CN102532550A - Preparation method and application of fluorine-containing alkyl silicon resin - Google Patents
Preparation method and application of fluorine-containing alkyl silicon resin Download PDFInfo
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- CN102532550A CN102532550A CN201110451064XA CN201110451064A CN102532550A CN 102532550 A CN102532550 A CN 102532550A CN 201110451064X A CN201110451064X A CN 201110451064XA CN 201110451064 A CN201110451064 A CN 201110451064A CN 102532550 A CN102532550 A CN 102532550A
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Abstract
The invention introduces a preparation method and application of fluorine-containing alkyl silicon resin. The preparation of the resin utilizes Nonafluorobutanesulfonyl fluoride (Perflurohexane sulphonyl fluoride) and r-aminopropyl triethoxy silane as raw materials to conduct amidation to obtain Nonafluorobutanesulfonyl fluoride (Perflurohexane sulphonyl fluoride) aminopropyl triethoxy silane which is exchanged with 1, 2-propylene glycol after refining, and enables alcohol with low molecular weight to be evaporated out to obtain fluorine-containing alkyl fluoride silicon resin. The fluorine-containing alkyl silicon resin has good chemical stability, chemical resistance and weather resistance after film formation, is applied to water dispersible slice-shaped zinc aluminum coating and abrasion-reducing coating. The prepared slice-shaped zinc aluminum coating has good hardness, adhesion, salt mist resistance and abrasion reducing performance.
Description
Technical field:
The present invention relates to fluorine-containing alkyl silicone preparation method and application thereof, relate in particular to two kinds of fluorine modified silicone resins, preparation method and its application.
Background technology:
Silicone resin contains Si-O and Si-C key; The Si-O key is identical with silicate inorganic thing structural unit with formation silicic acid, and the Si-C key has the character of partial organic substances simultaneously, makes it not only have the character of inorganics but also have organic character; And make it that weathering resistance arranged; Ozone resistance, nontoxic, good characteristics such as tasteless and physiology inertia.
Organofluorine compound is introduced fluorine atom in the compound; Because the electronegativity of fluorine atom is big, adjacent fluorine atom repels each other, and the C-C main chain is surrounded by a series of fluorine atom; Form the screening of nucleus of height; Protected the stability of C-C chain, made fluorochemicals have extremely stable chemicalstability, chemical-resistant and weathering resistance thereof.
We attempt fluorochemical monomer is introduced in the silicone resin, through the excellent resin of fluorine modified silicone resin obtained performance.But current application is perfluoro capryl class monomer widely, and its potential impact to environment and HUMAN HEALTH has received people's attention, has very high biological accumulation property and refractory organics, is classified as persistent pollutant by United Nations.Our design utilizes perfluoro butyl sulfonic acid fluoride or the perfluoro hexyl sulfonic acid fluoride and the γ-An Bingjisanyiyangjiguiwan of low carbon chain, then uses the exchange of 1,2 Ucar 35 alcohol to obtain the fluorine modified organic silicone resin.
Summary of the invention:
The objective of the invention is to design two kinds of fluorine-containing alkyl silicones, its preparation method and application thereof, the performance through fluorine modification raising silicone resin is applied to water dispersible sheet zinc-aluminium coating and anti-attrition coating.
Two kinds of fluorine-containing alkyl silicones of the present invention, its molecular formula is:
Wherein: n is 4 or 6, R
1For
The preparation method of fluorine-containing alkyl silicone of the present invention is characterized in that, makes solvent with ethanol; Triethylamine with perfluoro butyl (hexyl) sulfonic acid fluoride and γ-An Bingjisanyiyangjiguiwan, carries out amidate action as acid binding agent under 60-80 ℃ of condition; Obtaining perfluoro butyl (hexyl) sulphonyl triethoxyl silane, after underpressure distillation goes out triethylamine salt, is under the 90-110 ℃ of condition in temperature; With 1, the reaction of 2-Ucar 35 gets the perfluoroalkyl silicone resin.
In the preparation of the present invention; Described is solvent with ethanol; Perfluoro butyl (hexyl) sulfonic acid fluoride and γ-An Bingjisanyiyangjiguiwan are carried out amidate action; This step uses triethylamine to be catalyzer, and the triethylamine addition is that perfluoro butyl (hexyl) sulfonic acid fluoride is doubly measured for 1 mole, and the proportion of solvent accounts for the 70%-90% of gross weight in the reaction system.
In the preparation of the present invention, the mol ratio of perfluoro butyl (hexyl) sulfonic acid fluoride and γ-An Bingjisanyiyangjiguiwan is 1: 1; Midbody and 1, the mass ratio of 2-Ucar 35 are 1: 1,1: 2 or 1: 3.
Advantage of the present invention:
1. raw material is easy to get, and the preparation method is simple, and low to the production unit requirement, production technique is simple.
2. productive rate is high, and the fluorochemical monomer transformation efficiency is up to 98%.
3. hardness is high, and surface energy is low.
4. its good chemicalstability, chemical-resistant and weathering resistance are applied to water dispersible sheet zinc-aluminium coating and anti-attrition coating filmogen.
The practical implementation method:
Further specify the preparation method of two kinds of fluorine-containing alkyl silicones below through embodiment.
Embodiment 1
The preparation of fluorine silicon resin
Get the 1mol perfluoro butyl sulfonic acid fluoride and wait the mole γ-An Bingjisanyiyangjiguiwan; Under 70 ℃ of conditions, carry out amidate action, obtain midbody perfluoro butyl sulphonyl aminopropyl triethoxysilane, under 75 ℃ of the oil baths; After underpressure distillation goes out triethylamine salt; At 120 ℃ and 1, the reaction of 2-Ucar 35 gets fluorine-containing alkyl silicone.
Embodiment 2
Synthesizing of perfluoro butyl sulphonyl aminopropyl triethoxysilane
Synthesis technique is following: in being furnished with the there-necked flask of magneton, add 200ml ethanol, 1mol triethylamine and 1mol γ-aminopropyl triethyl silicane under the ice bath, drip the 1mol perfluoro butyl sulfonic acid fluoride, are warming up under 70 ℃ of conditions and react 8 hours.Intensification distills out ethanol, and under 75 ℃ of the oil baths, triethylamine salt is removed in underpressure distillation, perfluoro butyl sulphonyl aminopropyl triethoxysilane.
C
4F
9SO
2F+NH
2(CH
2)
3Si(OC
2H
5)
3→C
4F
9SO
2NH(CH
2)
3Si(OC
2H
5)
3
Embodiment 3
Synthesizing of fluorine-containing butyl silicone resin
Synthesis technique is following: in being furnished with the there-necked flask of magneton, get 1Kg perfluoro butyl sulphonyl aminopropyl triethoxysilane triethoxyl silane, add 2Kg1; The 2-Ucar 35; 120 ℃ were reacted 12 hours, then heated up 160 ℃ and steamed low-molecular-weight alcohols, got fluorine-containing butyl silicone resin.
Wherein: R
1For
Embodiment 4
Water dispersible sheet zinc-aluminium coating.
Get the fluorine-containing butyl silicone resin of 5Kg, 1Kg W 166 2000,1.1Kg OP-10, the 2.5Kg zinc flake, 0.3Kg flake aluminum, 0.1Kg skimmer change with PM 500 in the holder cylinder, disperse aluminum zinc powder 8 hours, get water dispersible sheet zinc-aluminium coating.
This coating can replace existing Dacroment: the screw nut dip-coating is in zinc-aluminium coating, then centrifugal, and 280 ℃ of oven dry 20min, dip-coating again is centrifugal after the cooling, 280 ℃ of oven dry 20min.
Performance Detection: hardness: 6H, sticking power: 0 grade (cross-hatching), salt-fog test (neutrality): greater than 700h.
Embodiment 5
Anti-attrition coating
Get the fluorine-containing butyl silicone resin of 5Kg, 3Kg W 166 2000,0.5Kg OP-10,1.4Kg water-based carbon black color paste, 0.1Kg skimmer change with PM 500 in the holder cylinder, disperse 0.5 hour, get anti-attrition coating.
Application of paints: with in the instance 4 with application Work piece immersion anti-attrition coating, then centrifugal, 250 ℃ the oven dry 20min.
Performance Detection: frictional coefficient: 0.08
Embodiment 6
The preparation of fluorine-containing hexyl silicone resin
Get 1mol perfluoro hexyl sulfonic acid fluoride and wait the mole γ-An Bingjisanyiyangjiguiwan; Under 65 ℃ of conditions, carry out amidate action, obtain midbody perfluoro hexyl sulphonyl aminopropyl triethoxysilane, under 75 ℃ of the oil baths; After underpressure distillation goes out triethylamine salt; At 120 ℃ and 1, the reaction of 2-Ucar 35 gets fluorine-containing hexyl silicone resin.
Embodiment 7
Perfluoro hexyl sulphonyl aminopropyl triethoxysilane is synthetic
Synthesis technique is following: in being furnished with the there-necked flask of magneton, add 200ml ethanol, 1mol triethylamine and 1mol γ-aminopropyl triethyl silicane under the ice bath, drip 1mol perfluoro hexyl sulfonic acid fluoride, are warming up under 65 ℃ of conditions and react 8 hours.Intensification distills out ethanol, and under 75 ℃ of the oil baths, triethylamine salt is removed in decompression, perfluoro hexyl sulphonyl aminopropyl triethoxysilane.
C
6F
13SO
2F+NH
2(CH
2)
3Si(OC
2H
5)
3→C
6F
13SO
2NH(CH
2)
3Si(OC
2H
5)
3
Embodiment 8
Fluorine-containing hexyl silicone resin is synthetic
Synthesis technique is following: in being furnished with the there-necked flask of magneton, gets 1Kg perfluoro hexyl sulphonyl aminopropyl triethoxysilane, adds 2Kg1, and the 2-Ucar 35,120 ℃ were reacted 12 hours, then heated up 160 ℃ and steamed low-molecular-weight alcohols, got fluorine-containing hexyl silicone resin.
Wherein: R
1For
Embodiment 9
Water dispersible sheet zinc-aluminium coating.
Get the fluorine-containing hexyl silicone resin of 5Kg, 1Kg W 166 2000,1.1Kg OP-10, the 2.5Kg zinc flake, 0.3Kg flake aluminum, 0.1Kg skimmer are in the holder cylinder, and PM 500 changes, and disperses aluminum zinc powder 8 hours, gets water dispersible sheet zinc-aluminium coating.
This paint spraying: the screw nut dip-coating is in zinc-aluminium coating, then centrifugal, 280 ℃ of oven dry 20min, dip-coating again is centrifugal after the cooling, 280 ℃ of oven dry 20min.
Performance Detection: hardness: 7H, sticking power: 0 grade (cross-hatching), salt-fog test (neutrality): greater than 750h.
Embodiment 10
Anti-attrition coating
Get 5Kg perfluoro hexyl silicone resin, 3Kg W 166 2000,0.5Kg OP-10,1.4Kg water-based carbon black color paste, 0.1Kg skimmer are in the holder cylinder, and PM 500 changes, and disperses 0.5 hour, gets anti-attrition coating.
Application of paints: with in the instance 9 with application. Work piece immersion anti-attrition coating, then centrifugal, 250 ℃ the oven dry 20min.
Performance Detection: frictional coefficient: 0.06.
Claims (7)
1. fluorine-containing alkyl silicone is characterized in that, its molecular structural formula is:
Wherein: n is 4 or 6.
2. molecular formula as claimed in claim 1 is characterized in that R
1Structural formula:
3. the preparation method of fluorine-containing alkyl silicone as claimed in claim 1 is characterized in that, perfluoro butyl (hexyl) sulfonic acid fluoride and γ-An Bingjisanyiyangjiguiwan amidation; Refining back is with 1; The 2-Ucar 35 reacts, and heating up and steam low-molecular-weight alcohols in alcohol exchange back, gets fluorine-containing alkyl silicone.
4. the preparation method of fluorine-containing alkyl silicone as claimed in claim 3 is characterized in that, makes solvent with ethanol; With perfluoro butyl (hexyl) sulfonic acid fluoride and γ-An Bingjisanyiyangjiguiwan, under 60-80 ℃ of condition, carry out amidate action, obtain perfluoro butyl (hexyl) sulphonyl aminopropyl triethoxysilane; After underpressure distillation goes out triethylamine salt, be under the 90-110 ℃ of condition, with 1 in temperature; The exchange of 2-Ucar 35 alcohol gets the perfluoroalkyl silicone resin.
5. perfluoroalkyl silicone resin preparation method as claimed in claim 4; It is characterized in that; Describedly make solvent with ethanol; The catalyzer that perfluoro butyl (hexyl) sulfonic acid fluoride and γ-An Bingjisanyiyangjiguiwan carry out amidate action is a triethylamine, and the triethylamine addition is that perfluoro butyl (hexyl) sulfonic acid fluoride is doubly measured for 1 mole, and the proportion of solvent accounts for the 70%-90% of gross weight in the reaction system.
6. fluorine-containing alkyl silicone preparation method as claimed in claim 4 is characterized in that the mol ratio of perfluoro butyl (hexyl) sulfonic acid fluoride and γ-An Bingjisanyiyangjiguiwan is 1: 1.
7. fluorine-containing alkyl silicone preparation method as claimed in claim 4 is characterized in that perfluoro butyl (hexyl) sulphonyl aminopropyl triethoxysilane and 1, the mass ratio of 2-Ucar 35 are 1: 2.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107266949A (en) * | 2017-07-25 | 2017-10-20 | 安徽瑞泰汽车零部件有限责任公司 | A kind of auto parts polymerization water conservation coating |
| JP2019065148A (en) * | 2017-09-29 | 2019-04-25 | 三菱マテリアル電子化成株式会社 | Liquid composition for forming film |
| CN111154070A (en) * | 2020-01-17 | 2020-05-15 | 中国科学院长春应用化学研究所 | Fluorine-containing polyurethane and preparation method thereof |
| CN113929912A (en) * | 2021-11-04 | 2022-01-14 | 枣阳市华威硅氟材料有限公司 | Perfluoroalkyl sulfonyl terminated alpha, omega-dihydroxy polydimethylsiloxane and synthesis method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1997824A1 (en) * | 2007-06-01 | 2008-12-03 | Shin-Etsu Chemical Co., Ltd. | Perfluoropolyether-modified aminosilane, surface treating agent, and aminosilane-coated article |
| CN101638482A (en) * | 2008-07-30 | 2010-02-03 | 比亚迪股份有限公司 | Polymer and preparation method thereof, antifouling coating composition and antifouling coating layer material |
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2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1997824A1 (en) * | 2007-06-01 | 2008-12-03 | Shin-Etsu Chemical Co., Ltd. | Perfluoropolyether-modified aminosilane, surface treating agent, and aminosilane-coated article |
| CN101638482A (en) * | 2008-07-30 | 2010-02-03 | 比亚迪股份有限公司 | Polymer and preparation method thereof, antifouling coating composition and antifouling coating layer material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107266949A (en) * | 2017-07-25 | 2017-10-20 | 安徽瑞泰汽车零部件有限责任公司 | A kind of auto parts polymerization water conservation coating |
| JP2019065148A (en) * | 2017-09-29 | 2019-04-25 | 三菱マテリアル電子化成株式会社 | Liquid composition for forming film |
| CN111154070A (en) * | 2020-01-17 | 2020-05-15 | 中国科学院长春应用化学研究所 | Fluorine-containing polyurethane and preparation method thereof |
| CN111154070B (en) * | 2020-01-17 | 2021-04-27 | 中国科学院长春应用化学研究所 | Fluorine-containing polyurethane and preparation method thereof |
| CN113929912A (en) * | 2021-11-04 | 2022-01-14 | 枣阳市华威硅氟材料有限公司 | Perfluoroalkyl sulfonyl terminated alpha, omega-dihydroxy polydimethylsiloxane and synthesis method thereof |
| CN113929912B (en) * | 2021-11-04 | 2022-09-27 | 枣阳市华威硅氟材料有限公司 | Perfluoroalkyl sulfonyl terminated alpha, omega-dihydroxy polydimethylsiloxane and synthesis method thereof |
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