CN108822265A - A kind of preparation method of organic silicon-fluorine resin - Google Patents
A kind of preparation method of organic silicon-fluorine resin Download PDFInfo
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- CN108822265A CN108822265A CN201810592617.5A CN201810592617A CN108822265A CN 108822265 A CN108822265 A CN 108822265A CN 201810592617 A CN201810592617 A CN 201810592617A CN 108822265 A CN108822265 A CN 108822265A
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- organic silicon
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- fluorine resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- Polymers & Plastics (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A kind of preparation method of organic silicon-fluorine resin, vinyl polysiloxane, solvent and initiator are added in reaction kettle by the method, styrene and fluorine-containing mixture of vinyl monomer are added dropwise after mixing evenly, after being added dropwise, temperature is increased to 70-75 DEG C, reacts 6-8h, it is cooled to room temperature, filtering, vacuum distillation remove solvent, obtain organic silicon-fluorine resin.Preparation method simple process of the present invention, mild condition, polymer relative molecular weight are big.Pass through polymerisation in solution graft reaction, under the premise of not changing the excellent performance of organic siliconresin, enable and prepare material with lower surface, the elasticity for improving material, refractive index and adhesive force, can be applied to antifouling paint, waterproofing agent, encapsulating material product, wide market.
Description
Technical field
The present invention relates to a kind of preparation methods of organic silicon-fluorine resin, and the invention further relates to a kind of answering for organic silicon-fluorine resin
With category organosilicon applied technical field.
Background technique
Organic siliconresin has many excellent performances because structure is special, such as high-low temperature resistant, hydrophobicity, gas permeability, flexibility
Performances such as good, but its mechanical property is poor, not organic solvent-resistant；Fluorocarbon resin is had excellent performance, and fluorine-containing side group can improve material
Solvent resistance, improve surface property, but it is expensive, and more excellent performance of fluorine silicon can be obtained using the advantages of the two
Resin.However in most of document report, there are mainly two types of methods for synthesis silicon-fluorine polymer object, and one is with the big list of polysiloxanes
Vegetative grafting is to fluorine carbon skeleton, and another kind is that perfluoro side chains are grafted on silicone matrix, as obtained by both methods
Polymer Molecular Weight it is lower, influence the performance of polymer.Therefore, under the premise of easy to operate, inexpensive, preparation
The organic silicon-fluorine resin haveing excellent performance is applied to the fields such as antifouling paint, waterproof material and sealing material, necessarily has wide
Market prospects.
Publication number CN101775095A discloses a kind of functional perfluoro resin and preparation method thereof；Publication number
CN102161723A discloses a kind of quarternary copolymerized fluorine resin of high flexibility and the preparation method and application thereof.But there is not yet organic
The report of the preparation method of fluosilicic resin.
Summary of the invention
The object of the present invention is in order to provide, one kind is ageing-resistant, solvent resistant, bear dirty, stability is good, waterproof performance is excellent
Organic silicon-fluorine resin is applied to fields, the present invention such as antifouling paint, waterproof material and sealing material and discloses a kind of organic silicon-fluorine
The preparation method of resin.
The technical solution that the present invention realizes is as follows, a kind of preparation method of organic silicon-fluorine resin, and the method is by vinyl
Silicone resin, solvent and initiator are added in reaction kettle, and styrene and fluorine-containing mixture of vinyl monomer are added dropwise after mixing evenly,
After being added dropwise, temperature is increased to 70-75 DEG C, reacts 6-8h, is cooled to room temperature, filters, and vacuum distillation removes solvent, is had
Machine fluosilicic resin.
The contents of ethylene of the vinyl polysiloxane is 2-10%, viscosity 1000-8000cs；The vinyl silicon tree
Rouge is one of methyl vinyl silicone, phenyl vinyl polysiloxane.
The solvent is one of toluene, dimethylbenzene, ethyl acetate, ethyl alcohol, methanol, isopropanol, acetone, tetrahydrofuran
Or more than one mixtures.
The initiator is one of azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl.
The fluorine-containing vinyl monomer is acrylic acid trifluoro ethyl ester, trifluoroethyl methacrylate, perfluorododecyl first
One of base acrylate, trifluoro propene, perfluoro styrene, perfluorobutyl ethylene.
The vinyl polysiloxane, solvent, initiator, styrene and fluorine-containing vinyl monomer mass ratio be 1:(1~
10)：(0.001~0.005)：(0.2~1)：(0.5~20).
The organic silicon-fluorine resin of the method preparation, is suitable for waterproofing agent, antifouling paint, encapsulating material.
The invention has the advantages that the present invention uses solution polymerization, by fluorine-containing material, styrene-grafted to ethylene
On base silicone resin, it is prepared into a kind of high performance organic silicon-fluorine resin；It avoids using noble metal involved in hydrosilylation
Make catalyst, cost is relatively low；Also influence of the emulsifier to performance in the emulsion polymerization avoided, and technique is more difficult to control.This hair
The organic silicon-fluorine resin of bright preparation contains multi-functional, and wherein it is good low can to ensure that be modified surface has for fluorine component
Surface energy, vinyl polysiloxane can provide crosslinking active point, provide the elasticity of product；In addition resinous polymer refractive index is high,
And be colorless and transparent solid, material surface color can not be changed after use, it is good with other resin compatibles.
Organic silicon-fluorine resin prepared by the present invention, application field is wide, can be configured to coating and apply outside timber, building
It is wall, fabric, antifouling in ocean；Waterproofing agent can be configured to applied to stone material, insulation board, building engineering field, be also used as
Encapsulating material is applied to LED, integrated circuit fields
Specific embodiment
Embodiment 1
It is 2% by 100g contents of ethylene, viscosity is the methyl vinyl silicone of 8000cs, and 100g toluene and 0.1g are even
Nitrogen bis-isobutyronitrile is added in reaction kettle, and 20g styrene and 50g acrylic acid trifluoro ethyl ester mixture, drop are added dropwise after mixing evenly
After adding, temperature being increased to 70 DEG C, 8h is reacted, is cooled to room temperature, is filtered, vacuum distillation removes toluene, obtains organic silicon-fluorine
Resin.
Embodiment 2
It is 10% by 100g contents of ethylene, viscosity is the phenyl vinyl polysiloxane of 1000cs, 1000g acetone and 0.5g
Azobisisoheptonitrile is added in reaction kettle, and 100g styrene and 100g trifluoro propene mixture are added dropwise after mixing evenly, is added dropwise
After, temperature is increased to 75 DEG C, 6h is reacted, is cooled to room temperature, is filtered, and vacuum distillation removes acetone, obtains organic silicon-fluorine tree
Rouge.
Embodiment 3
It is 2% by 100g contents of ethylene, viscosity is the methyl vinyl silicone of 8000cs, 500g dimethylbenzene and 0.5g
Azodiisobutyronitrile is added in reaction kettle, and 50g styrene is added dropwise after mixing evenly and 100g trifluoroethyl methacrylate is mixed
Object is closed, after being added dropwise, temperature is increased to 70 DEG C, reacts 6h, be cooled to room temperature, filter, vacuum distillation removes removal xylene, obtains
Organic silicon-fluorine resin.
Embodiment 4
By 100g contents of ethylene be 5%, viscosity be 4000cs methyl vinyl silicone, 800g ethyl acetate and
0.4g azo-bis-iso-dimethyl is added in reaction kettle, and 80g styrene and 200g perfluoro styrene are added dropwise after mixing evenly
Mixture after being added dropwise, increases temperature to 75 DEG C, reacts 8h, be cooled to room temperature, filter, and vacuum distillation removes ethyl acetate,
Obtain organic silicon-fluorine resin.
Table 1 is the index of organic silicon-fluorine resin film-forming performance prepared by the embodiment of the present invention 1-4.
The index of the organic silicon-fluorine resin film-forming performance of 1 embodiment 1-4 of table preparation
Claims (7)
1. a kind of preparation method of organic silicon-fluorine resin, which is characterized in that the described method comprises the following steps：
Vinyl polysiloxane, solvent and initiator are added in reaction kettle, styrene is added dropwise after mixing evenly and contain vinyl fluoride
Base monomer mixture, after being added dropwise, temperature is increased to 70-75 DEG C, reacts 6-8h, is cooled to room temperature, filters, and vacuum distillation removes
Solvent is removed, organic silicon-fluorine resin is obtained.
2. a kind of preparation method of organic silicon-fluorine resin according to claim 1, which is characterized in that the vinyl silicon tree
The contents of ethylene of rouge is 2-10%, viscosity 1000-8000cs；The vinyl polysiloxane is methyl vinyl silicone, benzene
One of base vinyl polysiloxane.
3. a kind of preparation method of organic silicon-fluorine resin according to claim 1, which is characterized in that the solvent is first
One or more of benzene, dimethylbenzene, ethyl acetate, ethyl alcohol, methanol, isopropanol, acetone, tetrahydrofuran mixture.
4. a kind of preparation method of organic silicon-fluorine resin according to claim 1, which is characterized in that the initiator is even
One of nitrogen bis-isobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl.
5. a kind of preparation method of organic silicon-fluorine resin according to claim 1, which is characterized in that described containing fluoride-based
Monomer is acrylic acid trifluoro ethyl ester, trifluoroethyl methacrylate, perfluorododecyl methacrylate, trifluoro propene, complete
One of fluorobenzene ethene, perfluorobutyl ethylene.
6. a kind of preparation method of organic silicon-fluorine resin according to claim 1, which is characterized in that the vinyl silicon tree
Rouge, solvent, initiator, styrene and fluorine-containing vinyl monomer mass ratio be 1:（1~10）：（0.001~0.005）：（0.2~
1）：（0.5~20）.
7. a kind of preparation method of organic silicon-fluorine resin according to claim 1, which is characterized in that the method preparation
Organic silicon-fluorine resin is suitable for waterproofing agent, antifouling paint, encapsulating material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810592617.5A CN108822265B (en) | 2018-06-11 | 2018-06-11 | Preparation method of organic silicon fluororesin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810592617.5A CN108822265B (en) | 2018-06-11 | 2018-06-11 | Preparation method of organic silicon fluororesin |
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| CN108822265A true CN108822265A (en) | 2018-11-16 |
| CN108822265B CN108822265B (en) | 2020-06-09 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8431624B2 (en) * | 2009-09-15 | 2013-04-30 | Novartis Ag | Prepolymers suitable for making ultra-violet absorbing contact lenses |
| CN106046912A (en) * | 2016-05-26 | 2016-10-26 | 清远市美乐仕油墨有限公司 | Waterproof slipping auxiliary for leather and method for preparing waterproof slipping auxiliary |
| CN106366259A (en) * | 2016-08-31 | 2017-02-01 | 秦瑶 | Fluorine-silicon nanoparticle modified styrene-acrylic emulsion |
| CN106957396A (en) * | 2017-04-10 | 2017-07-18 | 广东优科艾迪高分子材料有限公司 | A kind of automatically cleaning wear-resisting type organosilicon toughener and preparation method and application |
-
2018
- 2018-06-11 CN CN201810592617.5A patent/CN108822265B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8431624B2 (en) * | 2009-09-15 | 2013-04-30 | Novartis Ag | Prepolymers suitable for making ultra-violet absorbing contact lenses |
| CN106046912A (en) * | 2016-05-26 | 2016-10-26 | 清远市美乐仕油墨有限公司 | Waterproof slipping auxiliary for leather and method for preparing waterproof slipping auxiliary |
| CN106366259A (en) * | 2016-08-31 | 2017-02-01 | 秦瑶 | Fluorine-silicon nanoparticle modified styrene-acrylic emulsion |
| CN106957396A (en) * | 2017-04-10 | 2017-07-18 | 广东优科艾迪高分子材料有限公司 | A kind of automatically cleaning wear-resisting type organosilicon toughener and preparation method and application |
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| CN108822265B (en) | 2020-06-09 |
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