CN102532550B - 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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- CN102532550B CN102532550B CN201110451064.XA CN201110451064A CN102532550B CN 102532550 B CN102532550 B CN 102532550B CN 201110451064 A CN201110451064 A CN 201110451064A CN 102532550 B CN102532550 B CN 102532550B
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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 silicon resin 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, Si-O key is identical with silicate inorganic thing structural unit with formation silicic acid, Si-C key has the character of partial organic substances simultaneously, make it not only there is the character of inorganics but also there is organic character, and make it have weathering resistance, ozone resistance, nontoxic, the good characteristics such as tasteless and physiology inertia.
Organofluorine compound is introduced fluorine atom in compound; because the electronegativity of fluorine atom is large; adjacent fluorine atom repels mutually; and C-C main chain is surrounded by a series of fluorine atom; the screening of nucleus of height of formation; protect the stability of C-C chain, made fluorochemicals there is extremely stable chemical stability, chemical-resistant and weathering resistance thereof.
We attempt fluorochemical monomer to introduce in silicone resin, obtain the resin of excellent performance by fluorine modified silicone resin.But current application is perfluoro capryl class monomer widely, it has been subject to people concern to the potential impact of environmental and human health impacts, has very high bioconcentration and refractory organics, and united state classifies persistent pollutant as.Our design utilizes perfluoro butyl sulfonic acid fluoride or perfluoro hexyl sulfonic acid fluoride and the γ-aminopropyl triethoxysilane of low carbon chain, then uses 1,2 propylene glycol alcohol exchange to obtain fluorine modified organic silicone resin.
Summary of the invention:
The object of the invention is to design two kinds of fluorine-containing alkyl silicon resins, its preparation method and application thereof, improve the performance of silicone resin by fluorine modification, be applied to water dispersible sheet zinc-aluminium coating and anti-attrition coating.
Two kinds of fluorine-containing alkyl silicon resins of the present invention, its molecular formula is:
Wherein: n is 4 or 6, R
1for
The preparation method of fluorine-containing alkyl silicon resin of the present invention, it is characterized in that, make solvent with ethanol, triethylamine is as acid binding agent, by perfluoro butyl (hexyl) sulfonic acid fluoride and γ-aminopropyl triethoxysilane, under 60-80 DEG C of condition, carry out amidate action, obtain perfluoro butyl (hexyl) sulphonyl triethoxyl silane, underpressure distillation goes out after triethylamine salt, be under 90-110 DEG C of condition in temperature, react with 1,2-PD, obtain perfluoroalkyl silicone resin.
In preparation of the present invention, described taking ethanol as solvent, perfluoro butyl (hexyl) sulfonic acid fluoride and γ-aminopropyl triethoxysilane are carried out to amidate action, this step triethylamine is catalyzer, triethylamine addition is that 1 mole of perfluoro butyl (hexyl) sulfonic acid fluoride is doubly measured, and in reaction system, the proportion of solvent accounts for the 70%-90% of gross weight.
In preparation of the present invention, the mol ratio of perfluoro butyl (hexyl) sulfonic acid fluoride and γ-aminopropyl triethoxysilane is 1: 1; The mass ratio of intermediate and 1,2-PD is 1: 1,1: 2 or 1: 3.
Advantage of the present invention:
1. raw material is easy to get, and preparation method is simple, and low to production unit requirement, production technique is simple.
2. productive rate is high, and fluorochemical monomer transformation efficiency is up to 98%.
3. hardness is high, and surface can be low.
4. its good chemical stability, chemical-resistant and weathering resistance, be applied to water dispersible sheet zinc-aluminium coating and anti-attrition coating filmogen.
Specific implementation method:
Further illustrate the preparation method of two kinds of fluorine-containing alkyl silicon resins below by embodiment.
Embodiment 1
The preparation of fluorine silicon resin
Get 1mol perfluoro butyl sulfonic acid fluoride and wait mole γ-aminopropyl triethoxysilane, under 70 DEG C of conditions, carry out amidate action, obtain intermediate perfluoro butyl sulphonyl aminopropyl triethoxysilane, at 75 DEG C of oil baths, underpressure distillation goes out after triethylamine salt, react with 1,2-PD at 120 DEG C, obtain fluorine-containing alkyl silicon resin.
Embodiment 2
Synthesizing of perfluoro butyl sulphonyl aminopropyl triethoxysilane
Synthesis technique is as follows: in the there-necked flask of being furnished with magneton, add 200ml ethanol, 1mol triethylamine and 1mol γ-aminopropyl triethyl silicane, under ice bath, drip 1mol perfluoro butyl sulfonic acid fluoride, is warming up under 70 DEG C of conditions and reacts 8 hours.Intensification distills out ethanol, and at 75 DEG C of oil baths, triethylamine salt is removed in underpressure distillation, obtains 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 as follows: in the there-necked flask of being furnished with magneton, get 1Kg perfluoro butyl sulphonyl aminopropyl triethoxysilane triethoxyl silane, add 2Kg1,2-propylene glycol, 120 DEG C are reacted 12 hours, then heat up 160 DEG C and steam low-molecular-weight alcohols, obtain 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 polypropylene glycol 2000,1.1Kg OP-10,2.5Kg zinc flake, 0.3Kg flake aluminum, 0.1Kg defoamer, in holder cylinder, turns with per minute 500, disperses aluminum zinc powder 8 hours, obtains water dispersible sheet zinc-aluminium coating.
This coating can replace existing Dacroment: screw nut dip-coating is in zinc-aluminium coating, then centrifugal, 280 DEG C dry 20min, cooling after dip-coating again, centrifugal, 280 DEG C dry 20min.
Performance Detection: hardness: 6H, sticking power: 0 grade (cross-hatching), salt-fog test (neutrality): be greater than 700h.
Embodiment 5
Anti-attrition coating
Get the fluorine-containing butyl silicone resin of 5Kg, 3Kg polypropylene glycol 2000,0.5Kg OP-10,1.4Kg water-based carbon black color paste, 0.1Kg defoamer, in holder cylinder, turns with per minute 500, disperses 0.5 hour, obtains anti-attrition coating.
Application of paints: by example 4 by coated workpieces dip-coating anti-attrition coating, then centrifugal, 250 DEG C 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 mole γ-aminopropyl triethoxysilane, under 65 DEG C of conditions, carry out amidate action, obtain intermediate perfluoro hexyl sulphonyl aminopropyl triethoxysilane, at 75 DEG C of oil baths, underpressure distillation goes out after triethylamine salt, react with 1,2-PD at 120 DEG C, obtain fluorine-containing hexyl silicone resin.
Embodiment 7
Perfluoro hexyl sulphonyl aminopropyl triethoxysilane is synthetic
Synthesis technique is as follows: in the there-necked flask of being furnished with magneton, add 200ml ethanol, 1mol triethylamine and 1mol γ-aminopropyl triethyl silicane, under ice bath, drip 1mol perfluoro hexyl sulfonic acid fluoride, is warming up under 65 DEG C of conditions and reacts 8 hours.Intensification distills out ethanol, and at 75 DEG C of oil baths, triethylamine salt is removed in decompression, obtains 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 as follows: in the there-necked flask of being furnished with magneton, gets 1Kg perfluoro hexyl sulphonyl aminopropyl triethoxysilane, adds 2Kg1, and 2-propylene glycol, 120 DEG C are reacted 12 hours, then heat up 160 DEG C and steam low-molecular-weight alcohols, obtain 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 polypropylene glycol 2000,1.1Kg OP-10,2.5Kg zinc flake, 0.3Kg flake aluminum, 0.1Kg defoamer is in holder cylinder, and per minute 500 turns, and disperses aluminum zinc powder 8 hours, obtains water dispersible sheet zinc-aluminium coating.
This paint spraying: screw nut dip-coating is in zinc-aluminium coating, then centrifugal, 280 DEG C dry 20min, cooling after dip-coating again, centrifugal, 280 DEG C dry 20min.
Performance Detection: hardness: 7H, sticking power: 0 grade (cross-hatching), salt-fog test (neutrality): be greater than 750h.
Embodiment 10
Anti-attrition coating
Get 5Kg perfluoro hexyl silicone resin, 3Kg polypropylene glycol 2000,0.5Kg OP-10,1.4Kg water-based carbon black color paste, 0.1Kg defoamer is in holder cylinder, and per minute 500 turns, and disperses 0.5 hour, obtains anti-attrition coating.
Application of paints: by example 9 by application. Work piece immersion anti-attrition coating, then centrifugal, 250 DEG C dry 20min.
Performance Detection: frictional coefficient: 0.06.
Claims (6)
1. fluorine-containing alkyl silicon resin, is characterized in that, its molecular structural formula is:
R
1structural formula:
Wherein: n is 4 or 6.
2. the preparation method of a fluorine-containing alkyl silicon resin as claimed in claim 1, it is characterized in that, perfluoro butyl (hexyl) sulfonic acid fluoride and γ-aminopropyl triethoxysilane amidation, refining rear with 1, the reaction of 2-propylene glycol, after alcohol exchange, heat up and steam low-molecular-weight alcohols, obtain fluorine-containing alkyl silicon resin.
3. the preparation method of fluorine-containing alkyl silicon resin as claimed in claim 2, it is characterized in that, make solvent with ethanol, triethylamine is as acid binding agent, by perfluoro butyl (hexyl) sulfonic acid fluoride and γ-aminopropyl triethoxysilane, under 60-80 DEG C of condition, carry out amidate action, obtain perfluoro butyl (hexyl) sulphonyl aminopropyl triethoxysilane, underpressure distillation goes out after triethylamine salt, be under 90-110 DEG C of condition in temperature, with the exchange of 1,2-PD alcohol, obtain perfluoroalkyl silicone resin.
4. perfluoroalkyl silicone resin preparation method as claimed in claim 3, it is characterized in that, described makes solvent with ethanol, the catalyzer that perfluoro butyl (hexyl) sulfonic acid fluoride and γ-aminopropyl triethoxysilane carry out amidate action is triethylamine, triethylamine addition is that 1 mole of perfluoro butyl (hexyl) sulfonic acid fluoride is doubly measured, and in reaction system, the proportion of solvent accounts for the 70%-90% of gross weight.
5. fluorine-containing alkyl silicon resin preparation method as claimed in claim 4, is characterized in that, the mol ratio of perfluoro butyl (hexyl) sulfonic acid fluoride and γ-aminopropyl triethoxysilane is 1: 1.
6. fluorine-containing alkyl silicon resin preparation method as claimed in claim 4, is characterized in that, the mass ratio of perfluoro butyl (hexyl) sulphonyl aminopropyl triethoxysilane and 1,2-PD is 1: 2.
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| 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 |
| JP6986408B2 (en) * | 2017-09-29 | 2021-12-22 | 三菱マテリアル電子化成株式会社 | Method for Producing Liquid Composition for Film Formation |
| 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 |
| 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 |
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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| 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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