CN112480677A - Silicon rubber composition and preparation method and application thereof - Google Patents
Silicon rubber composition and preparation method and application thereof Download PDFInfo
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- CN112480677A CN112480677A CN201910857897.2A CN201910857897A CN112480677A CN 112480677 A CN112480677 A CN 112480677A CN 201910857897 A CN201910857897 A CN 201910857897A CN 112480677 A CN112480677 A CN 112480677A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/243—Two or more independent types of crosslinking for one or more polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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Abstract
The invention provides a silicon rubber composition and a preparation method and application thereof, wherein the preparation raw materials of the silicon rubber composition comprise polysiloxane containing hydroxyl, a cross-linking agent, a reactive flame retardant, a catalyst, a reinforcing filler and a structural control agent, and the reactive phosphorus-containing flame retardant has a structure shown in a formula I and contains a hydroxyl reaction group; the reactive phosphorus-containing flame retardant is used as a reaction monomer to participate in the cross-linking vulcanization process of polysiloxane, so that the flame retardant exists in the silicone rubber composition in the form of molecular chain fragments, the phenomenon of micromolecule precipitation is avoided, the phenomenon that some additive flame retardants are easily dissolved in water to precipitate or hydrolyze is also avoided, and efficient and stable environment-friendly flame retardance is really realized. The silicone rubber composition provided by the invention has excellent flame retardant property and mechanical property, and the preparation process is simple and universal, and has wide industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a silicone rubber composition, and a preparation method and application thereof.
Background
The silicon rubber is a polymer with Si-O-Si bond as a main chain and methyl, vinyl, phenyl, amido, chloropropyl and other groups as side chains, and the structural particularity of the silicon rubber determines that the silicon rubber has good stability, corrosion resistance, aging resistance, physiological inertia and radiation resistance. The silicon rubber has higher oxygen index than rubber taking carbon as a main chain, has low heat release rate during combustion, slow flame propagation speed and no dripping, and can form a ceramic carbon-silicon layer on the surface after combustion, thereby having very wide application in the fields of electronic devices, power transmission, mechanical parts and aerospace. Nevertheless, the silicone rubber is combustible, and can be continuously combusted when exposed to fire and easily smoldered, so that potential combustion risks exist; in addition, silicone rubber applied to the fields of electronic devices and aerospace usually works under the conditions of high temperature, high pressure and discharge, so that higher requirements are put forward on the flame retardant property of the silicone rubber. Based on the above, the research and preparation of the silicone rubber material with better flame retardant property have very important significance.
The mechanism of silicone rubber burning is due to the continued burning of the low molar mass cyclic polysiloxane formed by cracking in the presence of ambient oxygen, the residue after burning being mainly silica and other inorganic fillers. In general, there are three considerations that need to be considered when providing silicone rubber with flame retardant properties: firstly, oxygen is prevented from diffusing to the combustion surface of the silicon rubber, or inert gas for diluting combustion gas is generated; secondly, the silicon rubber is inhibited from cracking to generate free radicals; and thirdly, a barrier layer is formed on the combustion surface of the silicon rubber to prevent heat energy from being transmitted to the interior of the silicon rubber and inhibit the temperature from rising. At present, most researches on the flame retardant performance of silicone rubber are focused on adding a flame retardant into a silicone rubber substrate, and dispersing the flame retardant into the substrate in a physical blending mode to realize the flame retardant effect.
CN104672916A discloses a ceramifiable flame-retardant fire-resistant silicone rubber composite material and a preparation process thereof, wherein a flame retardant in the ceramifiable flame-retardant fire-resistant silicone rubber composite material is a mixture of platinum and any one of carbon black, various metal oxides, hydroxides, calcium carbonate and silicone resin, a synergistic flame retardant is zinc borate or red phosphorus, and a fire-resistant filler is one of white carbon black, mica, calcium carbonate, wollastonite, kaolin, talcum powder, glass powder or montmorillonite. CN106633917A discloses a silicone rubber material with a synergistic flame retardant of a nano flame retardant and a nitrogen-phosphorus intumescent flame retardant and a preparation method thereof, wherein the silicone rubber material is composed of silicone rubber, the nano flame retardant, the nitrogen-phosphorus intumescent flame retardant and a vulcanizing agent, the nano flame retardant is one or more of halloysite, hydrotalcite, montmorillonite, zirconium phosphate, graphite oxide, carbon nanotubes or layered double hydroxide, and the nitrogen-phosphorus intumescent flame retardant is at least one of 2,4,8, 10-tetraoxy-3, 9-diphosphaspiro [5,5] undecane-3, 9-dioxo-3, 9-dimelamine, tris (neopentyl glycol phosphate-phosphorus-methylene) amine, neopentyl glycol phosphate tricyanamine salt and ammonium polyphosphate. CN109553978A discloses a flame-retardant room-temperature vulcanized silicone rubber formula and a flame-retardant room-temperature vulcanized silicone rubber, wherein the flame-retardant room-temperature vulcanized silicone rubber formula comprises dihydroxy polydimethylsiloxane, a reinforcing filler, simethicone, a flame retardant, a crosslinking agent and a catalyst, wherein the flame retardant is obtained by compounding magnesium hydroxide and chitosan, and the chitosan is used as a flame-retardant synergist and can assist magnesium hydroxide to be uniformly dispersed in a silicone rubber matrix to realize a flame-retardant effect.
Then, in the prior art, when the metal platinum flame retardant is used alone, the flame retardant effect is poor, and the metal platinum flame retardant is easily polluted by elements such as N, P and the like to lose activity; although the flame retardant performance is good after the platinum flame retardant, the metal hydroxide and the metal oxide are compounded, the acid and alkali resistance of the metal flame retardant is poor, so that the application of the metal flame retardant is greatly limited; the additive type phosphorus-nitrogen halogen-free flame retardant is a novel environment-friendly flame retardant material, but molecules, decomposers or water-soluble substances of the additive type phosphorus-nitrogen halogen-free flame retardant can enter the environment due to the migration property and the precipitation property in the processes of production, storage, use and scrapping treatment, and most of the additive type phosphorus-nitrogen halogen-free flame retardant is easy to hydrolyze, so that the environment is polluted, and the real environment-friendly flame retardant cannot be realized.
Therefore, the development of a silicone rubber material which can really realize safety, environmental protection and flame retardance to meet the application requirements is a research focus in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a silicone rubber composition, a preparation method and an application thereof, wherein in the silicone rubber composition, a flame retardant is used as a reaction monomer to participate in the cross-linking vulcanization process of polysiloxane, and finally exists in the silicone rubber composition in the form of molecular chain fragments, so that the silicone rubber composition provided by the invention has excellent flame retardant performance, does not generate micromolecules to migrate and separate out, and really realizes safety and environmental protection.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a silicone rubber composition, which is prepared from the following raw materials:
the reactive phosphorus-containing flame retardant has a structure shown in a formula I:
wherein L is1、L2Each independently selected from a group containing a terminal hydroxyl group.
Z1、Z2Each independently selected from phosphorus-containing groups.
M1Selected from linear alkylene, branched alkylene or arylene.
M2Selected from any organic group that satisfies the chemical environment.
Y1、Y2Each independently selected from an inert group, a sulfur atom, an oxygen atom, or-H.
X1Selected from any organylene group that satisfies a chemical environment.
a. b, c, d, f, g, h are each independently selected from integers of 0 to 5, such as 0, 1, 2, 3, 4 or 5; and a and b are not 0 at the same time, f and g are not 0 at the same time, g and h are not 0 at the same time, and b + c + h is less than or equal to 5 and a + d + g is less than or equal to 5.
e is an integer of 0 to 100, such as 0, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 95, and specific values therebetween, which are not intended to be exhaustive for the sake of brevity and clarity.
In the silicon rubber composition provided by the invention, the raw materials for preparation comprise hydroxyl-containing polysiloxane, a cross-linking agent, a reactive flame retardant, a catalyst, a reinforcing filler and a structural control agent, wherein the flame retardant is a reactive phosphorus-containing flame retardant with hydroxyl groups. In the cross-linking and vulcanizing process of the silicon rubber composition, polysiloxane with hydroxyl is condensed with a reactive flame retardant with hydroxyl, and the hydroxyl in the flame retardant reacts with silicon hydroxyl to generate a Si-O-C bond, so that the flame retardant is chemically bonded to a polysiloxane chain segment. Therefore, in the silicone rubber composition provided by the invention, the flame retardant is used as one of the reaction monomers to participate in the cross-linking vulcanization process of the polysiloxane, and finally exists in the silicone rubber composition in the form of molecular chain fragments, so that the phenomenon of micromolecule precipitation is avoided, and the phenomenon that the additive type flame retardant is easily dissolved in water to precipitate or is hydrolyzed is also avoided.
In the present invention, the hydroxyl group-containing polysiloxane may be used in an amount of 61 parts by weight, 63 parts by weight, 65 parts by weight, 68 parts by weight, 70 parts by weight, 73 parts by weight, 75 parts by weight, 78 parts by weight, 80 parts by weight, 83 parts by weight, 85 parts by weight, 88 parts by weight, 90 parts by weight, 93 parts by weight, 95 parts by weight or 99 parts by weight, and specific points therebetween are not exhaustive for the invention and for the sake of brevity.
In the present invention, the crosslinking agent may be used in an amount of 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 13 parts by weight, 15 parts by weight, 16 parts by weight, 18 parts by weight or 20 parts by weight, and specific points therebetween are not exhaustive for the purpose of brevity and clarity.
In the present invention, the reactive phosphorus-containing flame retardant may be used in an amount of 1.3 parts by weight, 1.5 parts by weight, 2 parts by weight, 3 parts by weight, 5 parts by weight, 7 parts by weight, 9 parts by weight, 10 parts by weight, 13 parts by weight, 15 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight, or 40 parts by weight, and specific point values therebetween are not limited to space and for brevity, and the present invention does not exhaustively enumerate specific point values included in the range.
In the present invention, the catalyst may be used in an amount of 0.11 parts by weight, 0.13 parts by weight, 0.15 parts by weight, 0.18 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 1 part by weight, 3 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight or 8 parts by weight, and specific points therebetween are not exhaustive for the purpose of brevity and clarity.
In the present invention, the reinforcing filler may be used in an amount of 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 13 parts by weight, 15 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 23 parts by weight, 25 parts by weight, 28 parts by weight, or 30 parts by weight, and specific points therebetween are not exhaustive for the purpose of brevity and clarity.
In the present invention, the amount of the structural control agent may be 0.11 parts by weight, 0.13 parts by weight, 0.15 parts by weight, 0.18 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 1 part by weight, 3 parts by weight, 5 parts by weight, 7 parts by weight, 10 parts by weight, 13 parts by weight, 15 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 23 parts by weight or 25 parts by weight, and specific points between the above points are limited to space and for the sake of brevity, and the present invention is not exhaustive and does not list specific points included in the range.
Preferably, the terminal hydroxyl group includes an alcoholic hydroxyl group and a phenolic hydroxyl group.
Preferably, Z is1、Z2Each independently selected from
One of (1), R1Is selected from any one of saturated or unsaturated alkyl, aryl or heteroaryl, and is more preferablyIs methyl, ethyl or phenyl.
Preferably, said M1One selected from the group consisting of C1-C30 linear or branched alkylene, C6-C30 arylene, and C5-C7 heteroarylene, more preferably C1-C5 linear alkylene, C3-C5 branched alkylene, or phenyl, and still more preferably C1-C3 linear alkylene, C3 branched alkylene, or phenyl.
The C1 to C30 include C2, C3, C5, C7, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C29, and the like.
The C6-C30 include C7, C9, C10, C12, C14, C15, C17, C20, C22, C24, C26, C28, C29 and the like.
The C5-C7 comprises C5, C6 or C7.
The C1-C5 linear alkylene comprises methylene, ethylene, propylene, butylene or pentylene.
The C3-C5 branched chain alkylene group comprises C3, C4 or C5 branched chain alkylene group.
Preferably, said M2Selected from N, S, C1-C30 straight chain or branched chain alkyl, C6-C30 aryl, C5-C7 heteroaryl,
Wherein R is2-R9Each independently selected from one of C1-C10 straight chain or branched chain alkylene, L2、Y2、Z2Is connected to R2-R9N, m, i, k are each independently selected from integers of 0 to 100, such as 0, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 95, and the specific values therebetween, are not intended to be exhaustive or to limit the invention to the specific values encompassed by the scope, for reasons of brevity and clarity.
The C1 to C30 include C2, C3, C5, C7, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C29, and the like.
The C6-C30 include C7, C9, C10, C12, C14, C15, C17, C20, C22, C24, C26, C28, C29 and the like.
The C5-C7 comprises C5, C6 or C7.
Preferably, said R is2-R9Each independently selected from one of C1-C6 linear or branched chain alkylene groups, such as C1, C2, C3, C4, C5 or C6 linear or branched chain alkylene groups.
Preferably, n, m, i, k are each independently selected from integers of 0 to 30, such as 0, 1, 5, 10, 15, 20, 25 or 29, and the specific values therebetween are limited by space and for brevity, and the invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, said Y is1、Y2Each independently selected from-H or ═ O.
Preferably, said X1One selected from N, S, substituted or unsubstituted C1 to C30 linear or branched alkylene groups, substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted C5 to C7 heteroarylene groups, substituted or unsubstituted C1 to C30 alkyleneamino groups, substituted or unsubstituted C1 to C30 alkyleneacyl groups, substituted or unsubstituted C1 to C30 alkyleneester groups, substituted or unsubstituted C6 to C30 arylamino groups, substituted or unsubstituted C6 to C30 aryloyl groups or C6 to C30 arylester groups, further preferably substituted or unsubstituted C1 to C5 linear or branched alkylene groups, substituted or unsubstituted C1 to C5 alkyleneamino groups, substituted or unsubstituted C1 to C5 alkyleneacyl groups, and substituted or unsubstituted C1 to C5 alkyleneester groups, further preferably-NH-R-, -R '-NH-, -R' -O-, -RV-C (O) -, substituted or unsubstituted C1-C5 linear or branched alkylene, wherein, R, R', R ", R ″VEach independently selected from substituted or unsubstituted C1 to C10 straight or branched chain alkylene.
The term "substituted" as used herein means that any one or more hydrogen atoms on the designated atom is replaced with a substituent selected from the designated group, provided that the designated atom does not exceed a normal valence and that the result of the substitution is a stable compound. When the substituent is an oxo group or a keto group (i.e., ═ O), then 2 hydrogen atoms on the atom are substituted. The ketone substituent is absent on the aromatic ring. By "stable compound" is meant a compound that can be isolated from a reaction mixture sufficiently robustly to an effective purity and formulated to be effective.
The C1 to C30 include C2, C3, C5, C7, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C29, and the like.
The C6-C30 include C7, C9, C10, C12, C14, C15, C17, C20, C22, C24, C26, C28, C29 and the like.
The C5-C7 comprises C5, C6 or C7.
The C1-C5 comprise C1, C2, C3, C4 or C5.
Preferably, the reactive phosphorus-containing flame retardant has a structure as shown in formula II, formula III, formula IV, formula V or formula VI:
wherein L is1、L2Each independently selected from a group terminating in an alcoholic hydroxyl group or a phenolic hydroxyl group.
M1Is selected from one of C1-C3 (such as C1, C2 or C3) straight-chain alkylene, C3 branched-chain alkylene or phenyl.
M2Selected from N, -NH-RTStraight chain or branched chain alkyl of C1-C6,
Wherein R isTIs C1-C6 (such as C1, C2, C3, C4, C5 or C6) straight chain or branched chain alkyl, R2-R9Each independently selected from C1-C6 (e.g. C1, C2, C3, C4, C5 or C6) straight chain or branched chain alkylene, n, m, i and k each independentlyIntegers selected from 0 to 30, such as 0, 1, 3, 5, 8,10, 15, 20, 25 or 29, and specific values therebetween, are not exhaustive of the specific values included in the ranges for brevity and conciseness.
R1Is methyl or ethyl.
R、R'、R”、RV、RPEach independently selected from substituted or unsubstituted C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C10) straight or branched chain alkylene.
Y1、Y2Each independently selected from-H or ═ O.
a. b, g and h are respectively and independently selected from 0, 1 or 2, a and b are not 0 at the same time, f and g are not 0 at the same time, and g and h are not 0 at the same time.
e is an integer from 0 to 20, such as 0, 1, 3, 5, 8,10, 13, 15, 18, or 19, and the specific values therebetween are not exhaustive for the invention and for brevity.
f is 0 or 1.
Preferably, the reactive phosphorus-containing flame retardant is further preferably any one of or a combination of at least two of the compounds having the following structures:
wherein R isPAnd (b) one selected from substituted or unsubstituted C1-C5 (e.g., C1, C2, C3, C4, or C5) straight chain or branched chain alkylene.
e is an integer from 0 to 20, such as 0, 1, 3, 5, 8,10, 13, 15, 18, or 19, and the specific values therebetween are not exhaustive for the invention and for brevity.
Preferably, the hydroxyl group-containing polysiloxane comprises a hydroxyl group-containing silicone oil and/or a hydroxyl group-containing raw rubber.
Preferably, the hydroxyl-containing polysiloxane is a hydroxyl-terminated polysiloxane.
Preferably, the hydroxyl-terminated polysiloxane is selected from any one of or a combination of at least two of hydroxyl-terminated polyvinyl siloxane, hydroxyl-terminated polyphenyl siloxane, hydroxyl-terminated polymethyl siloxane, hydroxyl-terminated polyfluoro siloxane, hydroxyl-terminated polyamino siloxane, hydroxyl-terminated polychloropropyl siloxane or hydroxyl-terminated polyhydroxypropyl siloxane.
Preferably, the hydroxyl-containing polysiloxane is α, ω -dihydroxypolydimethylsiloxane.
Preferably, the viscosity of the α, ω -dihydroxypolydimethylsiloxane is 5000 to 30000CPS, such as 6000CPS, 8000CPS, 10000CPS, 12000CPS, 14000CPS, 16000CPS, 18000CPS, 20000CPS, 22000CPS, 24000CPS, 26000CPS, 28000CPS, or 29000CPS, and specific point values therebetween, limited to space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the ranges.
Preferably, the cross-linking agent is an orthosilicate.
Preferably, the orthosilicate is selected from any one or a combination of at least two of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate.
Preferably, the catalyst is an organotin compound.
Preferably, the organotin compound is selected from any one of dibutyltin dilaurate, dibutyltin diacetate, stannous octoate, dialkyltin dimaleate, alkyltin dithiolate or dioctyltin dilaurate or a combination of at least two thereof.
Preferably, the reinforcing filler is white carbon.
Preferably, the white carbon black is precipitated white carbon black or/and gas-phase white carbon black.
Preferably, the structural control agent is selected from any one of or a combination of at least two of cyclic silazane, hexamethyldisilazane, divinyltetramethylsilazane, diphenylsilanediol, hydroxy silicone oil or vinyl hydroxy silicone oil.
Preferably, the raw materials for preparing the silicone rubber composition also comprise a plasticizer.
Preferably, the plasticizer is contained in an amount of 0.5 to 50 parts by weight, for example, 0.51 part by weight, 0.53 part by weight, 0.55 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 3 parts by weight, 5 parts by weight, 7 parts by weight, 9 parts by weight, 11 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 48 parts by weight, based on 100 parts by weight of the content of the hydroxyl group-containing polysiloxane, and specific point values therebetween are not exhaustive, for the sake of brevity and simplicity, and the specific point values included in the range are not exhaustive.
Preferably, the reinforcing agent is selected from any one or a combination of at least two of MQ silicone resin, dimethyl silicone oil, phthalate, fatty acid dibasic acid ester or citrate.
Preferably, the raw materials for preparing the silicone rubber composition also comprise a solid filler.
Preferably, the solid filler is contained in an amount of 5 to 150 parts by weight, for example, 7 parts by weight, 9 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 50 parts by weight, 70 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 130 parts by weight, 140 parts by weight, or 150 parts by weight, based on 100 parts by weight of the content of the hydroxyl group-containing polysiloxane, and specific point values therebetween are not exhaustive, and the invention is not limited to the specific point values included in the range for brevity and conciseness.
Preferably, the solid filler is selected from any one or a combination of at least two of white carbon black, titanium dioxide, aluminum hydroxide, carbon black, zinc stearate, talcum powder, calcium carbonate, barium sulfate, montmorillonite, diatomite, kaolin, gypsum, mica or magnesium hydroxide.
Preferably, the raw materials for preparing the silicone rubber composition also comprise an auxiliary agent.
Preferably, the auxiliary agent is selected from any one of water, a release agent, a cyclohexylynol, a polyether, polyether silicone oil, polyethylene glycol, sorbitol fatty acid ester, a fluorocarbon surfactant, divinyl tetramethyl disiloxane or tetravinyl tetramethyl tetrasiloxane ring body or a combination of at least two of the above.
In another aspect, the present invention provides a method for preparing the silicone rubber composition as described above, comprising the steps of:
adding polysiloxane containing hydroxyl, reactive phosphorus-containing flame retardant, reinforcing filler and a structural control agent into a reaction device for reaction; and then adding a cross-linking agent and a catalyst, mixing, and vulcanizing in a mold to obtain the silicone rubber composition.
Preferably, the reaction temperature is 95-130 ℃, such as 96 ℃, 98 ℃, 100 ℃, 103 ℃, 105 ℃, 108 ℃, 110 ℃, 113 ℃, 115 ℃, 118 ℃, 120 ℃, 123 ℃, 125 ℃, 127 ℃ or 129 ℃, and the specific values therebetween are limited to space and conciseness, and the invention does not exhaustive list the specific values included in the range, and further preferably 120 ℃.
Preferably, the reaction is carried out under stirring conditions.
Preferably, the reaction time is 0.5-5 h, such as 0.6h, 0.8h, 1h, 1.5h, 2h, 2.3h, 2.5h, 2.8h, 3h, 3.3h, 3.5h, 3.8h, 4h, 4.5h or 4.9h, and specific values therebetween, which are not limited by space and for brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the mixing is performed under stirring conditions.
Preferably, the temperature of the mixing is room temperature.
Preferably, the mixing time is 0.1-2 h, such as 0.1h, 0.3h, 0.5h, 0.7h, 1h, 1.1h, 1.3h, 1.5h, 1.7h, 1.9h or 2h, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be exhaustive of the specific values included in the scope.
Preferably, the reaction device is selected from any one of an open mill, an internal mixer or a kneader.
Preferably, the vulcanization time is 12-36 h, such as 13h, 15h, 17h, 19h, 20h, 22h, 24h, 25h, 27h, 30h, 32h, 34h or 35h, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the temperature of the vulcanization is room temperature.
In another aspect, the present invention provides a use of the silicone rubber composition as described above in seals, gaskets, electronic encapsulation and potting materials.
Compared with the prior art, the invention has the following beneficial effects:
the raw materials for preparing the silicone rubber composition comprise polysiloxane containing hydroxyl, a cross-linking agent, a reactive flame retardant, a catalyst, a reinforcing filler and a structural control agent, wherein the reactive phosphorus-containing flame retardant contains hydroxyl and can be used as a reaction monomer to participate in the cross-linking vulcanization process of the polysiloxane, so that the flame retardant exists in the silicone rubber composition in a molecular chain fragment form finally, the phenomenon of micromolecule precipitation is avoided, the phenomenon that some additive flame retardants are easy to dissolve in water and precipitate or hydrolyze is also avoided, and the efficient environment-friendly flame retardance is really realized. The silicon rubber composition provided by the invention has the advantages that the combustibility can reach V-0 level, the combustibility is still V-0 level after washing, the tensile strength and the elongation at break are high, the tensile strength reaches 3.45-3.95 MPa, the elongation at break reaches 151-185%, the combustibility, the flame retardant stability and the mechanical property are excellent, the preparation process is simple and universal, and the industrial application prospect is wide.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
A reactive phosphorus-containing flame retardant with alcoholic hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of phosphite ester dimethyl ester and 1mol of 1, 6-hexanedial into a reaction kettle, controlling the temperature to be lower than 5 ℃ in an ice bath, dropwise adding 2mol of triethylamine under stirring, gradually heating to 50 ℃, continuing to react for 1.5h, and carrying out reduced pressure distillation to obtain a target product.
1H NMR(CDCl3，400MHz，TMS):δ4.79-5.11(m,2H,-OH),3.66-3.83(d,12H,-CH3),3.37-3.51(d,2H,-CH-),1.17-1.55(m,8H,-CH2-)。
Preparation example 2
A reactive phosphorus-containing flame retardant with alcoholic hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of phosphite ester dimethyl ester and 1mol of 1, 4-butanedialdehyde into a reaction kettle, controlling the temperature in an ice bath to be lower than 5 ℃, dropwise adding 2mol of triethylamine under stirring, gradually heating to 50 ℃, continuing to react for 1 hour, and carrying out reduced pressure distillation to obtain a target product.
1H NMR(CDCl3，400MHz，TMS):δ4.51-4.69(m,2H,-OH),3.54-3.72(d,12H,-CH3),3.39-3.51(d,2H,-CH-),1.91-2.05(t,4H,-CH2-)。
Preparation example 3
A reactive phosphorus-containing flame retardant with phenolic hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 1mol of tert-butyl p-benzoquinone, 0.5mol of water and 1mL of toluene into a reaction kettle, adding 1mol of dimethyl phosphite under the protection of nitrogen, and reacting at 85 ℃ for 24 hours under the stirring condition; toluene was removed by rotary evaporation, and the product was isolated by silica gel column to give the desired product as a yellow oil.
1H NMR(CDCl3400MHz, TMS): delta 9.21-9.45(s,2H, -OH),6.71-6.88(m,2H, H of the phenyl ring), 3.61-3.77(d,6H, -O-CH)3),1.47-1.51(s,9H,-CH3)。
Preparation example 4
A reactive phosphorus-containing flame retardant with hydroxyl has the following structure:
the preparation method comprises the following steps:
adding 1mol of diethyl phosphite and 1mol of 4-hydroxyphenylacetaldehyde into a reaction kettle, controlling the temperature to be 0-3 ℃ in an ice bath, dropwise adding 1mol of triethylamine under stirring, gradually heating to 50 ℃, continuing to react for 1 hour, and carrying out reduced pressure distillation to obtain a target product.
1H NMR(CDCl3400MHz, TMS). delta.9.09-9.23 (s,1H, -OH),6.84-7.03(s,1H, -OH),6.52-6.91(m,4H, H of the phenyl ring), 4.15-4.23(d,1H, -CH-),3.88-3.96(m,4H, -CH-)2-),2.77-2.98(t,2H,-CH2-),1.36-1.44(d,4H,-CH3)。
Preparation example 5
A reactive phosphorus-containing flame retardant with phenolic hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 1mol of 1, 4-benzoquinone, 0.5mol of water and 1mL of toluene into a reaction kettle, adding 1mol of diethyl phosphite under the protection of nitrogen, and reacting for 24 hours at 80 ℃ under the stirring condition; toluene was removed by rotary evaporation, and then the product was separated by a silica gel column to obtain the objective product as a pale yellow oil.
1H NMR(CDCl3400MHz, TMS): Δ 9.55-9.71(s,1H, -OH),7.27-7.43(br,1H, -OH),6.87-7.15(m,1H, H with the phenyl ring close to P), 6.62-6.78(m,2H, H with the phenyl ring), 3.90-4.17(m,4H, -CH)2-),1.25-1.39(t,6H,-CH3)。
Preparation example 6
A reactive phosphorus-containing flame retardant with alcoholic hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 1mol of diethanolamine, 1mol of dimethyl hydroxy phosphite, 500mL of ethanol, 0.1mol of sodium hydroxide and 0.1g of DMAP into a reaction kettle, stirring and heating under the protection of nitrogen until the ethanol flows back, and then carrying out temperature-holding reflux reaction for 24 hours; and (4) after the reaction is finished, washing with water to be neutral, and removing impurities to obtain a target product.
1H NMR(CDCl3，400MHz，TMS):δ4.26-4.28(t,2H,-OH),3.77-3.81(m,4H,-CH2-),3.58-3.74(d,6H,-CH3) 2.69-2.92(d,2H, — CH attached to P)2-)。
Preparation example 7
A reactive phosphorus-containing flame retardant with alcoholic hydroxyl groups has the following structure:
the preparation method comprises the following steps:
adding 2mol of phosphite ester dimethyl ester and 1mol of glyoxal into a reaction kettle, controlling the temperature in an ice bath to be lower than 5 ℃, dropwise adding 2mol of triethylamine under stirring, gradually heating to 50 ℃, continuing to react for 1h, and carrying out reduced pressure distillation to obtain a target product.
1H NMR(CDCl3，400MHz，TMS):δ4.01-4.18(2H,-OH),3.54-3.71(d,12H,-CH3),3.19-3.29(d,2H,-CH-)。
Examples 1 to 7
The silicone rubber composition is prepared from the following raw materials:
wherein the hydroxyl-containing polysiloxane is alpha, omega-dihydroxy polydimethylsiloxane with viscosity of 18000CPS, the cross-linking agent is ethyl orthosilicate, the reactive phosphorus-containing flame retardants are reactive phosphorus-containing flame retardants with hydroxyl groups provided in preparation examples 1-7 respectively, the catalyst is dibutyltin dilaurate, the reinforcing filler is fumed silica, and the structural control agent is polyhydroxy silane.
The preparation method comprises the following steps:
adding polysiloxane containing hydroxyl, reactive phosphorus-containing flame retardant, reinforcing filler and structured control agent into an internal mixer, and stirring and mixing for 2h at 120 ℃; then adding a cross-linking agent and a catalyst, and stirring and mixing for 1h at room temperature; transferring the mixture into a mold, and vulcanizing at room temperature for 24 hours to obtain the silicone rubber composition.
Example 8
The embodiment provides a silicone rubber composition, which is prepared from the following raw materials:
wherein, the polysiloxane containing hydroxyl is alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 27000CPS, the cross-linking agent is ethyl orthosilicate, the reactive phosphorus-containing flame retardants are respectively the reactive phosphorus-containing flame retardants with hydroxyl provided in the preparation example 1, the catalyst is dibutyltin dilaurate, the reinforcing filler is fumed silica, and the structural control agent is polyhydroxy silane.
The preparation method comprises the following steps:
adding polysiloxane containing hydroxyl, reactive phosphorus-containing flame retardant, reinforcing filler and structured control agent into an internal mixer, and stirring and mixing for 3.5h at 130 ℃; then adding a cross-linking agent and a catalyst, stirring and mixing for 2 hours at room temperature; transferring the mixture into a mold, and vulcanizing at room temperature for 36h to obtain the silicone rubber composition.
Example 9
The embodiment provides a silicone rubber composition, which is prepared from the following raw materials:
wherein, the polysiloxane containing hydroxyl is alpha, omega-dihydroxy polydimethylsiloxane with the viscosity of 10000CPS, the cross-linking agent is ethyl orthosilicate, the reactive phosphorus-containing flame retardants are respectively the reactive phosphorus-containing flame retardants with hydroxyl provided in the preparation example 1, the catalyst is dibutyltin dilaurate, the reinforcing filler is fumed silica, and the structural control agent is polyhydroxy silane.
The preparation method comprises the following steps:
adding polysiloxane containing hydroxyl, reactive phosphorus-containing flame retardant, reinforcing filler and structured control agent into an internal mixer, and stirring and mixing for 1h at 100 ℃; then adding a cross-linking agent and a catalyst, stirring and mixing for 0.5 hour at room temperature; transferring the mixture into a mold, and vulcanizing at room temperature for 18h to obtain the silicone rubber composition.
Comparative example 1
This comparative example differs from example 1 in that the reactive phosphorus-containing flame retardant was replaced with 8 parts by weight of ethyl orthosilicate.
Comparative example 2
This comparative example differs from example 1 in that triphenyl phosphate is substituted for the reactive phosphorus-containing flame retardant and the like in parts by weight.
Comparative example 3
This comparative example differs from example 1 in that the reactive phosphorus-containing flame retardant was replaced with 55 parts by weight of triphenyl phosphate.
Comparative example 4
This comparative example differs from example 1 in that the equivalent weight parts of the reactive phosphorus-containing flame retardant were replaced with aluminum tris (diethylphosphinate).
Comparative example 5
This comparative example is different from example 1 in that the content of the reactive phosphorus-containing flame retardant was 45 parts by weight.
Comparative example 6
This comparative example is different from example 1 in that the content of the reactive phosphorus-containing flame retardant was 0.5 parts by weight.
And (3) performance testing:
(1) tensile strength and elongation at break: the test is carried out according to the standard regulation of GB/T528-2009, and the test size of the sample is 150mm multiplied by 15mm multiplied by 5 mm;
(2) combustibility: testing according to UL-94 vertical burning test standard;
(4) flame retardant stability: the silicone rubber composition was soaked in water for 1 hour, dried, and measured for flammability again according to the UL-94 vertical burning test standard.
The silicone rubber compositions provided in examples 1 to 9 and comparative examples 1 to 6 were tested for tensile strength, elongation at break, flammability and flame retardant stability according to the methods described above, and the test results are shown in table 1:
TABLE 1
| Tensile Strength (MPa) | Elongation at Break (%) | Combustibility | Stability of flame retardance | |
| Example 1 | 3.94 | 185 | V-0 | V-0 |
| Example 2 | 3.73 | 174 | V-0 | V-0 |
| Example 3 | 3.67 | 169 | V-0 | V-0 |
| Example 4 | 3.81 | 177 | V-0 | V-0 |
| Example 5 | 3.59 | 162 | V-0 | V-0 |
| Example 6 | 3.68 | 178 | V-0 | V-0 |
| Example 7 | 3.61 | 171 | V-0 | V-0 |
| Example 8 | 3.76 | 163 | V-0 | V-0 |
| Example 9 | 3.45 | 151 | V-0 | V-0 |
| Comparative example 1 | 2.89 | 125 | V-2 | V-2 |
| Comparative example 2 | 3.01 | 115 | V-1 | V-2 |
| Comparative example 3 | 3.19 | 104 | V-0 | V-2 |
| Comparative example 4 | 2.91 | 109 | V-1 | V-2 |
| Comparative example 5 | 3.43 | 131 | V-0 | V-0 |
| Comparative example 6 | 2.96 | 109 | V-1 | V-1 |
As can be seen from the data in Table 1, the silicone rubber compositions in examples 1 to 9, to which the reactive phosphorus-containing flame retardant having hydroxyl groups is added, have significantly excellent flammability and flame retardant temperature properties, and also have improved mechanical properties, as compared to the silicone rubber composition in comparative example 1, which has no flame retardant, the tensile strength of 3.45 to 3.95MPa and the elongation at break of 151 to 185%. The reactive phosphorus-containing flame retardant with hydroxyl in example 1 is replaced by the equivalent additive flame retardant (comparative example 2 and comparative example 4), the combustibility and the mechanical property of the obtained silicone rubber composition are both obviously reduced, the flame retardant stability is poor, and the flame retardant property of the material is obviously reduced after washing; the combustibility of the material can be optimized by increasing the dosage of the additive flame retardant in the silicone rubber composition (comparative example 3), but the flame retardant stability of the material is still poor, which shows that the additive flame retardant has low flame retardant efficiency and obvious migration and precipitation phenomena compared with the reactive flame retardant with hydroxyl. If the content of the reactive phosphorus-containing flame retardant having hydroxyl groups in the silicone rubber composition is outside the range defined in the present invention, an excessively high content of the flame retardant (comparative example 5) may excessively plasticize the material to affect the toughness of the material and cause a waste of resources; if the content of the flame retardant is too low (comparative example 6), the flame retardancy cannot be effectively realized.
In conclusion, according to the raw material preparation provided by the invention, the silicon rubber composition obtained by introducing the reactive phosphorus-containing flame retardant with hydroxyl as a reaction monomer in the cross-linking vulcanization process has excellent flame retardance, and the flame retardance of the material can reach V-0 level; the flame retardant in the silicone rubber composition provided by the invention participates in the cross-linking vulcanization reaction and stably exists in the silicone rubber in the form of molecular chain fragments, so that the flame retardant performance of the material is stable, the phenomena of micromolecule precipitation, water solubility or hydrolysis are avoided, the material cannot be degraded in flame retardant performance due to the migration precipitation of the flame retardant in operations such as washing, and the flame retardant performance of the material after washing can still reach V-0 level; in addition, the introduction of the reactive phosphorus-containing flame retardant with hydroxyl groups has the effect of enhancing and toughening the silicone rubber composition, so that the silicone rubber composition provided by the invention has good mechanical properties.
The applicant states that the silicone rubber composition, the preparation method and the application of the invention are illustrated by the above examples, but the invention is not limited to the above examples, i.e. the invention does not mean that the invention must be implemented by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The silicone rubber composition is characterized in that the preparation raw materials of the silicone rubber composition comprise the following components:
the reactive phosphorus-containing flame retardant has a structure shown in a formula I:
wherein L is1、L2Each independently selected from a group containing a terminal hydroxyl group;
Z1、Z2each independently selected from phosphorus-containing groups;
M1selected from linear alkylene, branched alkylene or arylene;
M2selected from any organic group that satisfies a chemical environment;
Y1、Y2each independently selected from an inert group, a sulfur atom, an oxygen atom, or-H;
X1selected from any organylene group that satisfies a chemical environment;
a. b, c, d, f, g and h are respectively and independently selected from integers of 0-5, a and b are not 0 at the same time, f and g are not 0 at the same time, g and h are not 0 at the same time, and meanwhile, b + c + h is less than or equal to 5 and a + d + g is less than or equal to 5;
e is an integer of 0 to 100.
2. The silicone rubber composition according to claim 1, wherein the terminal hydroxyl groups include alcoholic hydroxyl groups and phenolic hydroxyl groups;
preferably, Z is1、Z2Each independently selected from
One of (1), R1Any one selected from saturated or unsaturated alkyl, aryl or heteroaryl, more preferably methyl, ethyl or phenyl;
preferably, said M1One selected from C1-C30 linear chain or branched chain alkylene, C6-C30 arylene or C5-C7 heteroarylene, more preferably C1-C5 linear chain alkylene, C3-C5 branched chain alkylene or phenyl, and more preferably C1-C3 linear chain alkylene, C3 branched chain alkylene or phenyl;
preferably, said M2Selected from N, S, C1-C30Straight chain or branched chain alkyl, C6-C30 aryl, C5-C7 heteroaryl,
Wherein R is2-R9Each independently selected from one of C1-C10 straight chain or branched chain alkylene, L2、Y2、Z2Is connected to R2-R9N, m, i, k are each independently selected from integers of 0 to 100;
preferably, said R is2-R9Each independently selected from one of C1-C6 straight chain or branched chain alkylene;
preferably, n, m, i and k are respectively and independently selected from integers of 0-30;
preferably, said Y is1、Y2Each is independently selected from-H or ═ O;
preferably, said X1One selected from N, S, substituted or unsubstituted C1 to C30 linear or branched alkylene groups, substituted or unsubstituted C6 to C30 arylene groups, substituted or unsubstituted C5 to C7 heteroarylene groups, substituted or unsubstituted C1 to C30 alkyleneamino groups, substituted or unsubstituted C1 to C30 alkyleneacyl groups, substituted or unsubstituted C1 to C30 alkyleneester groups, substituted or unsubstituted C6 to C30 arylamino groups, substituted or unsubstituted C6 to C30 aryloyl groups or C6 to C30 arylester groups, further preferably substituted or unsubstituted C1 to C5 linear or branched alkylene groups, substituted or unsubstituted C1 to C5 alkyleneamino groups, substituted or unsubstituted C1 to C5 alkyleneacyl groups, and substituted or unsubstituted C1 to C5 alkyleneester groups, further preferably-NH-R-, -R '-NH-, -R' -O-, -RV-C (O) -, substituted or unsubstituted C1-C5 linear or branched alkylene, wherein, R, R', R ", R ″VEach independently selected from substituted or unsubstitutedC1-C10 straight chain or branched chain alkylene.
3. The silicone rubber composition according to claim 1 or 2, wherein the reactive phosphorus-containing flame retardant preferably has a structure according to formula II, formula III, formula IV, formula V or formula VI:
wherein L is1、L2Each independently selected from a group terminating in an alcoholic hydroxyl group or a phenolic hydroxyl group;
M1one selected from C1-C3 straight chain alkylene, C3 branched chain alkylene or phenyl;
M2selected from N, -NH-RTStraight chain or branched chain alkyl of C1-C6,
Wherein R isTIs C1-C6 straight chain or branched chain alkyl, R2-R9Each independently selected from C1-C6 straight chain or branched chain alkylene, n, m, i and k are each independently selected from integers of 0-30;
R1is methyl or ethyl;
R、R'、R”、RV、RPeach independently selected from substituted or unsubstituted C1-C10 straight or branched chain alkylene;
Y1、Y2each is independently selected from-H or ═ O;
a. b, g and h are respectively and independently selected from 0, 1 or 2, a and b are not 0 at the same time, f and g are not 0 at the same time, and g and h are not 0 at the same time;
e is an integer of 0-20, f is 0 or 1;
preferably, the reactive phosphorus-containing flame retardant is further preferably any one of or a combination of at least two of the compounds having the following structures:
wherein R isPOne selected from substituted or unsubstituted C1-C5 straight chain or branched chain alkylene, and e is an integer of 0-20.
4. The silicone rubber composition according to any one of claims 1 to 3, wherein the hydroxyl group-containing polysiloxane comprises a hydroxyl group-containing silicone oil and/or a hydroxyl group-containing raw rubber;
preferably, the hydroxyl-containing polysiloxane is a hydroxyl-terminated polysiloxane;
preferably, the hydroxyl-terminated polysiloxane is selected from any one or a combination of at least two of hydroxyl-terminated polyvinyl siloxane, hydroxyl-terminated polyphenyl siloxane, hydroxyl-terminated polymethyl siloxane, hydroxyl-terminated polyfluoro siloxane, hydroxyl-terminated polyamino siloxane, hydroxyl-terminated polychloropropyl siloxane or hydroxyl-terminated polyhydroxypropyl siloxane;
preferably, the hydroxyl-containing polysiloxane is α, ω -dihydroxypolydimethylsiloxane;
preferably, the viscosity of the alpha, omega-dihydroxy polydimethylsiloxane is 5000-30000 CPS.
5. The silicone rubber composition according to any one of claims 1 to 4, wherein the crosslinking agent is an orthosilicate;
preferably, the orthosilicate is selected from any one or a combination of at least two of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate;
preferably, the catalyst is an organotin compound;
preferably, the organotin compound is selected from any one of dibutyltin dilaurate, dibutyltin diacetate, stannous octoate, dialkyltin dimaleate, alkyltin dithiolate or dioctyltin dilaurate or a combination of at least two thereof.
6. The silicone rubber composition according to any one of claims 1 to 5, wherein the reinforcing filler is white carbon black;
preferably, the white carbon black is precipitated white carbon black or/and gas-phase white carbon black;
preferably, the structural control agent is selected from any one of or a combination of at least two of cyclic silazane, hexamethyldisilazane, divinyltetramethylsilazane, diphenylsilanediol, hydroxy silicone oil or vinyl hydroxy silicone oil.
7. The silicone rubber composition according to any one of claims 1 to 6, wherein the raw material for preparing the silicone rubber composition further comprises a plasticizer;
preferably, the plasticizer is contained in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the hydroxyl group-containing polysiloxane;
preferably, the reinforcing agent is selected from any one or a combination of at least two of MQ silicon resin, dimethyl silicone oil, phthalate, fatty acid dibasic acid ester or citrate;
preferably, the raw materials for preparing the silicone rubber composition also comprise a solid filler;
preferably, the content of the solid filler is 5 to 150 parts by weight based on 100 parts by weight of the content of the hydroxyl group-containing polysiloxane;
preferably, the solid filler is selected from any one or a combination of at least two of white carbon black, titanium dioxide, aluminum hydroxide, carbon black, zinc stearate, talcum powder, calcium carbonate, barium sulfate, montmorillonite, diatomite, kaolin, gypsum, mica or magnesium hydroxide;
preferably, the raw materials for preparing the silicone rubber composition also comprise an auxiliary agent;
preferably, the auxiliary agent is selected from any one of water, a release agent, a cyclohexylynol, a polyether, polyether silicone oil, polyethylene glycol, sorbitol fatty acid ester, a fluorocarbon surfactant, divinyl tetramethyl disiloxane or tetravinyl tetramethyl tetrasiloxane ring body or a combination of at least two of the above.
8. A method for producing the silicone rubber composition according to any one of claims 1 to 7, characterized by comprising the steps of:
adding polysiloxane containing hydroxyl, reactive phosphorus-containing flame retardant, reinforcing filler and a structural control agent into a reaction device for reaction; and then adding a cross-linking agent and a catalyst, mixing, and vulcanizing in a mold to obtain the silicone rubber composition.
9. The preparation method according to claim 8, wherein the reaction temperature is 95-130 ℃, preferably 120 ℃;
preferably, the reaction is carried out under stirring conditions;
preferably, the reaction time is 0.5-5 h;
preferably, the mixing is performed under stirring conditions;
preferably, the temperature of the mixing is room temperature;
preferably, the mixing time is 0.1-2 h;
preferably, the reaction device is selected from any one of an open mill, an internal mixer or a kneader;
preferably, the vulcanizing time is 12-36 h;
preferably, the temperature of the vulcanization is room temperature.
10. Use of a silicone rubber composition according to any one of claims 1 to 7 in seals, gaskets, electronic packaging and potting materials.
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