CN102924734A - Fluorosilicone, preparation method and application of fluorosilicone - Google Patents
Fluorosilicone, preparation method and application of fluorosilicone Download PDFInfo
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- CN102924734A CN102924734A CN 201210496915 CN201210496915A CN102924734A CN 102924734 A CN102924734 A CN 102924734A CN 201210496915 CN201210496915 CN 201210496915 CN 201210496915 A CN201210496915 A CN 201210496915A CN 102924734 A CN102924734 A CN 102924734A
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- fluorine silicon
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Abstract
The invention relates to fluorosilicone, a preparation method and application of fluorosilicone. The preparation method comprises the following steps of: performing catalyzed condensation on raw materials under a function of a coupling agent to generate fluorosilicone resin by using organic silicon resin and inorganic fluororesin; and curing an obtained product to form a film. The fluorosilicone can be used as a coating agent to be applied to fabric post-finish, so that water-repellency effect is provided, and the moisture permeability required by fabric wearability is not lost. The synthetic process for preparing the fluorosilicone resin coating agent is simple, special processing equipment is not needed, raw materials for synthesis are industrial raw materials and the preparation method is suitable for industrial amplification production.
Description
Technical field
The present invention relates to a kind of fluorine silicon materials and synthetic method thereof, particularly a kind of fluorine silicon coating agent that is applied to fabric post-treatment and preparation method thereof.
Background technology
In recent years, coupling type fluorocarbon resin and fluorine-containing textile finishing agent research both at home and abroad and application were very active, and became gradually the hot subject of new coating agent, and numerous bibliographical informations about fluorocarbon resin and fluorine-containing textile finishing agent are also arranged simultaneously.Because fluorine element is the strongest element of electronegativity in the periodic table of elements, electronegativity (4.0), fluorine atom radius little (van der Waals radius 0.135nm), steady chemical structure.The C-C chain is tightly surrounded into screw type structure by fluorine atom in the fluorocarbon resin molecule; resin fluoroolefin and vinyl ester (or ether) alternative arrangement; chemical structure is firm; fluoroolefin protection C-C; carbon-oxygen bond is not subjected to ultraviolet pyrolytic damage, can not be destroyed by chemical mediator, therefore; fluorocarbon resin has many good characteristics, such as weathering resistance, erosion resistance, chemicals-resistant, low abrasion and the easy cleaning etc. of excellence.
As the coated material of novel high-performance, fluorocarbon resin is applied in architectural finish and textile finishing example gradually.The FEVE resin of selling on the domestic market adopts take trifluorochloroethylene as fluorochemical monomer the multi-component copolymer products such as same vinyl ester, undecylenic acid mostly.Such as the fluoro-resin (CAS NO.9010-75-7) of Wuxi Huambo painting company limited and Changshu Sanaifu Zhonghao New Chemical Materials Co., Ltd's production and sales, its general structural formula is as follows:
This class fluoro-resin is generally obtained by copolyreaction, and copolymerization brings good cost performance, and side chain carboxyl group has reactive behavior, so fluoro-resin has reactivity, and this class fluoro-resin can adapt to the demand of domestic market fully as coating or paint priming paint.It is poor that but the disadvantage of fluoroolefin multipolymer is water vapour permeability, can not be adapted to the tight protection in some surfaces but need to have the coatings applications needs of water vapour permeability concurrently.Coating-forming agent is when being used for fabric post-treatment, and coating is poor in the polymeric membrane water vapour permeability that the fabric fibre surface forms, and has directly affected the wearing comforts such as moisture absorbing and sweat releasing of textiles.
Summary of the invention
The objective of the invention is to overcome in the prior art fluorocarbon resin as the poor defective of its water vapour permeability of coating-forming agent, provide a kind of for still having good water repellency and water vapour permeability behind the textile finishing, and the constant organic-silicon-modified fluorocarbon resin of feel and preparation method thereof.
The technical scheme that realizes the object of the invention provides a kind of fluorine silicon resin, and its structural formula is:
The preparation method of described fluorine silicon resin comprises the steps:
1, by weight, 1 part of silicone resin, 0.5～2 part of fluoro-resin and 0.5～5 part of band aqua are joined in the reactor, stirring and dissolving is even, adds 0.01～0.05 part of dibutyl tin laurate and 0.01～0.1 part of coupling agent again, obtains reaction solution; Reaction solution is warming up to 70～110 ℃ of reflux water-dividing reactions 2～12 hours, obtains water white reaction mixture;
2, be 40～80 ℃ with reaction mixture in temperature, vacuum tightness is under the condition of 0.5～20mmHg after the underpressure distillation, obtains a kind of fluorine silicon resin.
Of the present invention is a kind of in hexanaphthene or the toluene with aqua.Described coupling agent is a kind of in epoxypropoxy methyl dimethoxysilane, the epoxypropoxy methyldiethoxysilane, or they are the mixture of 1:1 in mass ratio.
A kind of fabric coating finishing agent, it comprises fluorine silicon resin of the present invention.
Principle of the present invention is: the synthetic silicone resin take dimethyldichlorosilane(DMCS) and METHYL TRICHLORO SILANE as raw material; silicone resin obtains fluorine silicon resin by the coupling agent reaction with the fluorocarbon resin chemical bonding under catalyst action; be applied to fabric post-treatment good surface protection can be provided, also have good water vapour permeability.
In the technical solution used in the present invention, fluorine silicon resin is synthesized in silicone resin and fluorocarbon resin condensation reaction, and reaction formula is as follows:
Wherein, R=-CH
3Huo – CH
2CH
3M=3～10; N=5～15; P=3～10; Q=5～15; X=40～60; Y=5～10; Z=4～8.
The present invention is take reactive F resin and silicone resin as raw material, catalyzing and condensing under action of coupling agents, and the fluorine silicon resin that obtains can be used as coating-forming agent.Because the fluorine silicon resin of preparation contains fluorocarbon chain segment structure and polysiloxane structure simultaneously, the former can provide very good surface protection performance, and latter provides very good water vapour permeability.When being applied to fabric post-treatment as coating-forming agent, can give fabric certain water repellency, the wear behavior such as while water vapour permeability are kept, and the present invention's outstanding advantages compared with prior art is:
1, the present invention take dimethyldichlorosilane(DMCS) and METHYL TRICHLORO SILANE as raw material synthetic silicone resin, react by silicone resin and fluorocarbon resin again, obtain fluorine silicon resin, the starting material of use are Industrial raw material, wide material sources.
When 2, the present invention prepares fluorine silicon resin, reacted under action of coupling agents by silicone resin and fluorocarbon resin, make the epoxy reaction in fluorocarbon resin and the coupling agent molecule structure, simultaneously alkoxysilyl group and the silicone resin condensation in the coupling agent molecule, thus chemical bonding provided for silicone resin and fluorocarbon resin.The preparation technology who adopts is very easy, is particularly suitable for industrial amplification production.
3, the fluorine silicon resin that makes of the present invention is applied to textile finishing as coating-forming agent can provide good water repellency, and keeps good water vapour permeability; And the whiteness of fabric changes hardly before and after feel and the arrangement.
Description of drawings
Fig. 1 is the infrared spectrogram by the fluorine silicon resin of the embodiment of the invention 1 technical scheme preparation;
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) that the fluorine silicon resin of the embodiment of the invention 1 technical scheme preparation is used as cotton fibre surface after the coating-forming agent finishing of cotton textiles;
Fig. 3 is the scanning electron microscope (SEM) photograph figure (SEM) on cotton fibre surface in the cotton fabric of being untreated.
Embodiment
Technical solution of the present invention is further elaborated below in conjunction with embodiment and accompanying drawing.
Embodiment one
1, silicone resin is synthetic
Reactor is joined mechanical stirring, thermometer, constant voltage feed hopper, ice-water bath cooling and reflux condensing tube.
First with 650 gram dimethyldichlorosilane(DMCS)s and 1500 gram METHYL TRICHLORO SILANE mixings, preparation mix monomer.
In reactor, add 1200 gram water, be cooled to 0～25 ℃ after, above-mentioned mix monomer is added the constant voltage feed hopper, slowly drip monomer.The control temperature of reaction is lower than 25 ℃, drips mix monomer in 3 hours, adds 0～25 ℃ of reaction of rear insulation 3 hours.After finishing, reaction adds n-butyl acetate extraction 1200 grams * 3 times, combining extraction liquid, and washing 400 grams * 3 times add 120 gram anhydrous sodium sulfate drying 2h, cross the filtering siccative.
Filtrate is underpressure distillation desolventizing butylacetate under the 10mmHg at 50 ℃, vacuum tightness, obtains colourless, thickness and has mobile silicone resin product.
2, fluorine silicon resin preparation
Reactor is joined mechanical stirring, thermometer, oil bath heating, water trap and reflux condensing tube.
In reactor, add successively 120 gram hexanaphthenes, 65 gram silicone resin and 60 gram fluoro-resin (available from the fluoro-resin 212 of Wuxi Huambo painting company limited, carboxyl-content is 3.5%).Stirring and dissolving is even.After adding 1.2 gram dibutyl tin laurates (DBTL) and 3 gram epoxypropoxy methyl dimethoxysilanes, reaction solution is warming up to 72 ℃ of reflux water-dividing reactions 5 hours.
After reaction finished, stopped reaction was divided into water outlet 5 grams.Reaction solution is underpressure distillation desolventizing hexanaphthene under the 10mmHg at 50 ℃, vacuum tightness, obtains colourless thick fluorine silicon resin product 120 grams, and yield is 96%.
Referring to accompanying drawing 1, it is the infrared spectrogram of the present embodiment product.As can be known from Fig. 1, at 3426.2cm
-1The absorption peak at place is the charateristic avsorption band of Si-OH, 2966.6cm
-1The place is-CH
3The strong symmetry of middle C-H is flexible to be caused, at 1767.9cm
-1The place is the charateristic avsorption band of C=O key, 1267.8cm
-1, 802.0cm
-1Be Si-CH
3The stretching vibration of middle Si-C reaches-CH
3Flexural vibration cause, at 1092.8cm
-1The place is the charateristic avsorption band of Si-O-Si.
3, be applied to coating-forming agent to textile finishing
(1) preparation working fluid: the fluorine silicon resin that obtains is diluted to 50g/L with butylacetate, gets the textile finishing working fluid.
(2) textile finishing: selected cotton fabric and polyester cotton are infiltrated respectively in working fluid, mangle at padding machine behind the infiltration 30min, control pick-up 100%.Two soak two roll after with cotton at 80 ℃ of lower preliminary drying 2min, under 160 ℃, bake 3min at last.Take out the fabric that fabric obtains the fluorine silicon resin arrangement.
Fabric after the arrangement is carried out the water repellency test, according to GB/T 14577-93(ISO 9865-1991) the standard execution, use YB813 type textile water-proof performance tester, according to the water repellency of standard rating fabric face.Water vapour permeability test: adopt the test of TSY-T3 water vapour permeability tester, carry out GB 1037.Test result is referring to table 1.
Embodiment two
1, fluorine silicon resin preparation
Reactor is joined mechanical stirring, thermometer, oil bath heating, water trap and reflux condensing tube.
In reactor, add successively 120 gram hexanaphthenes, 45 gram silicone resin and 70 gram fluoro-resin (available from the fluoro-resin 212 of Wuxi Huambo painting company limited, carboxyl-content is 3.5%).Stirring and dissolving is even.After adding 1.1 gram dibutyl tin laurates and 2.8 gram epoxypropoxy methyl dimethoxysilanes, reaction solution is warming up to 70 ℃ of reflux water-dividing reactions 8 hours.
After reaction finished, stopped reaction was divided into water outlet 4.5 grams.Reaction solution is underpressure distillation desolventizing hexanaphthene under the 10mmHg at 50 ℃, vacuum tightness, obtains colourless thick fluorine silicon resin product 112 grams, and yield is 97%.
2, be applied to the coating-forming agent of textile finishing
(1) preparation working fluid: the fluorine silicon resin that obtains is diluted to 50g/L with butylacetate, gets the textile finishing working fluid.
(2) textile finishing: selected cotton fabric and polyester cotton are infiltrated respectively in working fluid, mangle at padding machine behind the infiltration 30min, control pick-up 100%.Two soak two roll after with cotton at 80 ℃ of lower preliminary drying 2min, under 160 ℃, bake 3min at last.Take out the fabric that fabric obtains the fluorine silicon resin arrangement.
Performance test after the textile finishing and result:
Water repellency and the water vapour permeability of fabric before and after relatively the fluorine silicon resin coating-forming agent is put in order, the result is referring to table 1.Wherein, selected fabric is cotton fabric and polyester-cotton fabric, and two kinds of finishing composition concentration are 50g/L, and baking temperature is 160 ℃.
What table 1 fluorine silicon resin was processed fabric refuses water grade and water vapour permeability
Annotate: the cotton fabric that the fluorine silicon resin that sample 1 obtains for embodiment 1 is processed, the cotton fabric that the fluorine silicon resin that sample 2 obtains for embodiment 2 is processed.
As can be seen from Table 1, because the effect of fluorine silicon resin finishing composition, two kinds of fabrics reach 70～80 minutes through the aftertreatment water repellency.Owing to baking down at high temperature, fluoro-containing group migrates to fiber surface, and the C-F key is the umbrella sample to be opened, and makes the fabric through the fluorine silicon resin arrangement have very low surface free energy, is unfavorable for that water droplet sprawls at fabric face, refuses preferably the water effect thereby have.It can also be seen that from table 1, the fabric moisture transmission rate is substantially constant before and after the fluorine silicon resin finishing composition is processed.This shows that the fluorine silicon resin finishing composition not only can improve the water repellency of fabric, and does not substantially change textiles and take desired water vapour permeability.
Embodiment 2 is processed the cotton fabric that obtains carry out scanning electron microscope (SEM) test, and the be untreated surface topography of cotton fibre in the cotton fabric of contrast test, the result sees respectively accompanying drawing 2 and accompanying drawing 3.As seen from Figure 2, cotton fabric is after fluorine silicon resin is processed, and the fluorine silicon resin film forms one deck densification and more uniform protective layer on the cotton fibre surface.Compare with Fig. 3, fluorine silicon protective film is so that the natural gauffer of fiber surface disappears, and it is smooth and plentiful that fiber surface becomes.
Claims (5)
1. fluorine silicon resin is characterized in that its structural formula is:
2. the preparation method of fluorine silicon resin as claimed in claim 1 is characterized in that comprising the steps:
(1) by weight, 1 part of silicone resin, 0.5～2 part of fluoro-resin and 0.5～5 part of band aqua are joined in the reactor, stirring and dissolving is even, adds 0.01～0.05 part of dibutyl tin laurate and 0.01～0.1 part of coupling agent again, obtains reaction solution; Reaction solution is warming up to 70～110 ℃ of reflux water-dividing reactions 2～12 hours, obtains water white reaction mixture;
(2) be 40～80 ℃ with reaction mixture in temperature, vacuum tightness is under the condition of 0.5～20mmHg after the underpressure distillation, obtains a kind of fluorine silicon resin.
3. the preparation method of a kind of fluorine silicon resin according to claim 2 is characterized in that: described is a kind of in hexanaphthene or the toluene with aqua.
4. the preparation method of a kind of fluorine silicon resin according to claim 2, it is characterized in that: described coupling agent is a kind of in epoxypropoxy methyl dimethoxysilane, the epoxypropoxy methyldiethoxysilane, or they are the mixture of 1:1 in mass ratio.
5. fabric coating finishing agent, it is characterized in that: it comprises fluorine silicon resin as claimed in claim 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
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| CN 201210496915 CN102924734A (en) | 2012-11-28 | 2012-11-28 | Fluorosilicone, preparation method and application of fluorosilicone |
| CN201310613405.8A CN103665386B (en) | 2012-11-28 | 2013-11-27 | A kind of fluorine silicon resin, preparation method and application thereof |
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| CN 201210496915 CN102924734A (en) | 2012-11-28 | 2012-11-28 | Fluorosilicone, preparation method and application of fluorosilicone |
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| CN201310613405.8A Expired - Fee Related CN103665386B (en) | 2012-11-28 | 2013-11-27 | A kind of fluorine silicon resin, preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610549A (en) * | 2015-01-29 | 2015-05-13 | 苏州大学 | Modified fluorine-containing silicone oil and preparation method thereof |
| CN107418341A (en) * | 2017-09-26 | 2017-12-01 | 安徽喜宝高分子材料有限公司 | A kind of resistant fluorine carbon wall finiss and preparation method thereof |
| CN107476062A (en) * | 2017-08-17 | 2017-12-15 | 武汉纺织大学 | A kind of afterfinish method of antifouling easily decontamination non-woven cloth |
| CN108822637A (en) * | 2018-06-04 | 2018-11-16 | 合肥博创机械制造有限公司 | A kind of engineering machinery fire-resistant anticorrosion paint and preparation method thereof |
| WO2019178873A1 (en) * | 2018-03-23 | 2019-09-26 | 南通纺织丝绸产业技术研究院 | Fluorosilicone resin and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN110041822A (en) * | 2019-02-25 | 2019-07-23 | 江苏常大绿恒环境工程有限公司 | A kind of preparation method of safety and environmental protection high-performance non-sticking lining material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3036161B2 (en) * | 1991-09-25 | 2000-04-24 | 三菱マテリアル株式会社 | Perfluoroalkyl group-containing silicone and method for producing the same |
| CN102295875B (en) * | 2011-06-29 | 2013-01-09 | 中科院广州化学有限公司 | Epoxy flooring coating containing epoxide group organosilicon hybrid, its preparation method and its application |
-
2012
- 2012-11-28 CN CN 201210496915 patent/CN102924734A/en active Pending
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- 2013-11-27 CN CN201310613405.8A patent/CN103665386B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610549A (en) * | 2015-01-29 | 2015-05-13 | 苏州大学 | Modified fluorine-containing silicone oil and preparation method thereof |
| CN104610549B (en) * | 2015-01-29 | 2017-03-29 | 苏州大学 | A kind of modified fluoride-containing silicone oil and preparation method thereof |
| CN107476062A (en) * | 2017-08-17 | 2017-12-15 | 武汉纺织大学 | A kind of afterfinish method of antifouling easily decontamination non-woven cloth |
| CN107418341A (en) * | 2017-09-26 | 2017-12-01 | 安徽喜宝高分子材料有限公司 | A kind of resistant fluorine carbon wall finiss and preparation method thereof |
| WO2019178873A1 (en) * | 2018-03-23 | 2019-09-26 | 南通纺织丝绸产业技术研究院 | Fluorosilicone resin and preparation method thereof |
| US11299593B2 (en) | 2018-03-23 | 2022-04-12 | Soochow University | Fluorosilicone resin and preparation method thereof |
| CN108822637A (en) * | 2018-06-04 | 2018-11-16 | 合肥博创机械制造有限公司 | A kind of engineering machinery fire-resistant anticorrosion paint and preparation method thereof |
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| CN103665386B (en) | 2016-02-03 |
| CN103665386A (en) | 2014-03-26 |
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Application publication date: 20130213 |