A kind of fluorine silicon raw rubber and preparation method thereof containing chain fluoroalkyl
Technical field
The present invention relates to fluorine silicon raw rubber technical fields, and in particular to a kind of fluorine silicon raw rubber and its preparation containing chain fluoroalkyl
Method.
Background technique
Fluorine silicone rubber is also known as γ-trifluoro propyl methyl polysiloxane, also introduces 0.2%~0.4% second in general strand
Alkenyl siloxane modification by copolymerization;For the viscid plasticity straight chain polymer compound of colorless and transparent height, main chain is made of silicon and oxygen atom,
The side group being connected with silicon is methyl, vinyl and trifluoro propyl, and molecular weight is between 50~800,000.Cooperate various additives, it can
It is kneaded into homogeneous sizing material.Under organic peroxide effect, various elastic rubber products can be sulfided into.Except with general silicon rubber
Characteristic outside, there are also performances such as preferable resistance to aviation fuel oil, hydraulic oil, machine oil, chemical reagent and solvents, can -55~+
Long-term work at 200 DEG C.
But since γ-trifluoro propyl methyl polysiloxane is short containing fluorine chain, fluorine content is only 36.5%, in oil resistant, resistance to
Hydrocarbon solvent etc. is difficult to achieve the effect that of great satisfaction, and solvent swell test shows that γ-trifluoro propyl methyl is poly-
The 72h swelling ratio of silicone rubber is at least 5%, is difficult to further decrease swelling ratio by common filling-modified method, this
Its application in many aspects can be made to be restricted, and it is relatively short in the service life of existing application field.With fluorine-containing
The growth of chain, such as by CF3CH2CH2Group CF3CF2CF2CF2CH2CH2、CF3CF2CF2CF2CF2CF2CH2CH2、CF3CF2CF2C
(CF3)2CH2CH2CH2Equal groups replace, and fluorine content can be improved to 61%~65%, fluorinated polysiloxane macromolecule polyalcohol it is upper
Stating performance can further improve.
Fluorinated polysiloxane macromolecular polymeric is prepared using the siloxanes ring body ring-opening polymerisation preparation containing chain fluoroalkyl
Object is in document Yutaka Furukawa.Journal of Applied Polymer Science, and 2001, vol.82,3333-
334 and document A.E.Shamaev.Russian Chemical Bulletin, International Edition, 2004,
Vol.53 (No.10): 2229-2232 has been reported that, however uses the siloxanes ring body ring-opening polymerisation preparation containing chain fluoroalkyl
The method difficulty or ease of fluorinated polysiloxane macromolecule polyalcohol obtain the product of high molecular weight, limit its answering in terms of rubber compound
With.In addition, the siloxanes ring body compound price containing chain fluoroalkyl is higher, the fluorinated polysiloxane obtained is also raised and has divided greatly
The cost of sub- polymer.
Summary of the invention
The purpose of the present invention is for prior art problem provide it is a kind of containing the fluorine silicon raw rubber of chain fluoroalkyl and this contain
The preparation method of the fluorine silicon raw rubber of chain fluoroalkyl.The molecular weight of fluorine silicon raw rubber containing chain fluoroalkyl of the invention is high, meets
Application in terms of rubber compound;Oil resistant, solvent resistance are more excellent compared with γ-trifluoro propyl methyl polysiloxane;Mechanics
Performance and thermal stability also correspondingly increase;Price has significant drop compared with the existing polysiloxanes containing chain fluoroalkyl simultaneously
It is low.
To achieve the goals above, present invention employs the following technical solutions: a kind of fluorine silicon containing chain fluoroalkyl is raw
The raw rubber of glue, every 100 mass parts includes following component according to the mass fraction:
The three ring body compound of siloxanes containing chain fluoroalkyl can use formula (Si (CH3)(Rf)O)3It indicates, wherein
RfFormula-(CH can be used2)mCnF2n+1It indicates, the integer that n is 3~8, m is 2 or 3.
Further, RfSelected from CF3CF2CF2CF2CH2CH2、CF3CF2CF2CF2CF2CF2CH2CH2、CF3CF2CF2C(CF3)2CH2CH2CH2One of.
The siloxanes ring body compound containing trifluoro propyl is selected from three (3,3,3- tri- of 2,4,6- trimethyl -2,4,6-
Fluoropropyl) in cyclotrisiloxane and 2,4,6,8- tetramethyl -2,4,6,8- four (3,3,3- trifluoro propyl) cyclotetrasiloxane one
Kind.
The siloxanes ring body compound containing vinyl is selected from three silicon of 2,4,6- trimethyl -2,4,6- triethylene basic ring
One of oxygen alkane and 2,4,6,8- tetramethyl -2,4,6,8- tetravinyl cyclotetrasiloxane.
The ethenyl blocking agent is selected from 1,3- divinyl -1,1,3,3- tetramethyl disiloxane and 1,3- diformazan
One of four ethylene disiloxane of base -1,1,3,3-.
A kind of preparation method of the fluorine silicon raw rubber of chain fluoroalkyl, includes the following steps:
First by the three ring body compound of siloxanes containing chain fluoroalkyl and the siloxanes ring body compound containing trifluoro propyl
It is added in three-necked flask, is stirred and heated to 80~140 DEG C, be dehydrated 0.5~1.5h at reduced pressure conditions;Then it is cooled to 30~
Siloxanes ring body compound, ethenyl blocking agent and acidic catalyst containing vinyl is added in 110 DEG C of reaction temperature, carries out
Ring-opening polymerization, the reaction time be 8~for 24 hours;When material viscosity reaches predetermined value, stops reaction, crude product is washed with water
To neutrality, the low-boiling-point substance in crude product is removed under reduced pressure, obtains the fluorine silicon raw rubber of chain fluoroalkyl.
Wherein, the raw rubber of every 100 mass parts is 10 by siloxanes three ring body compound of the mass fraction containing chain fluoroalkyl
~90 parts, the siloxanes ring body compound containing trifluoro propyl be 9~88 parts, the siloxanes ring body compound containing vinyl is 0.5
~3 parts, ethenyl blocking agent be 0.02~0.2 part;The raw rubber acidic catalyst dosage of every 100 mass parts is 0.04~3.5 matter
Measure part.
The three ring body compound of siloxanes containing chain fluoroalkyl can use formula (Si (CH3)(Rf)O)3It indicates, wherein
RfFormula-(CH can be used2)mCnF2n+1It indicates, the integer that n is 3~8, m is 2 or 3.
Further, RfSelected from CF3CF2CF2CF2CH2CH2、CF3CF2CF2CF2CF2CF2CH2CH2、CF3CF2CF2C(CF3)2CH2CH2CH2One of.
The siloxanes ring body compound containing trifluoro propyl is selected from three (3,3,3- trifluoro of 2,4,6- trimethyl -2,4,6-
Propyl) one of cyclotrisiloxane and 2,4,6,8- tetramethyl -2,4,6,8- four (3,3,3- trifluoro propyl) cyclotetrasiloxane.
The siloxanes ring body compound containing vinyl is selected from three silicon of 2,4,6- trimethyl -2,4,6- triethylene basic ring
One of oxygen alkane and 2,4,6,8- tetramethyl -2,4,6,8- tetravinyl cyclotetrasiloxane.
The ethenyl blocking agent is selected from 1,3- divinyl -1,1,3,3- tetramethyl disiloxane and 1,3- diformazan
One of four ethylene disiloxane of base -1,1,3,3-.
The acidic catalyst is selected from one of oleum, p-methyl benzenesulfonic acid, three fluosulfonic acid and trifluoroacetic acid.
Fluorine silicon raw rubber containing chain fluoroalkyl of the invention uses the three ring body compound of siloxanes containing chain fluoroalkyl
With the method for the siloxanes ring body copolymer compound containing trifluoro propyl, not only overcome prior art preparation contains chain fluoroalkyl
The relatively low problem of siloxane polymer molecular weight;And the three ring body compound of siloxanes containing chain fluoroalkyl is used with independent
The siloxane polymer that open loop obtains is compared, and the fluorine silicon raw rubber cost of the invention containing chain fluoroalkyl reduces.
Fluorine silicon raw rubber containing chain fluoroalkyl of the invention remove include three ring body compound of siloxanes containing chain fluoroalkyl,
Four kinds of siloxanes ring body compound containing trifluoro propyl, the siloxanes ring body compound containing vinyl and ethenyl blocking agent components
Outside, other components can also be added as needed, such as hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, 2,4,6- tri- second
Base -2,4,6- trimethyl cyclotrisiloxane, 2,4,6- trimethyl -2,4,6- triphenyl cyclotrisiloxane etc..
Three ring body compound of siloxanes containing chain fluoroalkyl is prepared using the prior art or literature method: 1) being prepared first
Fluoroalkyle compound containing double bond can use CnF2n+1X and Addition on ethylene generate CnF2n+1CH2CH2X, after through removing HX reaction life
At CnF2n+1CH=CH2, n is 4 or 6 in the above formulas, and X is Br or I;Or it is anti-with hexafluoropropylene dimmer and KF and allyl bromide, bromoallylene
It answers, generates CF3CF2CF2C(CF3)2CH2CH=CH2.2) with fluoroalkyle compound containing double bond and allyl chloride Si―H addition reaction
Generate fluoroalkyl dimethyl dichlorosilane (DMCS) (RFSiMeCl2).3) fluoroalkyl dimethyl dichlorosilane (DMCS) hydrolysis is obtained containing chain fluoroalkyl
Polysiloxane oligomers.4) Pintsch process obtains fluorine containing long-chain to the polysiloxane oligomers containing chain fluoroalkyl under alkaline condition
The three ring body compound of siloxanes of alkyl.
The present invention is by adopting the above-described technical solution, have the advantages that
1) molecular weight of the fluorine silicon raw rubber of the invention containing chain fluoroalkyl is high, meets the application in terms of rubber compound;
2) oil resistant, solvent resistance and the γ-trifluoro propyl after the fluorine silicon raw rubber vulcanization of the invention containing chain fluoroalkyl
Methyl polysiloxane is compared to more excellent;
3) mechanical property after the fluorine silicon raw rubber vulcanization of the invention containing chain fluoroalkyl and thermal stability are more excellent;
4) the fluorine silicon raw rubber cost of the invention containing chain fluoroalkyl reduces.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is furture elucidated.But the examples are only for explaining the invention for these, without
It is for limiting the scope of the invention.
D3F:2,4,6- trimethyl -2,4,6- three (3,3,3- trifluoro propyl) cyclotrisiloxane
D4F:2,4,6,8- tetramethyl -2,4,6,8- four (3,3,3- trifluoro propyl) cyclotetrasiloxane
D3Vi:2,4,6- trimethyl -2,4,6- trivinyl cyclotrisiloxane
D4Vi:2,4,6,8- tetramethyl -2,4,6,8- tetravinyl cyclotetrasiloxane
Vi2: 1,3- divinyl -1,1,3,3- tetramethyl disiloxane
Vi4: four ethylene disiloxane of 1,3- dimethyl -1,1,3,3-
Embodiment 1
Three ring body compound (Si (CH of siloxanes first by 50 mass parts containing chain fluoroalkyl3)
(CH2CH2CF2CF2CF2CF3)O)3Siloxanes ring body compound D with 49 mass parts containing trifluoro propyl3F is added in three-necked flask,
80 DEG C are stirred and heated to, is dehydrated 1.5h at reduced pressure conditions;Then it is cooled to 65 DEG C of reaction temperature, 0.9 mass parts are added
Siloxanes ring body compound D containing vinyl3Vi, 0.1 mass parts ethenyl blocking agent Vi2It is sent out with 0.1 mass parts acidic catalyst
Cigarette sulfuric acid carries out ring-opening polymerization, reaction time 20h;When material viscosity reaches predetermined value, stops reaction, be washed with water
Crude product is washed to neutrality, the low-boiling-point substance in crude product is removed under reduced pressure, obtains the fluorine silicon raw rubber of chain fluoroalkyl.Gpc analysis, molecule
Amount is 180,000.
Embodiment 2
Three ring body compound (Si (CH of siloxanes first by 10 mass parts containing chain fluoroalkyl3)
(CH2CH2CF2CF2CF2CF3)O)3Siloxanes ring body compound D with 88 mass parts containing trifluoro propyl3F is added in three-necked flask,
140 DEG C are stirred and heated to, is dehydrated 0.5h at reduced pressure conditions;Then it is cooled to 110 DEG C of reaction temperature, 1.95 mass are added
Siloxanes ring body compound D of the part containing vinyl3Vi, 0.05 mass parts ethenyl blocking agent Vi4With 0.04 mass parts acidic catalyst
Agent oleum carries out ring-opening polymerization, reaction time 8h;When material viscosity reaches predetermined value, stops reaction, use water
Crude product is washed to neutrality, the low-boiling-point substance in crude product is removed under reduced pressure, obtains the fluorine silicon raw rubber of chain fluoroalkyl.Gpc analysis, point
Son amount is 400,000.
Embodiment 3
Three ring body compound (Si (CH of siloxanes first by 90 mass parts containing chain fluoroalkyl3)
(CH2CH2CF2CF2CF2CF3)O)3Siloxanes ring body compound D with 9 mass parts containing trifluoro propyl4F is added in three-necked flask, stirs
It mixes and is heated to 120 DEG C, be dehydrated 1h at reduced pressure conditions;Then it is cooled to 90 DEG C of reaction temperature, 0.95 mass parts are added and contain
The siloxanes ring body compound D of vinyl4Vi, 0.05 mass parts ethenyl blocking agent Vi2With 1 mass parts acidic catalyst smoke
Sulfuric acid carries out ring-opening polymerization, reaction time 15h;When material viscosity reaches predetermined value, stops reaction, be washed with water
Crude product is removed under reduced pressure the low-boiling-point substance in crude product, obtains the fluorine silicon raw rubber of chain fluoroalkyl to neutrality.Gpc analysis, molecular weight
It is 370,000.
Embodiment 4
Three ring body compound (Si (CH of siloxanes first by 70 mass parts containing chain fluoroalkyl3)
(CH2CH2CF2CF2CF2CF3)O)3Siloxanes ring body compound D with 26.8 mass parts containing trifluoro propyl4Three-necked flask is added in F
In, 80 DEG C are stirred and heated to, is dehydrated 1.5h at reduced pressure conditions;Then it is cooled to 30 DEG C of reaction temperature, 3 mass parts are added
Siloxanes ring body compound D containing vinyl4Vi, 0.2 mass parts ethenyl blocking agent Vi2With 2 mass parts acidic catalyst trifluoros
Sulfonic acid carries out ring-opening polymerization, and the reaction time is for 24 hours;When material viscosity reaches predetermined value, stops reaction, be washed with water
Crude product is removed under reduced pressure the low-boiling-point substance in crude product, obtains the fluorine silicon raw rubber of chain fluoroalkyl to neutrality.Gpc analysis, molecular weight
It is 100,000.
Embodiment 5
Three ring body compound (Si (CH of siloxanes first by 60 mass parts containing chain fluoroalkyl3)
(CH2CH2CF2CF2CF2CF3)O)3Siloxanes ring body compound D with 38 mass parts containing trifluoro propyl4F is added in three-necked flask,
90 DEG C are stirred and heated to, is dehydrated 1.5h at reduced pressure conditions;Then it is cooled to 50 DEG C of reaction temperature, 1.98 mass parts are added
Siloxanes ring body compound D containing vinyl4Vi, 0.02 mass parts ethenyl blocking agent Vi4With 3.5 mass parts acidic catalysts
Three fluosulfonic acid carry out ring-opening polymerization, reaction time 18h;When material viscosity reaches predetermined value, stops reaction, use water
Crude product is washed to neutrality, the low-boiling-point substance in crude product is removed under reduced pressure, obtains the fluorine silicon raw rubber of chain fluoroalkyl.Gpc analysis, point
Son amount is 800,000.
Embodiment 6
Three ring body compound (Si (CH of siloxanes first by 60 mass parts containing chain fluoroalkyl3)
(CH2CH2CF2CF2CF2CF3)O)3Siloxanes ring body compound D with 39.4 mass parts containing trifluoro propyl3Three-necked flask is added in F
In, 100 DEG C are stirred and heated to, is dehydrated 1h at reduced pressure conditions;Then it is cooled to 70 DEG C of reaction temperature, 0.5 mass is added
Siloxanes ring body compound D of the part containing vinyl3Vi, 0.1 mass parts ethenyl blocking agent Vi4With 2 mass parts acidic catalysts pair
Toluenesulfonic acid carries out ring-opening polymerization, reaction time 15h;When material viscosity reaches predetermined value, stops reaction, use water
Crude product is washed to neutrality, the low-boiling-point substance in crude product is removed under reduced pressure, obtains the fluorine silicon raw rubber of chain fluoroalkyl.Gpc analysis, point
Son amount is 220,000.
Embodiment 7
Three ring body compound (Si (CH of siloxanes first by 50 mass parts containing chain fluoroalkyl3)
(CH2CH2CF2CF2CF2CF3)O)3Siloxanes ring body compound D with 48 mass parts containing trifluoro propyl3F is added in three-necked flask,
100 DEG C are stirred and heated to, is dehydrated 1h at reduced pressure conditions;Then it is cooled to 80 DEG C of reaction temperature, 1.97 mass parts are added
Siloxanes ring body compound D containing vinyl3Vi, 0.03 mass parts ethenyl blocking agent Vi2It is sent out with 2 mass parts acidic catalysts
Cigarette sulfuric acid carries out ring-opening polymerization, reaction time 15h;When material viscosity reaches predetermined value, stops reaction, be washed with water
Crude product is washed to neutrality, the low-boiling-point substance in crude product is removed under reduced pressure, obtains the fluorine silicon raw rubber of chain fluoroalkyl.Gpc analysis, molecule
Amount is 620,000.
Embodiment 8
Except the three ring body compound (Si (CH of siloxanes containing chain fluoroalkyl3)(CH2CH2CF2CF2CF2CF2CF2CF3)
O)3Substitution is outer, remaining is the same as embodiment 7.Gpc analysis, molecular weight are 600,000.
Embodiment 9
Except the three ring body compound (Si (CH of siloxanes containing chain fluoroalkyl3)(CH2CH2CH2C(CF3)2CF2CF2CF3)
O)3Substitution is outer, remaining is the same as embodiment 7.Gpc analysis, molecular weight are 630,000.
Embodiment 10
Three ring body compound (Si (CH of siloxanes first by 50 mass parts containing chain fluoroalkyl3)
(CH2CH2CF2CF2CF2CF3)O)3Siloxanes ring body compound D with 48 mass parts containing trifluoro propyl4F is added in three-necked flask,
100 DEG C are stirred and heated to, is dehydrated 1h at reduced pressure conditions;Then it is cooled to 80 DEG C of reaction temperature, 1.97 mass parts are added
Siloxanes ring body compound D containing vinyl4Vi, 0.03 mass parts ethenyl blocking agent Vi4With 2 mass parts acidic catalysts pair
Toluenesulfonic acid carries out ring-opening polymerization, reaction time 15h;When material viscosity reaches predetermined value, stops reaction, use water
Crude product is washed to neutrality, the low-boiling-point substance in crude product is removed under reduced pressure, obtains the fluorine silicon raw rubber of chain fluoroalkyl.Gpc analysis, point
Son amount is 700,000.
Embodiment 11
Three ring body compound (Si (CH of siloxanes first by 70 mass parts containing chain fluoroalkyl3)
(CH2CH2CF2CF2CF2CF3)O)3Siloxanes ring body compound D with 28 mass parts containing trifluoro propyl4F is added in three-necked flask,
100 DEG C are stirred and heated to, is dehydrated 1h at reduced pressure conditions;Then it is cooled to 80 DEG C of reaction temperature, 1.97 mass parts are added
Siloxanes ring body compound D containing vinyl4Vi, 0.03 mass parts ethenyl blocking agent Vi4With 2 mass parts acidic catalysts three
Fluoroacetic acid carries out ring-opening polymerization, reaction time 15h;When material viscosity reaches predetermined value, stops reaction, be washed with water
Crude product is washed to neutrality, the low-boiling-point substance in crude product is removed under reduced pressure, obtains the fluorine silicon raw rubber of chain fluoroalkyl.Gpc analysis, molecule
Amount is 680,000.
Embodiment 12
Three ring body compound (Si (CH of siloxanes first by 68 mass parts containing chain fluoroalkyl3)
(CH2CH2CF2CF2CF2CF3)O)3, siloxanes ring body compound D of 25 mass parts containing trifluoro propyl4The prestox of F and 5 mass parts
Cyclotetrasiloxane is added in three-necked flask, is stirred and heated to 100 DEG C, is dehydrated 1h at reduced pressure conditions;Then 80 DEG C are cooled to
Reaction temperature, be added siloxanes ring body compound D of 1.97 mass parts containing vinyl4Vi, 0.03 mass parts ethenyl blocking
Agent Vi4With 2 mass parts acidic catalyst trifluoroacetic acids, ring-opening polymerization, reaction time 15h are carried out;When material viscosity reaches
When to predetermined value, stops reaction, crude product is washed with water to neutrality, the low-boiling-point substance in crude product is removed under reduced pressure, obtains long-chain fluorine
The fluorine silicon raw rubber of alkyl.Gpc analysis, molecular weight are 660,000.
Comparative example 1
Three ring body compound (Si (CH of siloxanes first by 8 mass parts containing chain fluoroalkyl3)
(CH2CH2CF2CF2CF2CF3)O)3And 90 siloxanes ring body compound D of the mass parts containing trifluoro propyl4F is added in three-necked flask,
100 DEG C are stirred and heated to, is dehydrated 1h at reduced pressure conditions;Then it is cooled to 80 DEG C of reaction temperature, 1.97 mass parts are added
Siloxanes ring body compound D containing vinyl4Vi, 0.03 mass parts ethenyl blocking agent Vi4With 2 mass parts acidic catalysts three
Fluoroacetic acid carries out ring-opening polymerization, reaction time 15h;When material viscosity reaches predetermined value, stops reaction, be washed with water
Crude product is washed to neutrality, the low-boiling-point substance in crude product is removed under reduced pressure, obtains the fluorine silicon raw rubber of chain fluoroalkyl.Gpc analysis, molecule
Amount is 670,000.
Comparative example 2
Using conventional γ-trifluoro propyl methyl polysiloxane raw rubber sample, molecular weight is 700,000.
Oil resistivity test
By the raw rubber sample in embodiment 1~12 and comparative example 1~2 according to the specific gravity standard on the basis of ASTM D792
TM003 is prepared into the vulcanized test specimens that specification is 1 " × 1 " × 0.070 ', then uses the NuSil section on the basis of ASTM D471
The swelling test stone TM038 of skill company carries out the swellability test to vulcanized test specimens, and as a result see Table 1 for details.
The test of 1 swelling behavior of table
Mass change is smaller, illustrates that degree of swelling is lower, and solvent resistance is better.
Mechanics Performance Testing and thermal stability
Tensile strength is executed referring to ASTM D412, and tearing strength is executed referring to ASTM D624, and elongation is referring to ASTM
D412 is executed, and Shao Shi hardness is executed referring to ASTM D2240.Thermal stability passes through the mechanical property after 250 DEG C of hot air aging 72h
It can characterization.See Table 2 for details for test result.
2 Mechanics Performance Testing of table