occur being separated, affect the mechanical and physical performance of coating.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of end-vinyl fluorine silicon graftomer.
Another object of the present invention is the preparation method providing a kind 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.
Object of the present invention is realized 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, the hydrogen atom namely 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:
By 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 DEG C of reaction 4 ~ 24h, add 1 ~ 20 mass parts (methyl) acrylic acid hydroxy alkyl ester, 60 ~ 100 DEG C of reaction 2 ~ 12h, obtain end-vinyl fluorine silicon graftomer.
Described solvent refers at least one in tetrahydrofuran (THF) (THF), DMF (DMF) and N,N-dimethylacetamide (DMAC), is preferably the THF/DMAC mixed solvent that volume ratio is 1:3.
Described catalyzer refers at least one in dibutyl tin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tins and dibutyltin diacetate, preferred dibutyl tin dilaurate.
Described isocyanate-monomer nail phenylene diisocyanate (TDI), isophorone diisocyanate (IPDI), PPDI, trimethylammonium hexamethylene diisocyanate, 4, at least one in 4 '-diphenylmethanediisocyanate (MDI) and hexamethylene diisocyanate (HDI), at least one in preferred tolylene diisocyanate (TDI) and isophorone diisocyanate (IPDI).
At least one in described (methyl) acrylic acid hydroxy alkyl ester methacrylic acid hydroxyl ethyl ester, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate and methacrylate.
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 carboxyl fiuoroalkylacrylate 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 DEG C of reaction 8 ~ 36h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
At least one 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, N ' at least one in-dicyclohexylcarbodiimide (DCC).
Described catalyzer refers at least one in DMAP (DMAP), the chloro-1-hydroxy benzo triazole (HOBT) of 1-hydroxyl-7-azo benzotriazole (HOAT), 6-, Mono-n-butyltin (MBTO) and Dibutyltin oxide (DBTO).
Described end carboxyl fiuoroalkylacrylate polymer is prepared by following methods: by 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, 3h is reacted at 30 DEG C, removed under reduced pressure toluene, then 80 mass parts tetrahydrofuran (THF)s and 5 ~ 50 mass parts fluorochemical monomers are added, reaction 0.5h, after removed under reduced pressure tetrahydrofuran (THF), the 5 mass parts trifluoroacetic acids and the 60 mass parts dioxane mixing solutionss that the product obtained are placed in 60 DEG C are hydrolyzed 12h, obtain end carboxyl fiuoroalkylacrylate polymer.
Described fluorochemical monomer refers at least one in vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester, methacrylic acid-1H, 1H-perfluoro monooctyl ester and methacrylic acid 17 fluorine certain herbaceous plants with big flowers ester.
The application of above-mentioned end-vinyl fluorine silicon graftomer in preparation modified epoxy acrylate resin coating, comprise following steps: join in the solvent of 100 ~ 500 mass parts by 2 ~ 100 mass parts end-vinyl fluorine silicon graftomer, 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 one 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-hydroxycyclohexyl phenyl ketone (184), 2; at least one in 4,6-trimethylbenzoy-dipheny phosphine oxide (TPO), 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-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 can separately UV-light reaction or with 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, relative 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 utilizing end-vinyl fluorine silicon graftomer of the present invention to prepare has the performance such as excellent hydrophobic performance (water contact angle is up to 130 °), chemically-resistant, anti-pollution (3%) and ageing-resistant (1000h non-foaming, do not come off).
Accompanying drawing explanation
Fig. 1 is the IR spectrogram of the end-vinyl fluorine silicon graftomer that embodiment 1 prepares.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) preparation of end carboxyl vinylformic acid trifluoro ethyl ester polymkeric substance: by 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, 3h is reacted at 30 DEG C, removed under reduced pressure toluene, then 80 mass parts tetrahydrofuran (THF)s and 5 mass parts vinylformic acid trifluoro ethyl esters are added, mix reaction 0.5h, after removed under reduced pressure tetrahydrofuran (THF), the product obtained is hydrolyzed 12h in temperature is the 18 mass parts trifluoroacetic acids of 60 DEG C and 60 mass parts dioxane mixing solutionss, obtain end carboxyl vinylformic acid trifluoro ethyl ester polymkeric substance, number-average molecular weight obtains being 15000 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 Trade Co., Ltd.), end carboxyl vinylformic acid trifluoro ethyl ester polymkeric substance 75 mass parts that step (1) prepares, catalyzer Dibutyltin oxide (DBTO) 0.01 mass parts, at 180 DEG C of reaction 36h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
(3) preparation of end-vinyl fluorine silicon graftomer: by the fluorine silicon graftomer of the terminal hydroxy group end-blocking that 100 mass parts steps (2) prepare, 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 DEG C of reactions at 24h, then 5 mass parts hydroxyethyl methylacrylates are added at 60 DEG C of reaction 12h, obtain end-vinyl fluorine silicon graftomer, IR spectroscopic analysis is carried out to it, sees Fig. 1.
As seen from Figure 1,1638cm
-1and 1741cm
-1belong to carbon-carbon double bond stretching vibration peak and carbonylic stretching vibration peak respectively, 1300cm
-1, 1190cm
-1belong to CF respectively
3and CF
2cF asymmetrical stretching vibration, 3297cm
-1for 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: by 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, 3h is reacted at 30 DEG C, removed under reduced pressure toluene, then 80 mass parts tetrahydrofuran (THF)s and 15 trifluoroethyl methacrylates are added, mix reaction 0.5h, after removed under reduced pressure tetrahydrofuran (THF), the product obtained is hydrolyzed 12h in temperature is the 5 mass parts trifluoroacetic acids of 60 DEG C and 60 mass parts dioxane mixing solutionss, obtain end carboxyl trifluoroethyl methacrylate polymkeric substance, number-average molecular weight obtains being 1000 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 Trade Co., Ltd.), end carboxyl trifluoroethyl methacrylate polymkeric substance 50 mass parts that step (1) prepares, catalyzer Mono-n-butyltin (MBTO) 0.03 mass parts, at 160 DEG C of reaction 18h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
(3) the fluorine silicon graftomer of the terminal hydroxy group end-blocking step (2) of 100 mass parts prepared, 0.8 mass parts two (dodecyl sulphur) dibutyl tin, tolylene diisocyanate (TDI) 20 mass parts adds 350 mass parts N, in dinethylformamide (DMF) solvent, mix, 80 DEG C of reactions at 14h, then add hydroxyethyl methylacrylate 10 mass parts at 80 DEG C of reaction 8h, obtain end-vinyl fluorine silicon graftomer.
(4) preparation of modified epoxy acrylate resin coating: the end-vinyl fluorine silicon graftomer got in 3 mass parts steps (3) is dissolved in the DMAC solvent of 400 mass parts, add 97 mass parts epoxy acrylic resins, 5 mass parts light trigger 1-hydroxycyclohexyl phenyl ketone (184), stir, obtain modified epoxy acrylate resin coating.
Embodiment 3
(1) preparation of end carboxyl Hexafluorobutyl mathacrylate polymkeric substance: by 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, 3h is reacted at 30 DEG C, removed under reduced pressure toluene, then the Hexafluorobutyl mathacrylate of 80 mass parts tetrahydrofuran (THF)s and 10 mass parts is added, mix reaction 0.5h, after removed under reduced pressure tetrahydrofuran (THF), the product obtained being placed in temperature is that the 5 mass parts trifluoroacetic acids of 60 DEG C and 60 mass parts dioxane mixing solutionss are hydrolyzed 12h, obtain end carboxyl Hexafluorobutyl mathacrylate polymkeric substance, number-average molecular weight obtains being 5580 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 Trade Co., Ltd.), 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 DEG C of reaction 36h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
(3) preparation of end-vinyl fluorine silicon graftomer: by the fluorine silicon graftomer of the terminal hydroxy group end-blocking that 100 mass parts steps (2) prepare, 0.2 mass parts stannous octoate, 15 mass parts isophorone diisocyanates (IPDI) add 150 mass parts N, in dinethylformamide (DMF), mix, 90 DEG C of reactions at 10h, then add 18 mass parts Hydroxyethyl acrylates at 90 DEG C of reaction 4h, 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) is 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-acetone (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 polymer: by 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, 3h is reacted at 30 DEG C, removed under reduced pressure toluene, then 80 mass parts tetrahydrofuran (THF)s and 50 mass parts methacrylic acid 17 fluorine certain herbaceous plants with big flowers esters are added, mix reaction 0.5h, after removed under reduced pressure tetrahydrofuran (THF), the product obtained is hydrolyzed 12h in temperature is the 5 mass parts trifluoroacetic acids of 60 DEG C and 60 mass parts dioxane mixing solutionss, obtain end carboxyl methacrylic acid 17 fluorine certain herbaceous plants with big flowers ester polymer, number-average molecular weight obtains being 8000 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 Trade Co., Ltd.), 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 DEG C of reaction 8h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
(3) preparation of end-vinyl fluorine silicon graftomer: by the fluorine silicon graftomer of the terminal hydroxy group end-blocking that 100 mass parts steps (2) prepare, 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 DEG C of reactions at 4h, then add hydroxyethyl methylacrylate 1 mass parts at 100 DEG C 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) is 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-trimethylbenzoy-dipheny phosphine oxide (TPO) 4 mass parts; stir, obtain modified epoxy acrylate resin coating.
Embodiment 5
(1) preparation of end carboxyl dodecafluoroheptyl methacrylate polymkeric substance: by 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, 3h is reacted at 30 DEG C, removed under reduced pressure toluene, then 80 mass parts tetrahydrofuran (THF)s and 30 mass parts dodecafluoroheptyl methacrylates are added, mix reaction 0.5h, after removed under reduced pressure tetrahydrofuran (THF), the product obtained is hydrolyzed 12h in temperature is the 5 mass parts trifluoroacetic acids of 60 DEG C and 60 mass parts dioxane mixing solutionss, obtain end carboxyl dodecafluoroheptyl methacrylate polymkeric substance, number-average molecular weight obtains being 3000 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 Trade Co., Ltd.), 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 DEG C of reaction 10h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
(3) preparation of end-vinyl fluorine silicon graftomer: by the fluorine silicon graftomer of the terminal hydroxy group end-blocking that 100 mass parts steps (2) prepare, 0.5 mass parts dibutyltin diacetate, hexamethylene diisocyanate (HDI) 10 mass parts joins THF/DMAC mixed solvent 300 mass parts that volume ratio is 1:3, mix, 65 DEG C of reactions at 20h, then add Propylene glycol monoacrylate 8 mass parts at 65 DEG C 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) is 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: by 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, 3h is reacted at 30 DEG C, removed under reduced pressure toluene, then 80 mass parts tetrahydrofuran (THF)s and 20 mass parts methacrylic acid-1H are added,-1H-perfluoro monooctyl ester, mix reaction 0.5h, after removed under reduced pressure tetrahydrofuran (THF), the product obtained is hydrolyzed 12h in temperature is the 5 mass parts trifluoroacetic acids of 60 DEG C and 60 mass parts dioxane mixing solutionss, obtain end carboxyl methacrylic acid-1H,-1H-perfluoro monooctyl ester polymkeric substance, number-average molecular weight obtains being 4000 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 Trade Co., Ltd.), end carboxyl methacrylic acid-the 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 DEG C of reaction 20h, obtain the fluorine silicon graftomer of terminal hydroxy group end-blocking.
(3) preparation of end-vinyl fluorine silicon graftomer: by the fluorine silicon graftomer of the terminal hydroxy group end-blocking that 100 mass parts steps (2) prepare, 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 solvent, mix, 85 DEG C of reactions at 8h, then add methacrylate 20 mass parts at 85 DEG C of reaction 6h, 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) is 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 prepares 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-acetone (1173) are stirred, obtains blank.Performance is measured after irradiating solidification under coating being placed UV-light.
Wherein, with water contact angle: adopt contact angle measurement to measure the contact angle of distilled water in film coated surface, all measurements are all carried out under room temperature (25 DEG C); Acid resistance and salt resistant character test sample are put into 40wt% vitriol oil water and 5wt%NaCl solution soaks 24h, surveys its contact angle; Stain resistance: measure by GB/9780-1988; Artificial ageing resistance: measure by GB/T1865-88.The results are shown in Table 1.
Can be found out by table 1, compare pure epoxy acrylic resin, adds the hydrophobic properties of the surface of the coating of fluorine silicon graftomer, chemically-resistant and the performance such as ageing-resistant and all significantly improve; Along with the increase of the content of fluorine silicon graftomer, the over-all properties of coating also significantly improves thereupon; In addition, by comparative example, can find out when fluorochemical monomer side chain fluorine atom increases, 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 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 (10)
1. an 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 '-diphenyl methyl, 1,3,3-trimethylcyclohexyl, phenyl or tri-methyl hexamethylene;
R
ffor the Polyfluoroalkyl of C atomicity 1 ~ 8, the hydrogen atom namely in alkyl is by the some or all of displacement of fluorine atom.
2. the preparation method of an end-vinyl fluorine silicon graftomer according to claim 1, it is characterized in that comprising following concrete steps: by 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 DEG C of reaction 4 ~ 24h, add 1 ~ 20 mass parts (methyl) acrylic acid hydroxy alkyl ester, 60 ~ 100 DEG C 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 one in tetrahydrofuran (THF), DMF and N,N-dimethylacetamide; Described catalyzer refers at least one in dibutyl tin dilaurate, stannous octoate, two (dodecyl sulphur) dibutyl tins and dibutyltin diacetate; Described isocyanate-monomer nail phenylene diisocyanate, isophorone diisocyanate, PPDI, trimethylammonium hexamethylene diisocyanate, 4, at least one in 4 '-diphenylmethanediisocyanate and hexamethylene diisocyanate; At least one in described (methyl) acrylic acid hydroxy alkyl ester methacrylic acid hydroxyl ethyl ester, Hydroxyethyl acrylate, Rocryl 410, Propylene glycol monoacrylate and methacrylate.
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 one 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 carboxyl fiuoroalkylacrylate 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 DEG C of reaction 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 one 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, N ' at least one in-dicyclohexylcarbodiimide; Described catalyzer refers at least one in DMAP, 1-hydroxyl-7-azo benzotriazole, the chloro-1-hydroxy benzo triazole of 6-, 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 carboxyl fiuoroalkylacrylate polymer is prepared by following methods: by 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, 3h is reacted at 30 DEG C, removed under reduced pressure toluene, then 80 mass parts tetrahydrofuran (THF)s and 5 ~ 50 mass parts fluorochemical monomers are added, reaction 0.5h, after removed under reduced pressure tetrahydrofuran (THF), the 5 mass parts trifluoroacetic acids and the 60 mass parts dioxane mixing solutionss that the product obtained are placed in 60 DEG C are hydrolyzed 12h, obtain end carboxyl fiuoroalkylacrylate polymer.
8. the preparation method of end-vinyl fluorine silicon graftomer according to claim 7, it is characterized in that: described fluorochemical monomer refers at least one in vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester, methacrylic acid-1H, 1H-perfluoro monooctyl ester and methacrylic acid 17 fluorine certain herbaceous plants with big flowers ester.
9. the application of end-vinyl fluorine silicon graftomer according to 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 one in dinethylformamide and N,N-dimethylacetamide; Described light trigger refers to 2-hydroxy-2-methyl-1-phenyl-acetone, 1-hydroxycyclohexyl phenyl ketone, 2; at least one in 4,6-trimethylbenzoy-dipheny phosphine oxide, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-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 CN103396558A (en) | 2013-11-20 |
| CN103396558B true 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) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN107522865B (en) * | 2017-08-29 | 2021-06-25 | 无锡龙驰氟硅新材料有限公司 | Fluorosilicone polymer and preparation method and application thereof |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| 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 |
-
2013
- 2013-07-01 CN CN201310272030.3A patent/CN103396558B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| 光固化有机硅材料研究进展;刘长利等;《材料导报》;20060415;第20卷(第4期);第44-48页 * |
| 国内硅氟树脂涂料的研究新进展;肖文清等;《广州化工》;20110808;第39卷(第15期);第63-64页 * |
| 有机硅/丙烯酸酯/聚氨酯光固化树脂的合成及应用;陶永红等;《有机硅材料》;20040127;第18卷(第1期);第18-19页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103396558A (en) | 2013-11-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103396558B (en) | End-vinyl fluorine silicon graftomer and its preparation method and application | |
| CN103589298B (en) | One is coating material solidified and preparation method containing end-vinyl amphipathic fluoride graftomer complex light | |
| Malshe et al. | Fluorinated acrylic copolymers: Part I: Study of clear coatings | |
| Ghosal et al. | High-performance soya polyurethane networked silica hybrid nanocomposite coatings | |
| CN108587271B (en) | Water-based UV polyurethane coating and preparation method thereof | |
| CN103627003B (en) | A kind of fluorine silicon graftomer Graft Epoxy Resin and preparation method thereof | |
| CN102898932B (en) | Composite ultraviolet-curing coating containing vinyl-terminated fluorinated alkyl ester polymer, its preparation and application | |
| JP5704188B2 (en) | Waterproof / moisture-proof coating composition | |
| CN104830222B (en) | Dual-curable polyurethane paint with low surface energy and preparation method thereof | |
| CN103724558B (en) | A kind of strawberry type structure inorganic/organic fluoride-containing microballoon and preparation method thereof and application | |
| Li et al. | Near-infrared responsive smart superhydrophobic coating with self-healing and robustness enhanced by disulfide-bonded polyurethane | |
| CN101775144B (en) | Fluorine silicon resin, preparation method thereof and antifouling paint | |
| CN103588950B (en) | A kind of end-vinyl amphipathic fluoride graftomer and preparation method thereof and application | |
| CN101870187B (en) | Easily cleaned organic coating and preparation method thereof | |
| CN103333314A (en) | Cation photocuring fluorinated polyurethane resin and preparation method thereof | |
| CN102964546A (en) | Water-dispersible ultraviolet crosslinking fluorine-containing polymer and application thereof | |
| CN105482604A (en) | Water-based anti-doodling paint and preparation method thereof | |
| CN103601891B (en) | A kind of crosslinkable fluorine silicon resin and preparation thereof and application on super two thin material | |
| CN113462232A (en) | Water-proof antifouling photocureable coating and preparation method and application thereof | |
| CN110922526A (en) | Fluorine-containing polymer and protective coating agent containing same | |
| CN103589297B (en) | A kind of containing end-vinyl fluorine silicon graft copolymer photocuring composite coating and preparation method | |
| Chen et al. | High solid and low viscosity waterborne polyurethane acrylate with excellent anti-corrosion and anti-bacterial performances | |
| Popa et al. | Copolymerization of butyl acrylate with methyl methacrylate in a bubble column reactor and the use of copolymer in corrosion protection | |
| 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 | |
| CN102898567A (en) | Fluorine-containing epoxy resin, and preparation method and application thereof |
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 |