CN109705581B - Silicone rubber composition, silicone rubber and preparation method thereof - Google Patents
Silicone rubber composition, silicone rubber and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a silicone rubber composition, a silicone rubber and a preparation method thereof. The silicone rubber composition comprises raw rubber, a cross-linking agent, a noble metal catalyst and an inhibitor, wherein the inhibitor comprises at least one of long-chain branched fumarate with a structural formula shown in a formula (1), cyclic fumarate with a structural formula shown in a formula (2), polyfumarate with a structural formula shown in a formula (3), long-chain branched maleate with a structural formula shown in a formula (4), cyclic maleate with a structural formula shown in a formula (5) and polymaleate with a structural formula shown in a formula (6);
wherein R is1And R2Both are one of aliphatic alkyl and aryl with more than C8; r3、R4All are one of fatty alkyl groups of more than C2. The silicon rubber composition disclosed by the invention has good storage stability at room temperature, is sensitive to temperature, and can be better applied to the fields of packaging of electronic devices with temperature sensitivity and the like.
Description
Technical Field
The invention relates to the technical field of silicone rubber, in particular to an inhibitor, a preparation method and related application thereof.
Background
Existing silicone rubber compositions (also known as liquid silicone rubbers) include raw rubber, a noble metal catalyst, and a crosslinking agent. The raw rubber is generally subjected to a hydrosilylation reaction under the action of a noble metal catalyst such as platinum, rhodium, palladium and the like to prepare the silicone rubber. However, the noble metal catalyst has strong activity and can catalyze the crude rubber to obtain a silicone rubber finished product at room temperature. This is disadvantageous for storage and use of the silicone rubber composition. Therefore, it is necessary to add an inhibitor to the silicone rubber composition, which acts as: the inhibitor plays a role in inhibiting at room temperature and reduces the activity of the noble metal catalyst; under the conditions of heating or illumination and the like, the inhibition effect is removed, the activity of the noble metal catalyst is recovered again, and the silicon rubber composition is rapidly catalyzed to be crosslinked and cured into silicon rubber.
At present, the inhibitor commonly used in industry is often added in a relatively large amount to achieve a relatively good inhibition effect, which results in increased curing time and poor controllability of the silicone rubber composition. Moreover, some device packages that are sensitive to temperature use, such as those requiring curing temperatures below 100 c, even below 80 c, can be operated for longer periods of time.
Disclosure of Invention
In view of the above, it is necessary to provide a silicone rubber composition, a silicone rubber and a preparation method thereof, aiming at the problems of storage stability and process applicability of the silicone rubber composition.
A silicone rubber composition comprising a raw rubber, a crosslinking agent, a noble metal catalyst, and an inhibitor;
the inhibitor comprises at least one of long-chain branched fumarate with a structural formula shown as a formula (1), cyclic fumarate with a structural formula shown as a formula (2), polyfumarate with a structural formula shown as a formula (3), long-chain branched maleate with a structural formula shown as a formula (4), cyclic maleate with a structural formula shown as a formula (5) and polymaleate with a structural formula shown as a formula (6);
wherein R is1And R2Both are one of aliphatic alkyl and aryl with more than C8; r3And R4All are one of fatty alkyl groups of more than C2.
In one embodiment, the long chain branched fumaric acid ester comprises at least one of di-n-octyl fumarate, diisooctyl fumarate, dinonyl fumarate, di-n-decyl fumarate, didodecyl fumarate, ditetradecyl fumarate, dihexadecyl fumarate, dioctadecyl fumarate, didodecyl fumarate, di-dimethylbenzyl fumarate, or dibiphenyl fumarate.
In one embodiment, the cyclic fumarate comprises at least one of ethylene glycol cyclic fumarate, propylene glycol cyclic fumarate, butylene glycol cyclic fumarate, hexylene glycol cyclic fumarate, octylene glycol cyclic fumarate, decylene glycol cyclic fumarate, dodecylene glycol cyclic fumarate, tetradecylene glycol cyclic fumarate, hexadecylene glycol cyclic fumarate, octadecylene glycol cyclic fumarate, eicosylene glycol cyclic fumarate, docosyl glycol cyclic fumarate.
In one embodiment, the polyfumarate includes at least one of polyethylene glycol fumarate, polypropylene glycol fumarate, polybutylene fumarate, polyhexamethylene fumarate, polyoctylene glycol fumarate, polydecamethylene fumarate, polydodecyl glycol fumarate, polytetradecyl glycol fumarate, polyhexamethylene fumarate, polyooctadecyl glycol fumarate, polyeicosyl glycol fumarate, and polydocosyl glycol fumarate.
In one embodiment, the long chain branched maleate comprises at least one of di-n-octyl maleate, diisooctyl maleate, dinonyl maleate, di-n-decyl maleate, didodecyl maleate, ditetradecyl maleate, dihexadecyl maleate, dioctadecyl maleate, dieicosyl maleate, di (dimethylphenyl) maleate, and di-biphenyl maleate.
In one embodiment, the cyclic maleate includes at least one of ethylene glycol cyclic maleate, propylene glycol cyclic maleate, butylene glycol cyclic maleate, hexylene glycol cyclic maleate, octylene glycol cyclic maleate, decylene glycol cyclic maleate, dodecylene glycol cyclic maleate, tetradecylene glycol cyclic maleate, hexadecylene glycol cyclic maleate, octadecylene glycol cyclic maleate, eicosylene glycol cyclic maleate, docosyl glycol cyclic maleate.
In one embodiment, the polymaleic acid ester comprises at least one of polyethylene glycol maleate, polypropylene glycol maleate, polybutylene maleate, hexamethylene polymaleate, octanediol polymaleate, decamethylene polymaleate, dodecyl polymaleate, tetradecyl polymaleate, hexadecyl polymaleate, octadecyl polymaleate, eicosyl polymaleate, docosyl polymaleate.
In one embodiment, the mass of the cross-linking agent is 5-30% of the mass of the raw rubber.
In one embodiment, the noble metal catalyst is used in an amount of 1ppm to 200ppm in terms of noble metal in the silicone rubber composition, and the inhibitor is 5 times to 100 times the mass of the noble metal.
In one embodiment, the raw rubber comprises vinyl-containing polysiloxane, the cross-linking agent comprises organohydrogenpolysiloxane, and the molar ratio of silicon hydrogen bonds in the organohydrogenpolysiloxane to vinyl groups in the vinyl-containing polysiloxane is (1-2): 1.
In one embodiment, the vinyl-containing polysiloxane has a viscosity of 0.1 pas to 1000 pas at 25 ℃; and/or
The viscosity of the organohydrogenpolysiloxane at 25 ℃ is 0.5 mPas to 10000 mPas.
A preparation method of silicone rubber comprises the following steps:
providing a silicone rubber composition as described above;
and heating the silicon rubber composition, and carrying out curing reaction on the raw rubber and a cross-linking agent under the catalysis of the noble metal catalyst to obtain the silicon rubber.
In one embodiment, the temperature of the heating is 50 ℃ or higher.
The silicone rubber is obtained by the preparation method, and has a net structure.
In the silicone rubber composition, double bonds on the maleate or fumarate groups in the inhibitor can coordinate with the empty orbitals of the noble metal catalyst, so that the noble metal catalyst is temporarily poisoned, and the activity of the noble metal catalyst is reduced. Meanwhile, the inhibitor has a long chain group which can play a space shielding role on the noble metal catalyst, so that the using amount of the inhibitor can be reduced, the activity of the noble metal catalyst at room temperature can be further reduced, the catalytic action of the noble metal catalyst can be inhibited, and the room-temperature storage stability of the silicone rubber composition can be ensured. When the temperature is raised, the inhibitor is easy to separate from the noble metal catalyst due to large steric hindrance and loses coordination capacity, so that the noble metal catalyst can quickly recover the activity, and the silicon rubber composition can be quickly catalyzed to be solidified into silicon rubber, thereby ensuring the process applicability of the silicon rubber composition, and enabling the silicon rubber composition to be better applied to the fields of encapsulation of electronic devices with temperature sensitivity and the like. Meanwhile, the inhibitor in the silicone rubber composition has a high boiling point and is not easy to decompose.
The silicon rubber has the performances of heat resistance, cold resistance, dielectricity, ozone resistance, atmospheric aging resistance and the like, can be used for a long time at the temperature of minus 60-250 ℃, and can be widely applied to the fields of electronic packaging, medical appliances, consumer goods and the like.
Detailed Description
The silicone rubber composition, the silicone rubber and the preparation method thereof provided by the invention will be further explained below.
The silicone rubber composition provided by the invention comprises raw rubber, a cross-linking agent, a noble metal catalyst and an inhibitor, wherein the inhibitor comprises at least one of long-chain branched fumarate with a structural formula shown as a formula (1), cyclic fumarate with a structural formula shown as a formula (2), polyfumarate with a structural formula shown as a formula (3), long-chain branched maleate with a structural formula shown as a formula (4), cyclic maleate with a structural formula shown as a formula (5) and polymaleate with a structural formula shown as a formula (6);
wherein R is1And R2Both are one of aliphatic alkyl and aryl with more than C8; r3And R4All are one of fatty alkyl groups of more than C2.
Preferably, the R is selected in consideration of the source of raw materials and the ease of synthesis1And R2All are one of C8-C22 fatty alkyl and aryl, and R is3And R4All are one of C2-C22 fatty alkyl.
Further, said R1And R2The same is true.
Specifically, the long-chain branched fumaric acid ester comprises at least one of di-n-octyl fumarate, diisooctyl fumarate, dinonyl fumarate, di-n-decyl fumarate, didodecyl fumarate, ditetradecyl fumarate, dihexadecyl fumarate, dioctadecyl fumarate, didodecyl fumarate, di (dimethylphenyl) fumarate and dibiphenyl fumarate.
Specifically, the cyclic fumarate includes at least one of ethylene glycol cyclic fumarate, propylene glycol cyclic fumarate, butylene glycol cyclic fumarate, hexylene glycol cyclic fumarate, octylene glycol cyclic fumarate, decylene glycol cyclic fumarate, dodecylene glycol cyclic fumarate, tetradecylene glycol cyclic fumarate, hexadecylene glycol cyclic fumarate, octadecylene glycol cyclic fumarate, eicosylene glycol cyclic fumarate, and docosyl glycol cyclic fumarate.
Specifically, the polyfumarate comprises at least one of polyethylene glycol fumarate, polypropylene glycol fumarate, polybutylene fumarate, polyhexamethylene glycol fumarate, polyoctylene glycol fumarate, polydecamethylene glycol fumarate, and polydecamethylene glycol fumarate.
Specifically, the long chain branched maleate comprises at least one of di-n-octyl maleate, diisooctyl maleate, dinonyl maleate, di-n-decyl maleate, didodecyl maleate, ditetradecyl maleate, dihexadecyl maleate, dioctadecyl maleate, didicosyl maleate, di (dimethylphenyl) maleate, and dibenzyl maleate.
Specifically, the cyclic maleate includes at least one of ethylene glycol cyclic maleate, propylene glycol cyclic maleate, butylene glycol cyclic maleate, hexylene glycol cyclic maleate, octylene glycol cyclic maleate, decylene glycol cyclic maleate, dodecylene glycol cyclic maleate, tetradecylene glycol cyclic maleate, hexadecylene glycol cyclic maleate, octadecylene glycol cyclic maleate, eicosylene glycol cyclic maleate and docosyl glycol cyclic maleate.
Specifically, the polymaleic acid ester comprises at least one of polyethylene glycol maleate, polypropylene glycol maleate, polybutylene glycol maleate, hexanediol polymaleate, octanediol polymaleate, decanediol polymaleate, dodecyl glycol polymaleate, tetradecyl glycol polymaleate, hexadecyl glycol polymaleate, octadecyl glycol polymaleate, eicosyl glycol polymaleate and docosyl glycol polymaleate.
Therefore, in the inhibitor of the present invention, the double bond on the maleate or fumarate group can coordinate with the vacant orbital of the noble metal catalyst. After coordination, the activity of the noble metal catalyst is reduced.
Taking a platinum metal catalyst and a long-chain branched maleate inhibitor with a structural formula shown as formula (4) as an example, the formula for forming coordination is as follows:
meanwhile, the inhibitor contains long chain groups, can play a space shielding role on the noble metal catalyst, can reduce the using amount of the inhibitor, and can further reduce the activity of the noble metal catalyst at room temperature so as to inhibit the catalytic action of the noble metal catalyst.
When the temperature is raised, the inhibitor is easy to separate from the noble metal catalyst due to large steric hindrance, namely, reverse reaction occurs, the inhibitor loses coordination capacity, and the empty orbit of the noble metal catalyst is released again, so that the coordination catalysis effect of the inhibitor is recovered.
Therefore, in the silicone rubber composition, the inhibitor can control the catalytic performance of the noble metal catalyst, so that the room-temperature storage stability and the process applicability of the silicone rubber composition are ensured, and the silicone rubber composition can be better applied to the fields of packaging of electronic devices with temperature sensitivity and the like.
Meanwhile, the inhibitor in the silicone rubber composition has high boiling point, is not easy to decompose, has good compatibility with silicone rubber, and cannot migrate out of the silicone rubber to pollute products.
Specifically, the mass of the cross-linking agent is 5-30% of the mass of the raw rubber.
Wherein the crude rubber comprises vinyl-containing polysiloxane, the vinyl-containing polysiloxane is polydiorganosiloxane containing two or more vinyl groups, and the structural formula of the raw rubber is as follows:
Y3-a-dPhd(CH3)aSiO[(CH3)2SiO]e[(CH3)RSiO]fSi(CH3)aPhdY3-a-d；
wherein Y is CH3-、CH2One of CH-is selected; r is CH2CH-、Ph-、CF3CH2CH2-one of the above; a is more than or equal to 0 and less than or equal to 3; d is 0 or 1; e is greater than 0; f is more than or equal to 0; and a, e and f are integers.
The molecular weight of the vinyl-containing polysiloxane is not particularly limited, and the vinyl-containing polysiloxane may be any viscous substance having a low viscosity or a high viscosity and not having self-fluidity at room temperature.
Considering that when the viscosity is too low, the obtained silicone rubber has poor performance, and when the viscosity is too high, the processing and forming of the silicone rubber are not facilitated. Therefore, for the vinyl-containing polysiloxane having self-fluidity at room temperature, it is preferable that the viscosity of the vinyl-containing polysiloxane at 25 ℃ is 0.1 pas to 1000 pas.
The cross-linking agent comprises organohydrogenpolysiloxane, the organohydrogenpolysiloxane is organohydrogenpolysiloxane containing three or more than three silicon-hydrogen bonds (Si-H), and the structure of the organohydrogenpolysiloxane is as follows:
Ht(CH3)3-tSiO[(CH3)2SiO]b[(CH3)HSiO]cSi(CH3)3-tHt；
wherein t is more than or equal to 0 and less than or equal to 3, b is more than or equal to 0, and c is more than or equal to 2; and t, b and c are integers.
Preferably, the organohydrogenpolysiloxane has a viscosity of 0.5 to 10000 mPas at 25 ℃.
Considering that if the crosslinking is insufficient, the elastic properties of the silicone rubber are reduced; on the other hand, if the crosslinking is excessive, the mechanical strength after curing is deteriorated and the heat resistance and compression set are deteriorated. Preferably, the molar ratio of the silicon-hydrogen bond in the organohydrogenpolysiloxane to the vinyl group in the vinyl-containing polysiloxane is (1-2): 1.
Specifically, the noble metal catalyst includes at least one of a platinum-based catalyst, a palladium-based catalyst, a rhodium-based catalyst, a ruthenium-based catalyst, a zirconium-based catalyst, a cobalt-based catalyst, and a nickel-based catalyst.
Considering that when the amount of the noble metal catalyst is too small, the catalytic efficiency is too low and the reaction speed is slow, and when the amount is too large, the cost is high. Preferably, the noble metal catalyst is used in an amount such that the concentration of the noble metal in the silicone rubber composition is 1ppm to 200ppm, based on the noble metal. And the mass of the inhibitor is 5 to 100 times the mass of the noble metal in consideration of the inhibiting effect of the inhibitor.
It is understood that the inhibitor, long chain branched fumarate, long chain branched maleate, cyclic fumarate, cyclic maleate, polyfumarate, polymaleate may be used in combination.
Meanwhile, in view of catalytic efficiency of the noble metal catalyst, the noble metal catalyst is preferably a platinum-based catalyst such as platinum black, platinum chloride, a reactant of chloroplatinic acid and a monohydric alcohol, a complex of olefins, platinum bisacetoacetate, or the like. Further, the platinum group catalyst is preferably chloroplatinic acid or Karstedt's catalyst (kastedt catalyst). Wherein the Karstedt catalyst is a platinum (0) complex of divinyltetramethyldisiloxane.
Preferably, the silicone rubber composition further comprises a reinforcing agent, and the mechanical property of the silicone rubber can be improved through the reinforcing agent.
Furthermore, the reinforcing agent is used in an amount of 10 to 40 parts by weight based on the weight of the raw rubber.
Further, the reinforcing agent is silicon dioxide. The silica has a BET specific surface area of 50m or more2A/g, preferably of 100m2/g～400m2(ii) in terms of/g. The silica is fumed silica or precipitated silica.
Further, the silica is treated with a surface treatment agent. The surface treatment agent comprises at least one of organopolysiloxane, silazane, chlorosilane and alkoxysilane.
Preferably, the silicone rubber composition further comprises at least one of a filler and an additive.
Further, the filler comprises white carbon black.
Further, the additive comprises at least one of pigment, heat-resistant additive, adhesion promoter, release agent and conductive agent.
Further, the pigment comprises TiO2、Fe2O3And carbon black. The heat-resistant additive comprises at least one of metal oxide and hydroxide. The adhesion promoter comprises at least one of a carbon-functional silane and a siloxane.
The invention also provides a preparation method of the silicone rubber, which comprises the following steps:
(1) providing the above silicone rubber composition;
(2) and heating the silicon rubber composition, and carrying out curing reaction on the raw rubber and a cross-linking agent under the catalysis of the noble metal catalyst to obtain the silicon rubber.
Specifically, the heating temperature in the step (2) is not less than 50 ℃, preferably, the heating temperature is 50 ℃ to 150 ℃, and more preferably, 60 ℃ to 150 ℃.
The invention also provides silicon rubber which is obtained by the preparation method and has a net-shaped structure.
The silicon rubber has the performances of heat resistance, cold resistance, dielectricity, ozone resistance, atmospheric aging resistance and the like, can be used for a long time at the temperature of minus 60 ℃ to 250 ℃, and can be widely applied to the fields of electronic packaging, medical appliances, consumer goods and the like.
Hereinafter, the silicone rubber composition, the silicone rubber, and the preparation method thereof will be further described by the following specific examples.
Example 1:
preparation of Long chain branched fumaric acid esters (di-n-octyl fumarate is taken as an example).
Dissolving 260g of n-octanol in 1000g of cyclohexane, adding 110g of sodium carbonate, stirring, placing in a 2L three-neck glass flask, slowly dropwise adding 160g of fumaric chloride, slowly heating to 50 ℃ after 30 minutes of dropwise addition, and stirring overnight. The precipitate was removed by filtration. The filtrate was washed three times with 200mL and 5% aqueous sodium carbonate solution, three times with 200mL water, three times with 200mL saturated NaCl solution, dried with anhydrous magnesium sulfate, filtered, and the solvent was distilled off to obtain a crude product. Distillation under reduced pressure gave 310g of di-n-octyl fumarate, a yield of 90%.
By this method, the corresponding long-chain branched fumaric diester can be obtained by reacting fumaric chloride with different alcohols.
The fatty alcohol with the carbon number more than 12 is reacted with the fumaryl chloride to obtain the long-chain branched-chain difatty fumarate, and the obtained long-chain branched-chain difatty fumarate can be purified in a recrystallization mode.
Example 2:
preparation of cyclic fumarate (taking the cyclic dodecyl fumarate as an example).
20g of dodecyl glycol was dissolved in 500mL of cyclohexane, 15.3g of fumaric chloride was dissolved in 500mL of cyclohexane, and placed in two 1000mL round-bottom flasks, respectively, and 12g of anhydrous sodium carbonate and 500mL of cyclohexane were placed in a 2L three-necked flask. Simultaneously, the dodecyl glycol and the fumaric chloride cyclohexane solution are dripped into a 2L round-bottom flask, the dripping speed is controlled to be about 1mL/min, and the dripping is finished within 8 hours. Stirring was continued overnight. The precipitate was removed by filtration. The filtrate was washed three times with 200mL and 5% aqueous sodium carbonate solution, three times with 200mL water, three times with 200mL saturated NaCl solution, dried with anhydrous magnesium sulfate, filtered, and the solvent was distilled off to obtain a crude product. Vacuum distillation was carried out to obtain 22g of cyclododecanediol fumarate, which was a product, in a yield of 79%.
By this method, the corresponding cyclic fumarate can be obtained by reacting fumaric chloride with different diols.
Example 3:
preparation of Polyfumarate (as exemplified by polyethylene fumarate).
15.3g of fumaric chloride was dissolved in 50mL of ethyl acetate, and 6.2g of ethylene glycol and 11g of sodium carbonate were added thereto, followed by stirring at 60 ℃ overnight. The precipitate was removed by filtration. And washing the filtrate with 50mL and 5% sodium carbonate aqueous solution for three times, 50mL water for three times, 50mL saturated NaCl solution for three times, adding anhydrous magnesium sulfate for drying, filtering, adding the filtrate into methanol for precipitation, filtering and drying to obtain the polyethylene glycol fumarate polymer. The number average molecular weight was 11500g/moL as determined by gel permeation chromatography.
By the method, different diols are used for carrying out polymerization reaction with fumaroyl chloride, and the corresponding polyfumarate ester can be obtained.
Example 4:
preparation of a long chain branched maleate (as exemplified by tetradecanol maleate).
210g of tetradecanol is dissolved in 1000g of cyclohexane, 110g of sodium carbonate is added and stirred, the mixture is placed in a 2L three-neck glass flask, 160g of maleic chloride is slowly dripped, after 30 minutes of dripping, the temperature is slowly raised to 50 ℃, and the mixture is stirred overnight. The precipitate was removed by filtration. The filtrate was washed three times with 200mL and 5% aqueous sodium carbonate solution, three times with 200mL water, three times with 200mL saturated NaCl solution, dried with anhydrous magnesium sulfate, filtered, and the solvent was distilled off to obtain a crude product. Recrystallization from cyclohexane gave 252g of tetradecanol maleate, 85% yield.
By this method, the corresponding maleic acid ester with long chain branch can be obtained by reacting different alcohols with maleic acid chloride.
Example 5:
preparation of cyclic maleate (taking cyclic maleate tetradecyl glycol ester as an example).
21g of tetradecylene glycol and 15.3g of maleic chloride were dissolved in 500mL of cyclohexane and placed in two 1000mL round-bottom flasks, respectively, and 12g of anhydrous sodium carbonate and 500mL of cyclohexane were placed in a 2L three-necked flask. Meanwhile, tetradecyl diol and fumaric chloride cyclohexane solution are dripped into a 2L round-bottom flask, the dripping speed is controlled to be about 1mL/min, and dripping is finished within 8 hours. Stirring was continued overnight. The precipitate was removed by filtration. The filtrate was washed three times with 200mL and 5% aqueous sodium carbonate solution, three times with 200mL water, three times with 200mL saturated NaCl solution, dried with anhydrous magnesium sulfate, filtered, and the solvent was distilled off to obtain a crude product. Reduced pressure distillation was carried out to obtain 23g of tetradecyl diol maleate, a product, in 80% yield.
By this method, the corresponding cyclic maleate can be obtained by reacting different diols with maleyl chloride.
Example 6:
polymaleate preparation (as exemplified by polyhexamethylene maleate).
10g of maleic anhydride, 11.8g of hexanediol and a small amount of p-toluenesulfonic acid catalyst are added into a round-bottom flask, the mixture reacts for 2 hours at 100 ℃, the temperature is gradually increased to 210 ℃, and the mixture is stirred overnight under vacuum to obtain the poly (hexanediol maleate) polymer. The number average molecular weight was 9800g/moL as determined by gel permeation chromatography.
By the method, different diols are used for polymerization reaction with maleic anhydride, and the corresponding polymaleic acid ester can be obtained.
Example 7:
di-n-octyl fumarate synthesized in example 1 was used as the inhibitor of this example.
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 335 pas at 25 ℃, 10 parts by weight of an organohydrogenpolysiloxane having a viscosity of 50 mPas at 25 ℃, 1 part of a Kansted platinum catalyst having a platinum content of 1000ppm, and 0.01 part of di-n-octyl fumarate were mixed under vacuum to obtain a silicone rubber composition. Wherein, the molar ratio of the silicon-hydrogen bond in the organic hydrogen polysiloxane to the vinyl group in the vinyl-containing polysiloxane is 1:1, and the content of the metal platinum in the silicone rubber composition is 9 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
Example 8:
diphenyl fumarate was synthesized in the manner of example 1 and was used as the inhibitor in this example.
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 740 pas at 25 ℃, 20 parts by weight of an organohydrogenpolysiloxane having a viscosity of 0.5 mPas at 25 ℃, 0.12 part of a Kansted platinum catalyst having a platinum content of 1000ppm, and 0.001 part of diphenyl fumarate were mixed under vacuum to obtain a silicone rubber composition. Wherein the molar ratio of the silicon-hydrogen bond in the organohydrogenpolysiloxane to the vinyl group in the vinyl-containing polysiloxane is 1.2:1, and the content of the metal platinum in the silicone rubber composition is 1 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
Example 9:
the cyclic dodecyl glycol fumarate synthesized in example 2 was used as an inhibitor.
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 60 pas at 25 ℃, 12 parts by weight of an organohydrogenpolysiloxane having a viscosity of 50 mPas at 25 ℃, 2 parts by weight of a Kansted platinum catalyst having a platinum content of 1000ppm, and 0.2 part by weight of dodecyl glycol cyclic fumarate were mixed under vacuum to obtain a silicone rubber composition. Wherein the molar ratio of the silicon-hydrogen bond in the organohydrogenpolysiloxane to the vinyl group in the vinyl-containing polysiloxane is 1.3:1, and the content of the metal platinum in the silicone rubber composition is 8 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
Example 10:
cyclic hexadecyl diol fumarate was synthesized in the same manner as in example 2 and used as an inhibitor in this example.
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 980 pas at 25 ℃, 30 parts by weight of an organohydrogenpolysiloxane having a viscosity of 10000 mPas at 25 ℃, 2.4 parts by weight of a Kansted platinum catalyst having a platinum content of 5000ppm, and 0.06 part by weight of a hexadecyldiol cyclic fumarate were mixed under vacuum to obtain a silicone rubber composition. Wherein, the molar ratio of the silicon-hydrogen bond in the organic hydrogen polysiloxane to the vinyl group in the vinyl-containing polysiloxane is 2:1, and the content of the metal platinum in the silicone rubber composition is 100 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
Example 11:
the polyethylene glycol fumarate synthesized in example 3 was used as the inhibitor of this example.
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 1000 pas at 25 ℃, 10 parts by weight of an organohydrogenpolysiloxane having a viscosity of 480 mPas at 25 ℃, 1.1 part by weight of a platinum-5000 ppm Karster platinum catalyst, and 0.5 part by weight of polyethylene glycol fumarate were mixed under vacuum to obtain a silicone rubber composition. Wherein the molar ratio of the silicon-hydrogen bond in the organohydrogenpolysiloxane to the vinyl group in the vinyl-containing polysiloxane is 1.2:1, and the content of the metal platinum in the silicone rubber composition is 50 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
Example 12:
polydodecyl glycol fumarate was synthesized in the same manner as in example 3 and used as an inhibitor in this example.
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 1000 pas at 25 ℃, 10 parts by weight of an organohydrogenpolysiloxane having a viscosity of 480 mPas at 25 ℃, 1.1 part by weight of a platinum-5000 ppm Karster platinum catalyst, and 0.5 part by weight of polydodecyldiol fumarate were mixed under vacuum to obtain a silicone rubber composition. Wherein the molar ratio of the silicon-hydrogen bond in the organohydrogenpolysiloxane to the vinyl group in the vinyl-containing polysiloxane is 1.2:1, and the content of the metal platinum in the silicone rubber composition is 50 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
Example 13:
tetradecyl maleate synthesized in example 4 was used as the inhibitor in this example.
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 100 pas at 25 ℃, 10 parts by weight of an organohydrogenpolysiloxane having a viscosity of 600 mPas at 25 ℃, 1.1 part by weight of a platinum-containing 1000ppm Kansted platinum catalyst, and 0.011 part by weight of tetradecyl maleate were mixed under vacuum to obtain a silicone rubber composition. Wherein the molar ratio of the silicon-hydrogen bond in the organohydrogenpolysiloxane to the vinyl group in the vinyl-containing polysiloxane is 1.3:1, and the content of the metal platinum in the silicone rubber composition is 10 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
Example 14:
behenyl maleate was synthesized in the manner of example 4 and used as the inhibitor in this example.
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 320 Pa.s at 25 ℃, 10 parts by weight of an organohydrogenpolysiloxane having a viscosity of 480 mPa.s at 25 ℃, 0.11 part of a platinum-containing platinum catalyst having a platinum content of 1000ppm, and 0.01 part of behenyl maleate were mixed under vacuum to obtain a silicone rubber composition. Wherein the molar ratio of the silicon-hydrogen bond in the organohydrogenpolysiloxane to the vinyl group in the vinyl-containing polysiloxane is 1.3:1, and the content of the metal platinum in the silicone rubber composition is 1 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
Example 15:
the cyclic tetradecanediol maleate synthesized in example 5 was used as the inhibitor in this example.
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 0.1 pas at 25 ℃, 10 parts by weight of an organohydrogenpolysiloxane having a viscosity of 100 mPas at 25 ℃, 2.1 parts of a Kanstedt platinum catalyst having a platinum content of 10000ppm, and 1 part of tetradecyl diol cyclic maleate were mixed under vacuum to obtain a silicone rubber composition. Wherein the molar ratio of the silicon-hydrogen bond in the organohydrogenpolysiloxane to the vinyl group in the vinyl-containing polysiloxane is 1.25:1, and the content of the metal platinum in the silicone rubber composition is 200 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
Example 16:
cyclic behenyl maleate diol ester was synthesized as in example 5 and used as the inhibitor in this example.
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 60 pas at 25 ℃, 10 parts by weight of an organohydrogenpolysiloxane having a viscosity of 50 mPas at 25 ℃, 1 part by weight of a Kansted platinum catalyst having a platinum content of 5000ppm, 1 part by weight of a docosyl cyclic maleate, and 20 parts by weight of a catalyst having a BET specific surface area of 200m2The fumed silica per g was mixed under vacuum to give a silicone rubber composition. Wherein the molar ratio of silicon-hydrogen bonds in the organic hydrogen polysiloxane to vinyl groups in the vinyl-containing polysiloxane is 1.3:1, and the metal platinum is in the silicon rubber groupThe content of the compound was 40 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
Example 17:
the poly (hexanediol maleate) synthesized in example 6 was used as the inhibitor in this example.
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 60 pas at 25 ℃, 5 parts by weight of an organohydrogenpolysiloxane having a viscosity of 50 mPas at 25 ℃, 1 part by weight of a Karster platinum catalyst having a platinum content of 5000ppm, 1 part by weight of a poly (hexanediol maleate), and 20 parts by weight of a catalyst having a BET specific surface area of 200m2The fumed silica per g was mixed under vacuum to give a silicone rubber composition. Wherein the molar ratio of the silicon-hydrogen bond in the organohydrogenpolysiloxane to the vinyl group in the vinyl-containing polysiloxane is 1.3:1, and the content of the metal platinum in the silicone rubber composition is 40 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
Example 18:
polytetradecanediol maleate, synthesized by the method of example 6, was used as the inhibitor in this example.
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 60 pas at 25 ℃, 5 parts by weight of an organohydrogenpolysiloxane having a viscosity of 50 mPas at 25 ℃, 1 part by weight of a Kansted platinum catalyst having a platinum content of 5000ppm, 1 part by weight of a tetradecanediol polymaleate, and 20 parts by weight of a catalyst having a BET specific surface area of 200m2The fumed silica per g was mixed under vacuum to give a silicone rubber composition. Wherein the molar ratio of the silicon-hydrogen bond in the organohydrogenpolysiloxane to the vinyl group in the vinyl-containing polysiloxane is 1.3:1, and the content of the metal platinum in the silicone rubber composition is 40 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
Example 19:
behenyl maleate synthesized by the method of example 4 and tetradecyl glycol maleate synthesized in example 5 were mixed to prepare a mixture inhibitor of this example.
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 0.1 pas at 25 ℃, 10 parts by weight of an organohydrogenpolysiloxane having a viscosity of 100 mPas at 25 ℃, 2.1 parts by weight of a platinum catalyst having a platinum content of 5000ppm, 0.5 part by weight of a tetradecyl glycol cyclic maleate and 0.5 part by weight of a behenyl maleate were mixed under vacuum to obtain a silicone rubber composition. Wherein the molar ratio of the silicon-hydrogen bond in the organohydrogenpolysiloxane to the vinyl group in the vinyl-containing polysiloxane is 1.25:1, and the content of the metal platinum in the silicone rubber composition is 100 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
Comparative example 1
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 335 pas at 25 ℃, 10 parts by weight of an organohydrogenpolysiloxane having a viscosity of 50 mPas at 25 ℃, 1 part of a Kansted platinum catalyst having a platinum content of 1000ppm, and 0.01 part of diethyl maleate were mixed under vacuum to obtain a silicone rubber composition. Wherein, the molar ratio of the silicon-hydrogen bond in the organic hydrogen polysiloxane to the vinyl group in the vinyl-containing polysiloxane is 1:1, and the content of the metal platinum in the silicone rubber composition is 9 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
Comparative example 2
100 parts by weight of a vinyl-containing polysiloxane having a viscosity of 335 pas at 25 ℃, 10 parts by weight of an organohydrogenpolysiloxane having a viscosity of 50 mPas at 25 ℃, 1 part of a Kansted platinum catalyst having a platinum content of 1000ppm, and 0.01 part of diethyl fumarate were mixed under vacuum to obtain a silicone rubber composition. Wherein, the molar ratio of the silicon-hydrogen bond in the organic hydrogen polysiloxane to the vinyl group in the vinyl-containing polysiloxane is 1:1, and the content of the metal platinum in the silicone rubber composition is 9 ppm.
And heating and curing the silicone rubber composition to obtain the silicone rubber with a net structure. And tested for viscosity change, the results of which are shown in table 1.
TABLE 1
As can be seen from table 1, in the case where the amounts of the inhibitors added were the same, the curing time at room temperature was longer, but the curing time after increasing the temperature was shorter; and the addition of a high amount of inhibitor results in a prolonged curing time and an increase in the required curing temperature. Therefore, the inhibitor in the silicone rubber composition of the invention can effectively reduce the activity of the noble metal catalyst at room temperature and ensure the storage stability of the silicone rubber composition. The inhibitor is sensitive to temperature, and can restore the activity of the noble metal catalyst after being heated, quickly catalyze the silicon rubber composition to be cured into silicon rubber, has good process applicability, and can be applied to the packaging of electronic devices with temperature sensitivity.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (14)
1. A silicone rubber composition, characterized in that the silicone rubber composition comprises raw rubber, a crosslinking agent, a noble metal catalyst and an inhibitor;
the inhibitor comprises at least one of long-chain branched fumarate with a structural formula shown as a formula (1), cyclic fumarate with a structural formula shown as a formula (2), polyfumarate with a structural formula shown as a formula (3), long-chain branched maleate with a structural formula shown as a formula (4), cyclic maleate with a structural formula shown as a formula (5) and polymaleate with a structural formula shown as a formula (6);
wherein R is1And R2Both are one of aliphatic alkyl and aryl with more than C8; r3And R4All are one of fatty alkyl groups of more than C2.
2. The silicone rubber composition of claim 1, wherein the long chain branched fumaric acid ester comprises at least one of di-n-octyl fumarate, diisooctyl fumarate, dinonyl fumarate, di-n-decyl fumarate, didodecyl fumarate, ditetradecyl fumarate, dihexadecyl fumarate, dioctadecyl fumarate, didocosyl fumarate, di (dimethylphenyl) fumarate, and dibiphenyl fumarate.
3. The silicone rubber composition according to claim 1, wherein the cyclic fumarate comprises at least one of ethylene glycol cyclic fumarate, propylene glycol cyclic fumarate, butylene glycol cyclic fumarate, hexylene glycol cyclic fumarate, octylene glycol cyclic fumarate, decylene glycol cyclic fumarate, dodecylene glycol cyclic fumarate, tetradecylene glycol cyclic fumarate, hexadecylene glycol cyclic fumarate, octadecylene glycol cyclic fumarate, eicosylene glycol cyclic fumarate, and docosyl glycol cyclic fumarate.
4. The silicone rubber composition according to claim 1, wherein the polyfumarate comprises at least one of polyethylene glycol fumarate, polypropylene glycol fumarate, polybutylene fumarate, polyhexamethylene fumarate, polyoctylene glycol fumarate, polydecamethylene fumarate, polydodecyl glycol fumarate, polytetradecyl glycol fumarate, polyhexamethylene fumarate, polyooctadecyl glycol fumarate, polyeicosyl glycol fumarate, and polydocosyl glycol fumarate.
5. The silicone rubber composition of claim 1, wherein the long chain branched maleate ester comprises at least one of di-n-octyl maleate, diisooctyl maleate, dinonyl maleate, di-n-decyl maleate, didodecyl maleate, ditetradecyl maleate, dihexadecyl maleate, dioctadecyl maleate, dieicosyl maleate, di (dimethylphenyl) maleate, and di-biphenyl maleate.
6. The silicone rubber composition according to claim 1, wherein the cyclic maleate comprises at least one of ethylene glycol cyclic maleate, propylene glycol cyclic maleate, butylene glycol cyclic maleate, hexylene glycol cyclic maleate, octylene glycol cyclic maleate, decylene glycol cyclic maleate, dodecylene glycol cyclic maleate, tetradecylene glycol cyclic maleate, hexadecylene glycol cyclic maleate, octadecylene glycol cyclic maleate, eicosylene glycol cyclic maleate, docosyl glycol cyclic maleate.
7. The silicone rubber composition of claim 1, wherein the polymaleate comprises at least one of polyethylene glycol polymaleate, polypropylene glycol polymaleate, polybutylene glycol polymaleate, hexamethylene glycol polymaleate, octanediol polymaleate, decamethylene glycol polymaleate, dodecyl glycol polymaleate, tetradecyl glycol polymaleate, hexadecyl glycol polymaleate, octadecyl glycol polymaleate, eicosyl glycol polymaleate, docosyl glycol polymaleate.
8. The silicone rubber composition according to claim 1, wherein the mass of the crosslinking agent is 5% to 30% of the mass of the raw rubber.
9. The silicone rubber composition according to claim 8, wherein the noble metal catalyst is used in an amount such that the concentration of the noble metal in the silicone rubber composition is 1ppm to 200ppm in terms of noble metal, and the mass of the inhibitor is 5 times to 100 times the mass of the noble metal.
10. The silicone rubber composition according to claim 1, wherein the raw rubber comprises a vinyl-containing polysiloxane, the crosslinking agent comprises an organohydrogenpolysiloxane, and the molar ratio of silicon-hydrogen bonds in the organohydrogenpolysiloxane to vinyl groups in the vinyl-containing polysiloxane is (1-2): 1.
11. The silicone rubber composition according to claim 10, wherein the vinyl-containing polysiloxane has a viscosity of 0.1 Pa-s to 1000 Pa-s at 25 ℃; and/or
The viscosity of the organohydrogenpolysiloxane at 25 ℃ is 0.5 mPas to 10000 mPas.
12. The preparation method of the silicone rubber is characterized by comprising the following steps:
providing a silicone rubber composition according to any one of claims 1 to 11;
and heating the silicon rubber composition, and carrying out curing reaction on the raw rubber and a cross-linking agent under the catalysis of the noble metal catalyst to obtain the silicon rubber.
13. The method for preparing silicone rubber according to claim 12, wherein the heating temperature is not less than 50 ℃.
14. A silicone rubber obtained by the production method according to claim 12 or 13, wherein the silicone rubber has a network structure.
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