CN109852338A - Fluorosilicone rubber composition, preparation method and the sealant and coating prepared by the composition - Google Patents
Fluorosilicone rubber composition, preparation method and the sealant and coating prepared by the composition Download PDFInfo
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Abstract
The present invention relates to fluorine silicone rubber technical fields, and in particular to a kind of Fluorosilicone rubber composition, preparation method and the sealant and coating prepared by the composition.The Fluorosilicone rubber composition, by including following constituent: Hydroxy Terminated Fluorosilicone Rubber basis glue, filler, crosslinking agent, organic silicon reactive coupling agents and catalyst with specific content, further can also include molecular weight regulator and levelling agent, can air, room temperature environment in vulcanization form sealant；Sealant is formed by with good mechanical performance and oil resistant, chemical resistance.Meanwhile the Fluorosilicone rubber composition can also be dissolved in easy volatile solvent, and coating is made.The coating can be used for spraying or brushing the surface in touching oil or touching chemical reagent, to protect surfaces against corrosion.
Description
Technical field
The present invention relates to fluorine silicone rubber technical fields, and in particular to a kind of Fluorosilicone rubber composition, preparation method and
The sealant and coating prepared by the composition.
Background technique
China is completed by the Chinese Academy of Sciences preparation of fluoropolymer emulsion in the sixties, has synthesized fluorine silicone rubber sample；In 1966
Institute, section and Shanghai organic fluorine material research institute cooperation obtained the crude rubber of fluorinated silicone rubber for being equivalent to U.S. LS-420；The pilot scale seventies
Success SF series fluoride gel material；But the application in fields such as Aeronautics and Astronautics, automobiles is also seldom, and does not carry out industrialized production.
Fluorine-silicon compounded rubber stock is had excellent performance, but curing temperature is high and waste material is more, is gradually liquid fluorine silicon rubber in certain fields
Replaced glue；Add-on type liquid fluorine silicone rubber product producing process efficiency is higher, and scrap rate is almost nil, energy-efficient, but holds
Easily there is catalyst poisoning and vulcanizes not exclusively；The solidification strong applicability of condensed room temperature vulcanized glue is not very in intensity requirement
In the case where height, especially fields such as sealant and adhesive have the irreplaceable market advantage.With multiple groups part and two-component
Ketoxime removing type room temperature vulcanized fluorine silicone rubber is compared, and the single-component room temperature vulcanized fluorine silicone encapsulant of ketoxime removing type is in the base for solving oil resistivity
On plinth, there is advantage easy to use and environment amenable advantage.
CN101531881A discloses the adhesive of a kind of fluorine silicone rubber and metal, but its crosslinking method is thermal vulcanization,
And need to park several days, so that solvent (ketone and esters) volatilization is clean, in order to avoid generate bubble.Operate it is more complex, time-consuming and
Pollute air.
US5599893 shows to improve room temperature glue oil resistivity problem, is added to nine fluorine hexyl methyl dimethoxysilanes
Mode, to increase oil resistivity, but oil-resistant effect increase it is unobvious.
In consideration of it, overcoming the above defect in the prior art, providing the new Fluorosilicone rubber composition of one kind becomes this field
Technical problem urgently to be resolved.
Summary of the invention
In view of the above drawbacks of the prior art, the purpose of the present invention is to provide a kind of Fluorosilicone rubber compositions, its preparation
Method and the sealant and coating prepared by the composition.
The purpose of the present invention can be realized by technical solution below:
One aspect of the present invention provides a kind of Fluorosilicone rubber composition, and the composition is by each group comprising following parts by weight
The raw material divided is made: 100 parts of Hydroxy Terminated Fluorosilicone Rubber basis glue, 5-20 parts of filler, 3-15 parts of crosslinking agent, organic silicon coupling
1-5 parts of agent, 0.2-2 parts of catalyst, wherein the crosslinking agent and Hydroxy Terminated Fluorosilicone Rubber basis glue are in a manner of dealcoholysis
Reaction.
Preferably, the crosslinking agent is selected from methyltrimethoxysilane, vinyltrimethoxysilane, positive silicic acid first
One of ester, ethyl orthosilicate, phenyltrimethoxysila,e are a variety of.
Certain preferred embodiments according to the present invention, the raw material further include molecular weight regulator, are based on 100 parts by weight
Hydroxy Terminated Fluorosilicone Rubber basis glue, the molecular weight regulator be 1-10 parts.
Certain preferred embodiments according to the present invention, the raw material further include levelling agent, the hydroxyl based on 100 parts by weight
Fluorine silicon rubber base glue is blocked, the levelling agent is 1-5 parts.
Certain preferred embodiments according to the present invention, Hydroxy Terminated Fluorosilicone Rubber basis glue are to have following structure
One of polymer of formula is a variety of,
Wherein, R1=-(CH2)2(CF2)p1CF3, p1 is the integer of 0-7；R2For methyl, ethyl or phenyl；m1For 100-
1000 integer, n1For the integer of 0-500.
The viscosity of certain preferred embodiments according to the present invention, Hydroxy Terminated Fluorosilicone Rubber basis glue is
20000mpa.s to 90000mpa.s.
Preferably, the filler be white carbon black or white carbon black and selected from titanium dioxide, silicon powder, calcium carbonate, aluminium oxide,
One of iron oxide, fluoroplastics powder are a variety of.
It is highly preferred that the white carbon black is the modified white carbon black of fluorine containing silane.
Certain preferred embodiments according to the present invention, the molecular weight regulator are the compound for the formula that has following structure
One of or it is a variety of,
Wherein, R3=-(CH2)2(CF2)p2CF3, p2 is the integer of 0-7；R4For methyl, ethyl or phenyl；m2For 3-10's
Integer, n2For the integer of 0-5.
Certain preferred embodiments according to the present invention, the levelling agent are one had following structure in the compound of formula
Kind is a variety of,
Wherein, R5=-(CH2)2(CF2)p3CF3, p3 is the integer of 0-7；R6For methyl, ethyl or phenyl；m3For 3-20's
Integer, n3For the integer of 0-10.
Certain preferred embodiments according to the present invention, the organic silicon coupling agent include being selected from two tert-butoxy diethyls
Acyloxy silane, trifluoro propyl triethoxysilane, trifluoro propyl trimethoxy silane, trifluoro propyl methyl dimethoxy oxygroup silicon
Alkane, nine fluorine hexyl methyl dimethoxysilanes, gamma-aminopropyl-triethoxy-silane, N- (β-aminoethyl)-γ-aminopropyl front three
One of oxysilane is a variety of.
Certain preferred embodiments according to the present invention, the catalyst are selected from dibutyl tin dilaurate, two acetic acid
One of dibutyl tin, titanate compound, titanium complex are a variety of.
The present invention provides a kind of preparation methods of Fluorosilicone rubber composition, the described method comprises the following steps:
Step 1: under inert gas protection, Hydroxy Terminated Fluorosilicone Rubber basis glue and filler being added in reaction kettle and mixed
It closes uniform；
Step 2: being warming up to 120-150 DEG C, be evacuated to 50-100Pa, be sufficiently stirred 1-3 hours；
Step 3: being cooled to 50-60 DEG C, under inert gas protection, crosslinking agent, organic silicon coupling agent, catalysis is added
Agent is uniformly mixed.
Molecular weight regulator or/and stream is added after the step 1 in certain preferred embodiments according to the present invention
Flat agent is uniformly mixed.
Another aspect of the present invention provides a kind of sealant, is obtained by the Fluorosilicone rubber composition through room temperature vulcanization.
Another aspect of the present invention provides a kind of coating, includes the Fluorosilicone rubber composition.
The utility model has the advantages that
The present invention provides a kind of Fluorosilicone rubber compositions and preparation method thereof, by including described each with specific content
Constituent, Fluorosilicone rubber composition of the invention can air, room temperature environment in vulcanization form sealant；It is formed by
Sealant has good mechanical performance and oil resistant, chemical resistance.Meanwhile the composition can also be dissolved in easy volatile solvent
In, coating is made.The coating can be used for spraying or brushing the surface in touching oil or touching chemical reagent, to protect surface to exempt from
Corroded.
Specific embodiment
The present invention provides a kind of Fluorosilicone rubber composition, the composition by each component comprising following parts by weight original
Material is made: 100 parts of Hydroxy Terminated Fluorosilicone Rubber basis glue, 5-20 parts of filler, 3-15 parts of crosslinking agent, organic silicon coupling agent 1-5
Part, 0.2-2 parts of catalyst, wherein the crosslinking agent is reacted in a manner of dealcoholysis with Hydroxy Terminated Fluorosilicone Rubber basis glue.
Preferably, the crosslinking agent is selected from methyltrimethoxysilane, vinyltrimethoxysilane, positive silicic acid first
One of ester, ethyl orthosilicate, phenyltrimethoxysila,e are a variety of.
Preferably, relative to 100 parts of Hydroxy Terminated Fluorosilicone Rubber basis glue, the filler is 10-20 parts.
Preferably, relative to 100 parts of Hydroxy Terminated Fluorosilicone Rubber basis glue, the organic silicon coupling agent is 2-5 parts.
Preferably, relative to 100 parts of Hydroxy Terminated Fluorosilicone Rubber basis glue, the crosslinking agent is 3-8 parts.
Preferably, relative to 100 parts of Hydroxy Terminated Fluorosilicone Rubber basis glue, the catalyst is 0.2-1 parts.
Further, the raw material of the composition further includes molecular weight regulator, the hydroxy-end capped fluorine silicon based on 100 parts by weight
Rubber base glue, the molecular weight regulator are 1-10 parts, preferably 1-5 parts.
Further, the raw material of the composition further includes levelling agent, the Hydroxy Terminated Fluorosilicone Rubber base based on 100 parts by weight
Plinth glue, the levelling agent are 1-5 parts, preferably 1-3 parts.
Composition of the invention is easy to use, and use process does not have smell, environmentally friendly, corrosion-free to iron class material
Property.
Certain preferred embodiments according to the present invention, Hydroxy Terminated Fluorosilicone Rubber basis glue are to have following structure
One of compound of formula is a variety of,
Wherein, R1=-(CH2)2(CF2)p1CF3, p1 is the integer of 0-7, it is preferable that p1 is 0 or 3；R2For methyl, ethyl
Or phenyl, preferably methyl；m1For the integer of 100-1000, preferably 150-750, more preferably 300-600, n1For 0-500's
Integer, preferably 0-300.
Preferably, the viscosity of Hydroxy Terminated Fluorosilicone Rubber basis glue is 20000mpa.s to 90000mpa.s, more excellent
Selection of land is 26000mpa.s to 85000mpa.s.
Composition of the invention is introduced using Hydroxy Terminated Fluorosilicone Rubber basis glue as raw material and is increased product containing fluoroalkyl
Oil resistivity and solvent resistance, Hydroxy Terminated Fluorosilicone Rubber basis glue are also possible to mixture, by selecting different molecular weight
Hydroxy Terminated Fluorosilicone Rubber basis glue change viscosity to adjust the mechanical performance of product, to meet actual needs.
Other preferred embodiments according to the present invention, the filler is white carbon black or white carbon black and is selected from titanium dioxide
One of titanium, silicon powder, calcium carbonate, aluminium oxide, iron oxide, fluoroplastics powder are a variety of.
It is highly preferred that the white carbon black is the modified white carbon black of fluorine containing silane.
The size of the filler is that nanoscale is easy to disperse in the composition, plays reinforcement and increment because its partial size is small
The mechanical property of product can be improved in the effect of agent.Untreated white carbon black surface is usually hydrophilic, by using containing
Silicon fluoride is modified white carbon black, and the hydrophilic surface of white carbon black can be made to become hydrophobicity, with hydroxy-end capped fluorine silicon
When rubber base glue mixes, better dispersibility, the mechanical property of the products such as lift-off seal glue can be obtained.
Specifically, white carbon black is modified and can be carried out as follows using fluorine containing silane:
By 100 parts of white carbon blacks to be treated (can be common in the market fume colloidal silica or precipitated silica)
It is added in ethyl alcohol 100-200 parts of solution, it is evenly dispersed.Then 30- will be hydrolyzed in 10-30 parts of addition solution of hydrophobic coupling agent
It 60 minutes, flows back 2-3 hours under atmosphere of inert gases later.Then removing solvent, and it is warming up to 200-250 DEG C of drying 1-2
Hour saves up to modified white carbon black, coolant seal.
Wherein hydrophobic coupling agent can be with are as follows: (RCH2CH2)mSi(X)4-m, wherein m=1 or 2, X are alkoxy or amino；R
For-CF3、-(CF2)3CF3、-(CF2)5CF3With-(CF2)7CF3One of or it is a variety of；Or (R1CH2CH2)3(CH3)3(SiX)3, X
For oxygen or nitrogen；R1For-CF3、-(CF2)3CF3、-(CF2)5CF3With-(CF2)7CF3One of or it is a variety of.
More specifically, hydrophobic coupling agent can be trifluoro propyl methyl cyclotrisilazane or trifluoro propyl trimethoxy silicon
Alkane.
Other preferred embodiments according to the present invention, the molecular weight regulator are the chemical combination for the formula that has following structure
One of object is a variety of,
Wherein, R3=-(CH2)2(CF2)p2CF3, p2 is the integer of 0-7, it is preferable that p2 is 0 or 3；R4For methyl, ethyl
Or phenyl, preferably methyl；m2For the integer of 3-10, n2For the integer of 0-5.
The molecular weight regulator is the Hydroxy Terminated Fluorosilicone Rubber basis glue of low molecular weight.Preparing fluorosilicone gum combination
During object, the molecular weight of polymer in the adjustable Fluorosilicone rubber composition of molecular weight regulator used herein, from
And adjust the comprehensive performance of gained Fluorosilicone rubber composition.Specifically, the molecular weight regulator of the application can be prepared as follows: will
100 parts of fluorine-containing cyclosiloxane such as (trifluoro propyl methyl cyclotrisiloxane) or (nine fluorine hexyl methyl cyclotrisiloxane) and two
0-50 parts of such as octamethylcy-clotetrasiloxanes of methyl cyclosiloxane class compound, in 50-100 parts of polar solvents (such as tetrahydro furan
Mutter, acetonitrile, ethyl acetate or acetone) in after dissolution, Bronsted acid (such as sulfonic acid, resin cation, sulfuric acid, hydrochloric acid) 10- is added
15 parts, as catalyst, it is heated to reflux temperature, after carrying out back flow reaction 10-15 hours, removal acid layer is stood, then spends
Ionized water is cleaned, then be warming up to 120-150 DEG C of removing low-boiling-point substance to get.
Other preferred embodiments according to the present invention, the levelling agent are to have following structure in the compound of formula
It is one or more,
Wherein, R5=-(CH2)2(CF2)p3CF3, p3 is the integer of 0-7, it is preferable that p3 is 0 or 3；R6For methyl, ethyl
Or phenyl, preferably methyl；m3For the integer of 3-20, n3For the integer of 0-10.
The levelling agent is the fluorine silicon rubber base glue of the methyl blocking of low molecular weight.Preparing Fluorosilicone rubber composition
In the process, levelling agent used herein can be used for compensating mobility, be convenient for product constructing operation.The levelling agent of the application can be with
Following preparation: by fluorine-containing cyclosiloxane 100 parts of such as (trifluoro propyl methyl cyclotrisiloxane) or (nine fluorine hexyl methyl rings three
Siloxanes) and MM (hexamethyldisiloxane) or 30 parts of MDM (octamethyltrisiloxane), 5-10 parts of Bronsted acids of addition (such as
Sulfonic acid, sulfuric acid, hydrochloric acid, resin cation) in, it is washed after reaction 7-9 hours in 80-120 DEG C, and 120-150 DEG C of removing low boiling
Object obtains transparent uniform oily substance X.Then again by 100 parts of 10-20 parts of product X, fluorine-containing cyclosiloxane such as (trifluoros
Hydroxypropyl methyl cyclotrisiloxane) or (nine fluorine hexyl methyl cyclotrisiloxane) and dimethicone class compound 0-50
Part such as octamethylcy-clotetrasiloxane adds catalyst (such as tetramethylammonium hydroxide, potassium hydroxide, the hydrogen-oxygen of catalytic amount
Change sodium or their fluorine silicon alkoxide), under atmosphere of inert gases, it is warming up to 130-160 DEG C of reaction 6-8 hours, then be warming up to
180-200 DEG C of removing low-boiling-point substance, can obtain the levelling agent of the application.
Other preferred embodiments according to the present invention, the organic silicon coupling agent are selected from two tert-butoxy diethyls
Acyloxy silane, trifluoro propyl triethoxysilane, trifluoro propyl trimethoxy silane, trifluoro propyl methyl dimethoxy oxygroup silicon
Alkane, nine fluorine hexyl methyl dimethoxysilanes, gamma-aminopropyl-triethoxy-silane, N- (β-aminoethyl)-γ-aminopropyl front three
One of oxysilane is a variety of.
The organic silicon coupling agent in the present invention is conducive to increase the degree of cross linking of composition, to increase the machine of product
Tool performance.
Other preferred embodiments according to the present invention, the catalyst are selected from dibutyl tin dilaurate, two vinegar
One of sour dibutyl tin, titanate compound, titanium complex are a variety of.
Preferably, the catalyst is dibutyl tin dilaurate.
Another aspect of the present invention provides a kind of preparation method of Fluorosilicone rubber composition, and the method includes following
Step:
Step 1: under inert gas protection, Hydroxy Terminated Fluorosilicone Rubber basis glue and filler being added in reaction kettle and mixed
It closes uniform；
Further, the reaction kettle mentioned in this preparation method can be planetary mixer.
Specifically, under nitrogen protection, planet is put by 100 parts and filler 5-20 parts of Hydroxy Terminated Fluorosilicone Rubber basis glue
Stirrer for mixing is uniform.
Step 2: being warming up to 120-150 DEG C, be evacuated to 50-100Pa, be sufficiently stirred 1-3 hours；
Further, after the step 1 and before the step 2, molecular weight regulator or levelling agent, mixing is added
Uniformly.
Specifically, after the step 1 and before the step 2, molecular weight regulator 1-10 parts or levelling agent is added
It 1-5 parts, is uniformly mixed, is warming up to 120-130 DEG C, is evacuated to 50Pa, be sufficiently stirred 2-3 hours.
In some embodiments, after the step 1 and before the step 2, while molecular weight regulator 1- is added
It 10 parts and levelling agent 1-5 parts, is mixed evenly, is warming up to 120-130 DEG C, be evacuated to 50Pa, be sufficiently stirred 2-3 hours.
Step 3: being cooled to 50-60 DEG C, under inert gas protection, crosslinking agent, organic silicon coupling agent, catalysis is added
Agent is uniformly mixed.
Specifically, it is cooled to 50-60 DEG C, under nitrogen protection, crosslinking agent 3-15 parts, organic silicon coupling agent 1-5 is added
Part, 0.2-2 parts of catalyst are mixed and stirred for uniform, standing 1 hour, then are sealed packaging.
Another aspect of the present invention provides a kind of sealant, is obtained by the Fluorosilicone rubber composition through room temperature vulcanization.
The Fluorosilicone rubber composition of aforementioned seal packaging can carry out single-component room temperature vulcanized, formation sealant in air.It is described close
Sealing is good to aluminium sheet substrate cementability, can be applied to electronics, automobile and building trade.
Another aspect of the present invention provides a kind of coating, includes the Fluorosilicone rubber composition.By will be of the invention
Fluorosilicone rubber composition is dissolved in volatile solvent, such as ethyl acetate or methyl acetate, and water absorbing agent is added, such as methyl three
Methoxy silane, vinyltrimethoxysilane, trifluoro propyl trimethoxy silane, stir evenly to form coating.The coating can
To be corroded with protecting surfaces against for spraying or brushing the surface in touching oil or touching chemical reagent.
Specific implementation of the invention is described in detail below in conjunction with specific embodiment:
The preparation of modified white carbon black:
100 parts of fume colloidal silicas are added in 150 parts of solution of ethyl alcohol, it is evenly dispersed.Then by hydrophobic coupling agent trifluoro
It is hydrolyzed about 45 minutes in 20 parts of the hydroxypropyl methyl cyclotrisilazane above-mentioned solution of addition, flows back under atmosphere of inert gases later
2-3 hours.Then removing solvent, and 200 DEG C of drying are warming up to 2 hours up to modified white carbon black, coolant seal saves.
The preparation of molecular weight regulator:
By nine fluorine hexyl methyl cyclotrisiloxane, 100 parts and 25 parts octamethylcy-clotetrasiloxanes, in 100 parts of polar solvents four
After being dissolved in hydrogen furans, 10 parts of sulfonic acid are added as catalyst, is heated to reflux temperature, it is quiet after carrying out back flow reaction 10 hours
Removal acid layer is set, is then cleaned with deionized water, then is warming up to 150 DEG C of removing low-boiling-point substances.Gained molecular weight regulator knot
Structure formula is as follows:
Wherein, R3=-(CH2)2(CF2)p2CF3, p2 3, R4For methyl, m2For 3-6, n2For 1-3.
The preparation of levelling agent:
By 100 parts of nine fluorine hexyl methyl cyclotrisiloxane and 30 parts of MM (hexamethyldisiloxane), 10 parts of Bronsted acids are added
In sulfonic acid, is washed after being reacted 8 hours in 100 DEG C, and 150 DEG C of removing low-boiling-point substances, obtain transparent uniform oily substance X.Then
Again by 15 parts of product X, nine fluorine hexyl methyl cyclotrisiloxane, 100 parts and 25 parts octamethylcy-clotetrasiloxanes, adds and urge
The catalyst tetramethylammonium hydroxide of change amount is warming up to 150 DEG C and reacts 7 hours, then be warming up to 180- under atmosphere of inert gases
200 DEG C of removing low-boiling-point substances, can obtain the levelling agent of the application.Gained levelling agent structural formula is as follows:
Wherein, R5=-(CH2)2(CF2)p3CF3, p3 3, R6For methyl, m3For 3-10, n3For 1-5.
Embodiment 1
Under nitrogen protection, planet is added in the Hydroxy Terminated Fluorosilicone Rubber basis glue that 400g viscosity is 85000mpa.s to stir
It mixes in machine, the white carbon black and 50g titanium dioxide of the processing of 30g fluorine silazane is added, open planetary mixer, stir evenly, then
10g levelling agent is added, stirs evenly, then be warming up to 120 DEG C, in the case where vacuum degree is 50pa, stirs 3 hours.It is passed through recirculated water, is dropped
Temperature is to 60 DEG C, under nitrogen protection, 4g gamma-aminopropyl-triethoxy-silane, 5g trifluoro propyl trimethoxy silane, 20g is added
Methyltrimethoxysilane and 10g vinyltrimethoxysilane, 1g dibutyl tin dilaurate mix to uniformly.
1 hour is stood, RTV-01 is obtained.
Hydroxy Terminated Fluorosilicone Rubber basis used glue are as follows:
Wherein, R1=-(CH2)2(CF2)p1CF3, p1 0, R2For methyl, m1For 650-750, n1It is 0.
Embodiment 2
Under nitrogen protection, the Hydroxy Terminated Fluorosilicone Rubber basis glue and 200g viscosity for being 85000mpa.s by 200g viscosity
It is added in planetary mixer for the Hydroxy Terminated Fluorosilicone Rubber basis glue of 26000mpa.s, the white of 60g fluorine silazane processing is added
Carbon black is opened planetary mixer, is stirred evenly, and 20g molecular weight regulator is then added, stirs evenly, then be warming up to 130 DEG C,
In the case where vacuum degree is 50pa, stir 2 hours.It is passed through recirculated water, is cooled to 60 DEG C, under nitrogen protection, 4g N- (β-ammonia is added
Ethyl)-γ-aminopropyltrimethoxysilane, 10g trifluoro propyl trimethoxy silane, 5g methyltrimethoxysilane, 20g second
Alkenyl trimethoxy silane and 2g dibutyl tin dilaurate mix to uniformly.1 hour is stood, RTV-02 is obtained.
Hydroxy Terminated Fluorosilicone Rubber basis used glue are as follows:
Wherein, R1=-(CH2)2(CF2)p1CF3, p1 3, R2For methyl, m1For the integer of 250-300, n1It is 0.
Wherein, R1=-(CH2)2(CF2)p1CF3, p1 3, R2For methyl, m1For the integer of 150-250, n1It is 0.
Comparative example 1
It carries out in the same manner as in Example 1, the difference is that, unmodified white carbon black substituting modification hard charcoal is added
It is black, RTV-03 is prepared.
Performance test:
RTV-03 prepared by RTV-01-RTV-02 and comparative example 1 to embodiment 1-2 preparation has carried out room temperature sulphur
Change, has carried out the survey of hardness, tensile strength, elongation at break, tearing strength, stretching strength, surface drying time and cementability respectively
Examination.Wherein, the test condition of hardness and method are carried out according to ASTM D2240 standard, and the test condition and method of tensile strength are pressed
It is carried out according to ASTM D412 standard, the test condition and method of elongation at break are carried out according to ASTM D412 standard, tearing strength
Test condition and method according to ASTM D624 standard carry out.
Surface drying time: being under the conditions of certain environment temperature and humidity, by the exposure of gained RTV-01-RTV-03 composition
During room temperature vulcanization in atmospheric environment, its surface is touched with finger, stickiness disappears, the tack-free time.
Stretching strength: when model stretches 100%, the active force by opposite direction.
Cementability: so that RTV-01-RTV-03 composition room temperature vulcanization on substrate forms sealant, Zhi Houzai
The active force for implementing opposite direction on substrate and sealant, separates their, generally will form two states: cohesional failure and viscous
Close destroy, wherein cohesional failure refer to substrate glued construction, after being destroyed by external force, in the state that sealant layer ruptures；It is viscous
It closes to destroy and refer to and substrate glued construction, after being destroyed by external force, state that clung body is separated with rubber layer.
Oil resistivity condition: test sample impregnates 70 hours volume changes at 25 DEG C in the C of resistance to fuel oil.
Table 1 shows the result of above-mentioned each performance test.
Table 1RTV-01-RTV-03 composition room temperature vulcanization test
As shown in Table 1, the RTV-01 being prepared according to the embodiment of the present application 1-2 --- RTV-02 composition passes through packet
Each constituent of the application containing certain content shows excellent mechanical performance and the adhesiveness to aluminium sheet substrate.Comparison
The oil resistance and mechanical performance for the RTV-03 composition that example 1 is prepared are relatively poor.
Moreover, when use the Hydroxy Terminated Fluorosilicone Rubber basis glue containing nine fluorine hexyl side chains be formed by sealant for
The volume change for the C of resistance to fuel oil can be reduced to 7%-10%, as can be seen from Table 1, use in embodiment 2 and contain nine fluorine hexyl sides
The Hydroxy Terminated Fluorosilicone Rubber basis glue of chain, which is formed by sealant, can be reduced to 9% for the volume change for the C of resistance to fuel oil
(within 10%) is 18%-25% relative to volume change of the sealant general at present to the C of resistance to fuel oil, shows the present invention
Fluorosilicone rubber composition be formed by sealant with the excellent C of resistance to fuel oil performance, illustrating to introduce can increase containing fluoroalkyl
The oil resistance of product.
In addition, comparative example 1 and comparative example 1 using trifluoro propyl methyl cyclotrisilazane as can be seen that be modified white
The sealant of carbon black can be reduced to 12%-17%, and its tensile strength and tearing strength ratio for the volume change for the C of resistance to fuel oil
10%-25% is increased using the sealant of unmodified white carbon black, this also illustrates to can be improved using modified white carbon black close
The oil resistivity and mechanical performance of sealing.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (16)
1. a kind of Fluorosilicone rubber composition, which is characterized in that the composition by each component comprising following parts by weight raw material
Be made: 100 parts of Hydroxy Terminated Fluorosilicone Rubber basis glue, 5-20 parts of filler, 3-15 parts of crosslinking agent, 1-5 parts of organic silicon coupling agent,
0.2-2 parts of catalyst, wherein the crosslinking agent is reacted in a manner of dealcoholysis with Hydroxy Terminated Fluorosilicone Rubber basis glue.
2. Fluorosilicone rubber composition according to claim 1, which is characterized in that the crosslinking agent is selected from methyl trimethoxy oxygen
One of base silane, vinyltrimethoxysilane, methyl orthosilicate, ethyl orthosilicate, phenyltrimethoxysila,e are more
Kind.
3. Fluorosilicone rubber composition according to claim 1, which is characterized in that the raw material further includes molecular-weight adjusting
Agent, the Hydroxy Terminated Fluorosilicone Rubber basis glue based on 100 parts by weight, the molecular weight regulator are 1-10 parts.
4. Fluorosilicone rubber composition according to claim 1 or 3, which is characterized in that the raw material further includes levelling agent, base
In the Hydroxy Terminated Fluorosilicone Rubber basis glue of 100 parts by weight, the levelling agent is 1-5 parts.
5. Fluorosilicone rubber composition according to claim 1, which is characterized in that Hydroxy Terminated Fluorosilicone Rubber basis glue
For one of polymer for having following structure formula or a variety of,
Wherein, R1=-(CH2)2(CF2)p1CF3, p1 is the integer of 0-7；R2For methyl, ethyl or phenyl；m1For 100-1000's
Integer, n1For the integer of 0-500.
6. Fluorosilicone rubber composition according to claim 5, which is characterized in that Hydroxy Terminated Fluorosilicone Rubber basis glue
Viscosity be 20000mpa.s to 90000mpa.s.
7. Fluorosilicone rubber composition according to claim 1, which is characterized in that the filler is white carbon black or white carbon black
With selected from one of titanium dioxide, silicon powder, calcium carbonate, aluminium oxide, iron oxide, fluoroplastics powder or a variety of.
8. Fluorosilicone rubber composition according to claim 7, which is characterized in that the white carbon black is that fluorine containing silane is modified
White carbon black.
9. Fluorosilicone rubber composition according to claim 3, which is characterized in that the molecular weight regulator is with following
One of compound of structural formula is a variety of,
Wherein, R3=-(CH2)2(CF2)p2CF3, p2 is the integer of 0-7；R4For methyl, ethyl or phenyl；m2For the whole of 3-10
Number, n2For the integer of 0-5.
10. Fluorosilicone rubber composition according to claim 4, which is characterized in that the levelling agent is to have following structure
One of compound of formula is a variety of,
Wherein, R5=-(CH2)2(CF2)p3CF3, p3 is the integer of 0-7；R6For methyl, ethyl or phenyl；m3For the whole of 3-20
Number, n3For the integer of 0-10.
11. Fluorosilicone rubber composition according to claim 1, which is characterized in that the organic silicon coupling agent includes choosing
From ditert-butyldiacetyl oxygen-base silane, trifluoro propyl triethoxysilane, trifluoro propyl trimethoxy silane, trifluoro propyl
Methyl dimethoxysilane, nine fluorine hexyl methyl dimethoxysilanes, gamma-aminopropyl-triethoxy-silane, N- (β-aminoethyl)-
One of γ-aminopropyltrimethoxysilane is a variety of.
12. Fluorosilicone rubber composition according to claim 1, which is characterized in that the catalyst is selected from tin dilaurate
One of dibutyl tin, dibutyltin diacetate, titanate compound, titanium complex are a variety of.
13. a kind of preparation method of Fluorosilicone rubber composition of any of claims 1-12, the method includes with
Lower step:
Step 1: under inert gas protection, Hydroxy Terminated Fluorosilicone Rubber basis glue and filler being added in reaction kettle and mixed equal
It is even；
Step 2: being warming up to 120-150 DEG C, be evacuated to 50-100Pa, be sufficiently stirred 1-3 hours；
Step 3: being cooled to 50-60 DEG C, under inert gas protection, crosslinking agent, organic silicon coupling agent, catalyst is added, mixes
It closes uniform.
14. preparation method according to claim 13, which is characterized in that after the step 1, molecular-weight adjusting is added
Agent or/and levelling agent are uniformly mixed.
15. a kind of sealant is obtained by Fluorosilicone rubber composition of any of claims 1-12 through room temperature vulcanization.
16. a kind of coating includes Fluorosilicone rubber composition of any of claims 1-12, by the fluorine silicone rubber group
Object is closed to be dissolved in easy volatile solvent and obtain.
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| CN109852338B (en) | 2021-04-16 |
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