CN112608477A - Linear organic fluorine-containing polysiloxane and preparation method and application thereof - Google Patents
Linear organic fluorine-containing polysiloxane and preparation method and application thereof Download PDFInfo
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- CN112608477A CN112608477A CN202011494089.3A CN202011494089A CN112608477A CN 112608477 A CN112608477 A CN 112608477A CN 202011494089 A CN202011494089 A CN 202011494089A CN 112608477 A CN112608477 A CN 112608477A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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Abstract
The invention belongs to the technical field of fluorine-containing polymers, and particularly relates to linear organic fluorine-containing polysiloxane and a preparation method and application thereof. After the reaction is finished, decompressing and distilling to remove unreacted substances to obtain the fluorine-containing polysiloxane. Wherein the Rf organic group containing a fluorine atom is preferably X ((CF)3)2C)n‑O‑CmF2m+1The method has the advantages that the method is relatively simple, the byproducts are less, the post-treatment is convenient, the viscosity, the fluorine content and the like of the polysiloxane can be controlled through the raw material proportion, and the quality of the obtained product is higher. The fluorine-containing polysiloxane modified polyurethane can be used as a fluorine-containing polysiloxane material in the fields of coating, release agent, pressure-sensitive adhesive, lubricant, defoaming agent and the like.
Description
Technical Field
The invention belongs to the technical field of fluorine-containing polymers, and particularly relates to linear organic fluorine-containing polysiloxane and a preparation method and application thereof.
Background
Fluorine has the largest electronegativity, lower atomic polarizability (0.557) and smaller atomic radius (0.13nm), so that the C-F bond has shorter bond length and higher bond energy. The fluorocarbon polymer is not easy to react with oxygen, so that the fluorocarbon polymer has good oxygen resistance and chemical stability. Meanwhile, the C-F bond plays a good shielding role on the main chain of the organic matter, so that the organic matter has better stability. Fluorine atoms are introduced into an organic high molecular polymer, which has excellent properties such as acid resistance, oil repellency, water repellency, tack resistance, and stain resistance.
The fluorine-containing polysiloxane main chain has excellent flexibility, and fluorinated groups with low surface free energy and extremely stable chemical properties are used in the side chain and the main chain, so that the fluorine-containing polysiloxane has excellent performances of high and low temperature resistance, oxidation resistance, water resistance, oil resistance, solvent resistance, low surface free energy, low dielectric constant and the like, and is often applied to the fields of rubber, coating, release agents, pressure-sensitive adhesives, lubricants, defoaming agents and the like.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the linear organic fluorine-containing polysiloxane can be used as a main agent, a cross-linking agent, a platinum catalyst and the like to prepare a release agent, and can react with other raw materials to obtain a product after hydrolysis treatment of a fluorine-containing monomer.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the linear organic fluorine-containing polysiloxane has the following chemical structural formula:
wherein X, Y and Z are integers in the following range, X is more than or equal to 0 and less than or equal to 500, Y is more than or equal to 1 and less than or equal to 1000, and Z is more than or equal to 2 and less than or equal to 2000;
v is an alkenyl group of 2 to 10 (preferably 2 to 6) carbon atoms or a hydrogen atom;
rf is an organic fluorine-containing group;
R1is a substituted or unsubstituted monovalent radical of 1 to 10 (preferably 1 to 4) carbon atomsHaving no aliphatic unsaturation;
R2is alkyl of 1 to 8 carbon atoms;
q is a capping group, preferably a hydrogen atom, a methyl group or an alkenyl group.
Preferably, said Rf is X ((CF)3)2C)n-O-CmF2m+1R-, wherein X is H or F, R is a divalent hydrocarbon group of 2 to 6 carbons, preferably an alkyl group of 2 to 3 carbons, in which the fluorine segment is bonded to the silicon atom; n is an integer from 1 to 10, preferably n ═ 1; m is an integer of 1 to 20, preferably m is 2 to 3. The fluorine content in the molecule is 20-50%, preferably 30-40%. Organopolysiloxanes having a fluorine content of more than 50% are of too poor quality, while organopolysiloxanes having a fluorine content of less than 20% are also less effective.
Preferably, the content of alkenyl groups in the linear organopolysiloxane is from 0.1 to 5% or the content of hydrogen atoms in the linear organopolysiloxane is from 10 to 20%; the fluorine content of the linear organic fluorine-containing polysiloxane is 20-50%, and the viscosity at 25 ℃ is 100-3000 mPa.s, preferably 200-1500 mPa.s. At a viscosity of less than 100 mPas, as measured by a rotational viscometer, the corresponding composition has poor film properties and cannot achieve the desired peeling effect. At viscosities above 3000 mPas, the corresponding compositions are difficult to coat.
The preparation method of the linear organic fluorine-containing polysiloxane comprises the steps of firstly hydrolyzing fluorine-containing monomers, then mixing the hydrolyzed fluorine-containing monomers with vinyl siloxane or hydrogen-containing siloxane, alkyl siloxane and an end-capping reagent, reacting for 2-12h and copolymerizing at the temperature of 50-130 ℃ under the action of a catalyst, wherein the linear organic fluorine-containing polysiloxane is prepared from the following raw materials in percentage by mole:
the vinyl siloxane is
Or vinyl silicone oils, wherein a ═ 2 to 8, and V is an alkenyl group of 2 to 10 (preferably 2 to 6) carbon atoms, preferably ethylAlkenyl and allyl radicals, R1Is an alkyl group of 1 to 10 carbon atoms, preferably an alkyl group of 1 to 4 carbon atoms, preferably methyl or ethyl.
The hydrogen-containing siloxane is
Or high hydrogen silicone oil, wherein, c is 3-6, R1Is an alkyl group of 1 to 10 carbon atoms, preferably an alkyl group of 1 to 4 carbon atoms, preferably methyl or ethyl.
The alkyl siloxane is
Or alkyl silicone oils, wherein, b ═ 3-6, R2Is an alkyl group of 1 to 8 carbon atoms, preferably a methyl or ethyl group.
The end-capping reagent is
Wherein d is 0 to 30 and Y is a hydrogen atom, a methyl group or an alkenyl group.
The catalyst is one of potassium hydroxide, sodium hydroxide, tetramethyl ammonium hydroxide, sulfuric acid, phosphoric acid, hydrochloric acid or trifluoro methylsulfonic acid, preferably trifluoro methylsulfonic acid, and the amount of the catalyst is 0.1-0.4% of the weight of the fluorine-containing monomer.
The invention can be used for synthesizing and preparing coatings, release agents, pressure-sensitive adhesives, lubricants and defoaming agents and can be used as fluorine-containing polysiloxane materials.
Compared with the prior art, the invention has the following beneficial effects:
the method is relatively simple, has fewer byproducts and convenient post-treatment, can control the viscosity, the fluorine content and the like of the polysiloxane by the raw material proportion, and the obtained product has higher quality.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
1mol of fluorine-containing monomer (CF)3)2CFO(CF2CF2)2CH2CH2Si(Cl)2CH3Hydrolysis treatment, 0.67mol hexamethylhexavinylcyclohexasiloxane
2.27mol of hexamethylcyclotrisiloxane
0.0042mol of a silane blocking agent
And (2) mixing, adding into a reaction kettle, heating to 80 ℃ under the protection of nitrogen, adding trifluoromethanesulfonic acid with the mass fraction of 0.3% of fluorine-containing monomer for catalysis, reacting for 10 hours, cooling, neutralizing, filtering, and removing low-boiling-point substances to obtain fluorine-containing polysiloxane with the fluorine content of 32%, the vinyl content of 1.5% and the viscosity of 360 mPas.
Example 2
1mol of fluorine-containing monomer (CF)3)2CFO(CF2CF2)2CH2CH2Si(Cl)2CH3Hydrolysis treatment, 0.5mol of trimethylcyclotrisiloxane
1.83mol of alkylsiloxane
0.0042mol of a silane blocking agent
And (2) mixing, adding into a reaction kettle, heating to 80 ℃ under the protection of nitrogen, adding trifluoromethanesulfonic acid with the mass fraction of 0.3% of fluorine-containing monomer for catalysis, reacting for 10 hours, cooling, neutralizing, filtering, and removing low-boiling-point substances to obtain the fluorine-containing polysiloxane with the fluorine content of 33.4%, the hydrogen content of 16.3% and the viscosity of 310mPa & s.
Example 3
1mol of fluorine-containing monomer (CF)3)2CHO(CF2CF2)2CH2CH2Si(Cl)2CH3Hydrolysis treatment, 0.2mol hexamethylhexavinylcyclohexasiloxane
1.45mol of hexamethylcyclotrisiloxane
0.0031mol of a silane-terminated base agent
And (2) mixing, adding into a reaction kettle, heating to 80 ℃ under the protection of nitrogen, adding trifluoromethanesulfonic acid with the mass fraction of 0.3% of fluorine-containing monomer for catalysis, reacting for 10 hours, cooling, neutralizing, filtering, and removing low-boiling-point substances to obtain the fluorine-containing polysiloxane with the fluorine content of 44%, the vinyl content of 2.1% and the viscosity of 520mPa & s.
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (10)
1. A linear organofluorine-containing polysiloxane characterized by: has the following chemical structural formula:
wherein X, Y and Z are integers in the following range, X is more than or equal to 0 and less than or equal to 500, Y is more than or equal to 1 and less than or equal to 1000, and Z is more than or equal to 2 and less than or equal to 2000;
v is an alkenyl group of 2 to 10 carbon atoms or a hydrogen atom;
rf is an organic fluorine-containing group;
R1is 1-10 carbon atomsA substituted or unsubstituted monovalent group of a molecule having no aliphatic unsaturation;
R2is alkyl of 1 to 8 carbon atoms;
q is a blocking group, and is a hydrogen atom, a methyl group or an alkenyl group.
2. The linear organofluorine-containing polysiloxane according to claim 1, characterized in that: said Rf is X ((CF)3)2C)n-O-CmF2m+1R-, wherein X is H or F, and R is a divalent hydrocarbon group containing 2-6 carbons and having a fluorine segment connected with a silicon atom; n is an integer of 1 to 10; m is an integer of 1 to 20; the fluorine content in Rf molecule is 20-50%.
3. The linear organofluorine-containing polysiloxane according to claim 1, characterized in that: the content of alkenyl groups in the linear organopolysiloxane is 0.1-5% or the content of hydrogen atoms in the linear organopolysiloxane is 10-20%; the fluorine content of the linear organic fluorine-containing polysiloxane is 20-50%, and the viscosity at 25 ℃ is 100-3000mPa & s.
4. A method for producing a linear organofluorine-containing polysiloxane according to any one of claims 1 to 3, characterized by: firstly, hydrolyzing fluorine-containing monomer, then mixing with other raw materials, reacting for 2-12h at the temperature of 50-130 ℃ under the action of a catalyst, and copolymerizing to obtain the fluorine-containing monomer, wherein the raw materials comprise the following components in percentage by mole:
5. the method for producing a linear organofluorine-containing polysiloxane according to claim 4, characterized in that: the vinyl siloxane is
Or vinyl silicone oil, wherein a is 2-8 and V is alkenyl of 2-10 carbon atomsGroup, R1Is an alkyl group of 1 to 10 carbon atoms.
6. The method for producing a linear organofluorine-containing polysiloxane according to claim 4, characterized in that: the hydrogen-containing siloxane is
Or high hydrogen silicone oil, wherein, c is 3-6, R1Is an alkyl group of 1 to 10 carbon atoms.
7. The method for producing a linear organofluorine-containing polysiloxane according to claim 4, characterized in that: the alkyl siloxane is
Or alkyl silicone oils, wherein, b ═ 3-6, R2Is an alkyl group of 1 to 8 carbon atoms.
8. The method for producing a linear organofluorine-containing polysiloxane according to claim 4, characterized in that: the end-capping reagent is
Wherein d is 0 to 30 and Y is a hydrogen atom, a methyl group or an alkenyl group.
9. The method for producing a linear organofluorine-containing polysiloxane according to claim 4, characterized in that: the catalyst is one of potassium hydroxide, sodium hydroxide, tetramethyl ammonium hydroxide, sulfuric acid, phosphoric acid, hydrochloric acid or trifluoro methylsulfonic acid, and the amount of the catalyst is 0.1-0.4% of the weight of the fluorine-containing monomer.
10. Use of a linear organofluorine-containing polysiloxane according to any one of claims 1 to 3, characterized in that: is used for synthesizing and preparing coating, parting agent, pressure-sensitive adhesive, lubricant and defoaming agent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115975428A (en) * | 2021-10-15 | 2023-04-18 | 山东东岳高分子材料有限公司 | Anchoring agent for fluorine-silicon release agent and application thereof |
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| CA1221372A (en) * | 1982-12-29 | 1987-05-05 | Gunter Von Au | Fluoroalkyloxyalkyl containing organopolysiloxanes |
| US20110040063A1 (en) * | 2009-08-14 | 2011-02-17 | Shin -Etsu Chemical Co., Ltd. | Preparation of triorganosiloxy end-capped organopolysiloxane |
| CN103694892A (en) * | 2013-12-05 | 2014-04-02 | 深圳市冠恒新材料科技有限公司 | Fluorine-containing polysiloxane release agent and preparation method thereof |
| CN107602861A (en) * | 2017-08-28 | 2018-01-19 | 哈尔滨工业大学无锡新材料研究院 | A kind of waterborne flame retardant fluorine containing silicone oil and preparation method thereof |
| CN107619479A (en) * | 2017-08-23 | 2018-01-23 | 无锡龙驰氟硅新材料有限公司 | A kind of fluorine silicon mould release and preparation method thereof |
| CN110256677A (en) * | 2019-07-15 | 2019-09-20 | 广州道林合成材料有限公司 | Epoxy-modified trifluoro propyl silicone oil and preparation method thereof |
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2020
- 2020-12-17 CN CN202011494089.3A patent/CN112608477A/en active Pending
Patent Citations (6)
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| CA1221372A (en) * | 1982-12-29 | 1987-05-05 | Gunter Von Au | Fluoroalkyloxyalkyl containing organopolysiloxanes |
| US20110040063A1 (en) * | 2009-08-14 | 2011-02-17 | Shin -Etsu Chemical Co., Ltd. | Preparation of triorganosiloxy end-capped organopolysiloxane |
| CN103694892A (en) * | 2013-12-05 | 2014-04-02 | 深圳市冠恒新材料科技有限公司 | Fluorine-containing polysiloxane release agent and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115975428A (en) * | 2021-10-15 | 2023-04-18 | 山东东岳高分子材料有限公司 | Anchoring agent for fluorine-silicon release agent and application thereof |
| CN115975428B (en) * | 2021-10-15 | 2023-07-18 | 山东东岳高分子材料有限公司 | Anchoring agent for fluorine-silicon release agent and application thereof |
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