CN115181270A - Ternary polymerization fluorosilicone rubber and preparation method thereof - Google Patents

Ternary polymerization fluorosilicone rubber and preparation method thereof Download PDF

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CN115181270A
CN115181270A CN202210863290.7A CN202210863290A CN115181270A CN 115181270 A CN115181270 A CN 115181270A CN 202210863290 A CN202210863290 A CN 202210863290A CN 115181270 A CN115181270 A CN 115181270A
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fluorosilicone rubber
ternary
polymerization
ternary polymerization
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李书兵
陈泽雨
孙刚
李岩松
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Hubei Xingrui Silicon Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention relates to ternary polymerization fluorosilicone rubber and a preparation method thereof, wherein the molecular formula of the ternary polymerization fluorosilicone rubber is (CH) 3 ) 2 (CH 2 CH)SiO[(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), wherein a, b and c are positive integers, trifluoropropyl methyl cyclotrisiloxane, methyl vinyl cyclosiloxane and dimethyl cyclosiloxane are used as raw materials, nitrogen bubbling negative pressure dehydration is carried out for 1 to 3 hours at the temperature of 60 to 100 ℃, then a blocking agent is added, a catalyst is added after uniform stirring, and the reaction is carried out for 0.5 to 1.5hour at the temperature of 70 to 100 DEG under stirringAnd then heating to 105-115 ℃ for reaction for 1-3 h, and heating to 150-190 ℃ for short time, thus obtaining the ternary polymerization fluorosilicone rubber. According to the ternary polymerization fluorosilicone rubber and the preparation method thereof provided by the invention, the advantages of the conventional fluorosilicone rubber and the silicone rubber are integrated, the cost is lower than that of the conventional fluorosilicone rubber, and the ternary polymerization fluorosilicone rubber has the characteristics of good oil resistance, solvent resistance, low surface energy, high and low temperature resistance, electrical property and the like, and meanwhile, the processability is good, so that the ternary polymerization fluorosilicone rubber has a wider application field.

Description

Terpolymer fluorosilicone rubber and preparation method thereof
Technical Field
The invention relates to a ternary polymerization fluorosilicone rubber and a preparation method thereof, belonging to the technical field of organic chemistry.
Background
The main chain structure of silicon rubber is formed by silicon and oxygen atoms alternatively, the side chain is usually formed by connecting two organic groups, usually methyl and a small amount of vinyl, on the silicon atom, various additives for silicon rubber bonding can be mixed and refined into homogeneous rubber, and then various elastic products can be obtained under the action of a vulcanizing agent, and the vulcanized rubber has good physiological inertia, high and low temperature resistance, aging resistance, ozone resistance and weather resistance. The method is widely applied to chemical industry, instruments, automobiles, machinery, aviation, cables, electronic and electric appliances and medical and health departments. However, the silicone rubber has poor oil resistance and solvent resistance, and cannot meet the application requirements of special fields.
The fluorine-containing group is introduced into the silicone rubber, namely the fluorosilicone rubber, so that the fluorosilicone rubber has the advantages of both the fluororubber and the silicone rubber, and the application field is wider. The fluorosilicone rubber is usually polymerized by trifluoropropyl methyl cyclotrisiloxane under the action of a catalyst, and a small amount of vinyl is carried on a molecular chain.
Because the price of the conventional fluorosilicone rubber is about ten times that of the silicon rubber, and part of application fields with requirements on oil resistance and solvent resistance are processed by adopting a fluororubber, silicon rubber or fluorosilicone rubber blending mode, the processing mode is difficult, vulcanized products are easy to layer, and the new performance of the products is influenced.
Due to the difference of the side groups, the reaction activities of the trifluoropropylmethyl cyclotrisiloxane, the methylvinyl cyclosiloxane and the dimethyl cyclosiloxane are greatly different. Under the alkaline condition, the reaction rate of trifluoropropylmethyl cyclotrisiloxane is 100 times that of octamethylcyclotetrasiloxane, the trifluoropropylmethyl cyclotrisiloxane is easy to have the phenomenon of back biting in the ring-opening reaction process, the linear siloxane content in the equilibrium state is 10-20%, and although the phenomenon can be weakened to a certain extent through the adjustment of the auxiliary agent and the catalyst, the quality of the fluorosilicone rubber can still be influenced.
The invention provides ternary polymerization fluorosilicone rubber and a preparation method thereof, which can adjust the proportion of fluorine-containing groups according to the specific requirements of the product application field on oil resistance and solvent resistance, and prepare the oil-resistant and solvent-resistant ternary polymerization fluorosilicone rubber with excellent processing performance, low cost and narrow molecular weight distribution.
Disclosure of Invention
Aiming at the difficulties in the preparation of the existing ternary polymerization fluorosilicone rubber and the requirements of an organic silicon product on oil resistance and solvent resistance, the invention provides ternary polymerization fluorosilicone rubber and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the ternary polymerization fluorosilicone rubber has the molecular formula of (CH) 3 ) 2 (CH 2 CH)SiO [(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), ternary copolymerized fluorine silicone rubber is divided into [ (CH) 3 )(CH 2 CH 2 CF 3 )SiO]、[(CH 3 )(CH 2 CH)SiO]、[(CH3) 2 SiO]The chain unit molar ratio a, b and c is 1:0.0004 to 0.1:0.1 to 10.
As a preferred scheme, the molecular formula of the ternary polymerization fluorosilicone rubber is (CH) 3 ) 2 (CH 2 CH)SiO [(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), wherein a: b: c =1:0.03:9.
as a preferred scheme, the molecular formula of the ternary polymerization fluorosilicone rubber is (CH) 3 ) 2 (CH 2 CH)SiO [(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), wherein a: b: c =9:0.02:1.
as a preferred scheme, the molecular formula of the ternary polymerization fluorosilicone rubber is (CH) 3 ) 2 (CH 2 CH)SiO [(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), wherein a: b: c =1:0.006:2.
as a preferred scheme, the molecular formula of the ternary polymerization fluorosilicone rubber is (CH) 3 ) 2 (CH 2 CH)SiO [(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), wherein a: b: c =1:1:8.
in the ternary polymerization fluorosilicone rubber with the molecular formula, the preparation method of the ternary polymerization fluorosilicone rubber comprises the following steps:
(1) Uniformly mixing trifluoropropylmethylcyclotrisiloxane, methylvinylcyclosiloxane and dimethylcyclosiloxane;
(2) Carrying out nitrogen bubbling negative pressure dehydration for 1 to 3 hours at the temperature of 60 to 100 ℃;
(3) Adding an end capping agent, stirring uniformly, then adding a catalyst, stirring at 70-100 ℃ for reaction for 0.5-1.5 h for preliminary polymerization, and then heating to 105-115 ℃ for reaction for 1-3 h for further polymerization;
(4) And heating to 150-190 ℃ for short-time release to obtain the ternary polymerization fluorosilicone rubber.
The methylvinylcyclosiloxane is trimethyltrivinylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, pentamethylpentavinylcyclopentasiloxane, hexamethylhexavinylcyclohexasiloxane or a mixture thereof.
In the trifluoropropylmethylcyclotrisiloxane, the methylvinylcyclosiloxane and the dimethylcyclosiloxane [ (CH) 3 )(CH 2 CH 2 CF 3 )SiO]、[(CH 3 )(CH 2 CH)SiO]、[(CH3) 2 SiO]The chain link molar ratio is 1:0.0004 to 0.1:0.1 to 10.
The dehydration temperature is 60 to 100 ℃, the dehydration time is 1 to 3h, and the dehydration pressure is-0.095 MPa to-0.01 MPa.
The purity of the nitrogen is more than or equal to 99.999 percent.
The end-capping agent is tetramethyldivinyl disiloxane or vinyl-terminated silicone oil with the viscosity of 5 to 50cs.
The catalyst is tetramethylammonium hydroxide alkali glue, and the dosage of the catalyst is 30 to 90ppm.
Compared with the prior art, the invention has the following beneficial effects:
(1) the fluorine-containing group is introduced into the molecular chain of the silicone rubber in a copolymerization mode, the oil resistance of the copolymerized rubber is in direct proportion to the content of the fluorine group when the content of the fluorine group is more than 10 percent, and the phenomena of easy layering and poor performance when the conventional silicone rubber product is introduced in a blending mode and vulcanized by introducing the fluorine-containing group are effectively avoided.
(2) The process adopts a step-by-step polymerization mode, refines the polymerization process, and enables the copolymerization reaction to be carried out orderly, thereby effectively avoiding the phenomenon of low conversion rate when the ring-opening reaction of trifluoropropyl methyl cyclotrisiloxane is balanced under the alkaline condition, and the obtained ternary polymerization fluorosilicone rubber has narrow molecular weight distribution and excellent processing performance.
(3) The fluorine content of the ternary copolymer fluorosilicone rubber can be flexibly adjusted according to the requirements of products on oil resistance and solvent resistance, the processing is convenient, and the cost is low.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
300g of trifluoropropylmethylcyclotrisiloxane, 0.75g of tetramethyltetravinylcyclotetrasiloxane and 300g of octamethylcyclotetrasiloxane are added to a three-necked flask; heating to 80 ℃ in an oil bath kettle, bubbling nitrogen, and dehydrating for 1h under-0.099 MPa; adding 0.16g of tetramethyl divinyl disiloxane, stirring uniformly, adding 2g of tetramethyl ammonium hydroxide alkali gel and 2% of alkali gel alkali content, stirring and reacting for 1h at 70 ℃, and heating to 105 ℃ for reacting for 2h for further polymerization; the temperature is increased to 170 ℃ for breaking medium and removing low. The molecular formula of the obtained ternary polymerization fluorosilicone rubber is (CH) 3 ) 2 (CH 2 CH)SiO [(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), wherein a: b: c =1:0.0045, molecular weight 89W, fluorine group content 32.1%, volatile matter 1.42%, conversion 83.9%, and appearance colorless and transparent.
Example 2
300g of trifluoropropylmethylcyclotrisiloxane, 0.75g of pentamethylpentavinylcyclopentasiloxane and 300g of octamethylcyclotetrasiloxane are added to a three-necked flask; heating to 80 ℃ in an oil bath kettle, bubbling nitrogen, and dehydrating for 1h under-0.099 MPa; adding 0.16g of tetramethyl divinyl disiloxane, stirring uniformly, adding 2g of tetramethyl ammonium hydroxide alkali gel and 2% of alkali gel alkali content, stirring and reacting for 1h at 70 ℃, then heating to 105 ℃ and reacting for 2h for further polymerization; heating to 170 ℃ for breaking medium and removing. The molecular formula of the obtained ternary polymerization fluorosilicone rubber is (CH) 3 ) 2 (CH 2 CH)SiO [(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), wherein a: b: c =1:0.0045, molecular weight 88W, fluorine group content 31.5%, volatile matter 1.35%, conversion 84.1%, and appearance colorless and transparent.
Example 3
300g of trifluoropropylmethylcyclotrisiloxane,0.35g of pentamethylpentavinylcyclopentasiloxane, 0.4g of tetramethyltetravinylcyclotetrasiloxane and 300g of octamethylcyclotetrasiloxane were charged into a three-necked flask; heating to 80 ℃ in an oil bath kettle, bubbling nitrogen, and dehydrating for 1h under-0.099 MPa; adding 0.16g of tetramethyl divinyl disiloxane, stirring uniformly, adding 2g of tetramethyl ammonium hydroxide alkali gel and 2% of alkali gel alkali content, stirring and reacting for 1h at 70 ℃, then heating to 105 ℃ and reacting for 2h for further polymerization; heating to 170 ℃ for breaking medium and removing. The molecular formula of the obtained ternary polymerization fluorosilicone rubber is (CH) 3 ) 2 (CH 2 CH)SiO[(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), wherein a: b: c =1, 2.1, molecular weight 86W, fluorine group content 31.9%, volatile matter 1.47%, conversion 83.8%, and appearance colorless and transparent.
Example 4
160g of trifluoropropylmethylcyclotrisiloxane, 1.2g of tetramethyltetravinylcyclotetrasiloxane and 640g of octamethylcyclotetrasiloxane were added to a three-necked flask; heating to 80 ℃ in an oil bath kettle, bubbling nitrogen, and dehydrating for 1h under-0.099 MPa; adding 0.34g of tetramethyl divinyl disiloxane, stirring uniformly, adding 2g of tetramethyl ammonium hydroxide alkali gel and 2% of alkali gel alkali content, stirring and reacting for 1h at 70 ℃, and heating to 105 ℃ for reacting for 2h for further polymerization; heating to 170 ℃ for breaking medium and removing. The molecular formula of the obtained ternary polymerization fluorosilicone rubber is (CH) 3 ) 2 (CH 2 CH)SiO [(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), wherein a: b: c =1, the weight ratio is 8.4, the molecular weight is 60W, the fluorine group content is 10.3%, the volatile matter is 1.42%, the conversion rate is 83.9%, and the appearance is colorless and transparent.
Example 5
700g of trifluoropropylmethylcyclotrisiloxane and 0.68 g of tetramethyltetravinylcyclotetrasiloxaneAlkyl and 40g octamethylcyclotetrasiloxane were added to a three-necked flask; heating to 80 ℃ in an oil bath kettle, bubbling nitrogen, and dehydrating for 1h under-0.099 MPa; adding 0.19g of tetramethyl divinyl disiloxane, stirring uniformly, adding 2g of tetramethyl ammonium hydroxide alkali gel and 2% of alkali gel alkali content, stirring and reacting for 1h at 70 ℃, and heating to 105 ℃ for reacting for 2h for further polymerization; heating to 170 ℃ for breaking medium and removing. The molecular formula of the obtained ternary polymerization fluorosilicone rubber is (CH) 3 ) 2 (CH 2 CH)SiO [(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), wherein a: b: c = 8.3.
Example 6
160g of trifluoropropylmethylcyclotrisiloxane, 86g of tetramethyltetravinylcyclotetrasiloxane and 600g of octamethylcyclotetrasiloxane are added to a three-necked flask; heating to 80 deg.C in oil bath, and dehydrating at-0.099 MPa for 1 hr under bubbling of nitrogen gas; adding 0.16g of tetramethyl divinyl disiloxane, stirring uniformly, adding 2g of tetramethyl ammonium hydroxide alkali gel and 2% of alkali gel alkali content, stirring and reacting for 1h at 70 ℃, and heating to 105 ℃ for reacting for 2h for further polymerization; raising the temperature to 155 ℃ for breaking the medium and removing the low. The molecular formula of the obtained ternary polymerization fluorosilicone rubber is (CH) 3 ) 2 (CH 2 CH)SiO [(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH) with the following components, wherein a: b: c = 1.
Example 7
140g of the ternary copolymer fluorosilicone rubber, 70g of the precipitated white carbon black and 5g of the hydroxyl silicone oil obtained in the embodiment 1 are uniformly mixed on an open mill, heat treated for 3 hours at 190 ℃ in an oven, placed for 20g, added with 2.5g of a vulcanizing agent, and vulcanized for 5 minutes at 175 ℃ on a flat vulcanizing machine, so that the obtained sheet is free of layering. After immersion in 3# standard oil at 150 ℃ for 70h, the volume change rate was +8%.
Example 8
140g of the terpolymer fluorosilicone rubber, 70g of precipitated white carbon black and 5g of hydroxyl silicone oil in example 4 are uniformly mixed on an open mill, heat treated for 3 hours at 190 ℃ in an oven, placed for 20g, added with 2.5g of a vulcanizing agent, and vulcanized for 5 minutes at 175 ℃ on a flat vulcanizing machine, so that the obtained sheet has no layering phenomenon. After immersion in standard oil # 3 at 150 ℃ for 70h, the volume change was +7%.
Example 9
140g of the terpolymer fluorosilicone rubber, 70g of precipitated white carbon black and 5g of hydroxyl silicone oil in example 5 are uniformly mixed on an open mill, heat treated for 3 hours at 190 ℃ in an oven, placed for 20g, added with 2.5g of a vulcanizing agent, and vulcanized for 5 minutes at 175 ℃ on a flat vulcanizing machine, so that the obtained sheet has no layering phenomenon. After immersion in standard oil # 3 at 150 ℃ for 70h, the volume change was +5%.
Example 10
140g of the ternary copolymer fluorosilicone rubber, 70g of the precipitated white carbon black and 5g of the hydroxyl silicone oil obtained in the embodiment 6 are uniformly mixed on an open mill, heat treated for 3 hours at 190 ℃ in an oven, placed for 20g, added with 2.5g of a vulcanizing agent, and vulcanized for 5 minutes at 175 ℃ on a flat vulcanizing machine, so that the obtained sheet is free of layering. After immersion in 3# standard oil at 150 ℃ for 70h, the volume change rate was +9%.
Comparative example 1
300g of trifluoropropylmethylcyclotrisiloxane, 0.75g of tetramethyltetravinylcyclotetrasiloxane and 300g of octamethylcyclotetrasiloxane are added to a three-necked flask; heating to 80 ℃ in an oil bath kettle, bubbling nitrogen, and dehydrating for 1h under-0.099 MPa; adding 0.16g of tetramethyl divinyl disiloxane, uniformly stirring, heating to 115 ℃, adding 2g of tetramethyl ammonium hydroxide alkali glue and 2% of alkali glue alkali content, and reacting for 3 hours; the temperature is increased to 170 ℃ for breaking medium and removing low. The obtained silicone rubber has the molecular weight of 25W, the fluorine content of 12.5 percent, the volatile component of 1.41 percent, the conversion rate of 52.9 percent and turbid appearance.
Comparative example 2
160g of trifluoropropylmethylcyclotrisiloxane, 1.2g of tetramethyltetravinylcyclotetrasiloxane and 640g of octamethylcyclotetrasiloxane were added to a three-necked flask; heating to 80 deg.C in oil bath, and dehydrating at-0.099 MPa for 1 hr under bubbling of nitrogen gas; adding 0.34g of tetramethyl divinyl disiloxane, uniformly stirring, heating to 115 ℃, adding 2g of tetramethyl ammonium hydroxide alkali glue and 2% of alkali glue alkali content, and reacting for 3 hours; the temperature is increased to 170 ℃ for breaking medium and removing low. The obtained silicone rubber has the molecular weight of 42W, the fluorine content of 3.5 percent, the volatile component of 1.48 percent, the conversion rate of 68.2 percent and turbid appearance.
Comparative example 3
300g of trifluoropropylmethylcyclotrisiloxane and 300g of octamethylcyclotetrasiloxane were added to a three-necked flask; heating to 80 deg.C in oil bath, and dehydrating at-0.099 MPa for 1 hr under bubbling of nitrogen gas; adding 0.16g of tetramethyl divinyl disiloxane, stirring uniformly, heating to 115 ℃, adding 2g of tetramethyl ammonium hydroxide alkali gel and 2% of alkali gel alkali content, and reacting for 3 hours; the temperature is increased to 170 ℃ for breaking medium and removing low. The obtained silicone rubber has the molecular weight of 25W, the fluorine content of 12.6 percent, the volatile component of 1.42 percent, the conversion rate of 52.8 percent and turbid appearance.
Comparative example 4
Adding 0.75g of tetramethyltetravinylcyclotetrasiloxane and 300g of octamethylcyclotetrasiloxane into a three-neck flask; heating to 80 deg.C in oil bath, and dehydrating at-0.099 MPa for 1 hr under bubbling of nitrogen gas; adding 0.16g of tetramethyl divinyl disiloxane, stirring uniformly, heating to 115 ℃, adding 2g of tetramethyl ammonium hydroxide alkali gel and 2% of alkali gel alkali content, and reacting for 3 hours; the temperature is increased to 170 ℃ for breaking medium and removing low. The obtained silicone rubber has the molecular weight of 56W, the volatile component of 1.15 percent, the conversion rate of 84.1 percent and colorless and transparent appearance.
Comparative example 5
And (3) taking 140g of the silicon rubber, 70g of the precipitated white carbon black and 5g of the hydroxyl silicone oil in the comparative example 4, uniformly mixing the materials on an open mill, carrying out heat treatment for 3h at 190 ℃ in an oven, standing for 20g, adding 2.5g of a vulcanizing agent, and vulcanizing for 5min at 175 ℃ on a flat vulcanizing machine to obtain the non-layered tablet. After immersion in 3# standard oil at 150 ℃ for 70h, the volume change rate was +38%.
Comparative example 6
And (3) uniformly mixing 70g of the fluorosilicone rubber obtained in the comparison document 1, 70g of the methyl vinyl silicone rubber, 70g of the precipitated white carbon black and 5g of the hydroxyl silicone oil on an open mill, carrying out heat treatment for 3h at 190 ℃ in an oven, standing for 20g, adding 2.5g of a vulcanizing agent, and vulcanizing for 5min at 175 ℃ on a flat vulcanizing machine to obtain the obviously layered tablet. After immersion in 3# standard oil at 150 ℃ for 70h, the volume change rate +24%.
As can be seen from the comparison, the ternary polymerization fluorosilicone rubber provided by the invention has the advantages of high conversion rate, good solvent resistance and excellent vulcanization performance.

Claims (10)

1. The ternary polymerization fluorosilicone rubber is characterized in that the molecular formula of the ternary polymerization fluorosilicone rubber is (CH) 3 ) 2 (CH 2 CH)SiO[(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH)，
Ternary copolymerized fluorine silicon rubber is divided into [ (CH) 3 )(CH 2 CH 2 CF 3 )SiO]、[(CH 3 )(CH 2 CH)SiO]、[(CH3) 2 SiO]The chain link molar ratio a: b: c is 1:0.0004 to 0.1:0.1 to 10 parts by weight.
2. The terpolymer fluorosilicone rubber according to claim 1, wherein the molecular formula of the terpolymer fluorosilicone rubber is as follows:
(CH 3 ) 2 (CH 2 CH)SiO[(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), wherein a: b: c = 1.
3. The terpolymer fluorosilicone rubber according to claim 1, wherein the formula of the terpolymer fluorosilicone rubber is:
(CH 3 ) 2 (CH 2 CH)SiO[(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), wherein a: b: c = 1.
4. The terpolymer fluorosilicone rubber according to claim 1, wherein the formula of the terpolymer fluorosilicone rubber is:
(CH 3 ) 2 (CH 2 CH)SiO[(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), wherein a: b: c =8.3:0.015:1.
5. the terpolymer fluorosilicone rubber according to claim 1, wherein the molecular formula of the terpolymer fluorosilicone rubber is as follows:
(CH 3 ) 2 (CH 2 CH)SiO[(CH 3 )(CH 2 CH 2 CF 3 )SiO] a [(CH 3 )(CH 2 CH)SiO] b [(CH 3 ) 2 SiO] c Si(CH 3 ) 2 (CH 2 CH), wherein a: b: c =1:1:8.
6. a preparation method of ternary polymerization fluorosilicone rubber is characterized by comprising the following steps:
(1) Uniformly mixing trifluoropropylmethylcyclotrisiloxane, methylvinylcyclosiloxane and dimethylcyclosiloxane;
(2) Carrying out nitrogen bubbling negative pressure dehydration on the mixture in the step (1);
(3) Adding a blocking agent into the step (2), uniformly stirring, and then adding a catalyst to perform a polymerization reaction;
(4) And (4) performing medium-breaking and low-removing on the polymer obtained in the step (3) to obtain the ternary polymerization fluorosilicone rubber.
7. The method for preparing the ternary copolymerized fluorosilicone rubber according to claim 5, wherein the methylvinylcyclosiloxane in the step (1) is a mixture of one or more of trimethyltrivinylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, pentamethylpentavinylcyclopentasiloxane, and hexamethylhexavinylcyclohexasiloxane.
8. The preparation method of the ternary copolymer fluorosilicone rubber as claimed in claim 7, wherein in the nitrogen bubbling negative pressure dehydration step in the step (2), the dehydration temperature is 60 to 100 ℃, the dehydration time is 1 to 3 hours, and the dehydration pressure is-0.095 MPa to-0.01 MPa; the purity of the nitrogen is more than or equal to 99.999 percent.
9. The preparation method of the ternary copolymer fluorosilicone rubber as claimed in claim 8, wherein the end-capping agent in step (3) is tetramethyldivinyldisiloxane or vinyl-terminated silicone oil with viscosity of 5 to 50cs, the catalyst is tetramethylammonium hydroxide alkali glue, and the dosage of the catalyst is 30 to 90ppm.
10. The preparation method of the ternary polymerization fluorosilicone rubber as claimed in claim 6, wherein in the step (3), polymerization is carried out in a stepwise temperature rise mode, wherein the initial polymerization temperature is 70 to 100 ℃ and the time is 0.5 to 1.5 hours; further heating and polymerizing at the temperature of 105-115 ℃ for 1-3h; the low temperature of the medium-breaking dehydration in the step (4) is 150 to 190 ℃.
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