CN105400209A - Preparation method for high-temperature vulcanized silicone rubber enhanced by precipitation-process white carbon black for extrusion molding - Google Patents
Preparation method for high-temperature vulcanized silicone rubber enhanced by precipitation-process white carbon black for extrusion molding Download PDFInfo
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- CN105400209A CN105400209A CN201510949016.1A CN201510949016A CN105400209A CN 105400209 A CN105400209 A CN 105400209A CN 201510949016 A CN201510949016 A CN 201510949016A CN 105400209 A CN105400209 A CN 105400209A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions 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; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2312/00—Crosslinking
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Abstract
The invention discloses a preparation method for high-temperature vulcanized silicone rubber enhanced by precipitation-process white carbon black for extrusion molding. The preparation method comprises mixing polysiloxane containing at least two silicon-bonded vinyls, precipitation-process white carbon black and a plasticizer, so as to form high-temperature vulcanized silicone rubber, and then adding a vulcanizing agent, so as to obtain the high-temperature vulcanized silicone rubber product which is long in shelf life and does not foam even under a vulcanization condition in hot air.
Description
Technical field
The present invention relates to the preparation method of the high-temperature silicon disulfide rubber that a kind of extrusion moulding precipitated silica strengthens, belong to Material Field.
Background technology
High-temperature silicon disulfide rubber is the organopolysiloxane rubber with high molecular, is equipped with the various additives such as reinforced filling, constitution controller, vulcanizing agent, homogeneous phase sizing material mixing in mixing machinery.Because of its excellent high-low temperature resistant, weather-resistant, antifatigue, insulativity, highly air-permeable, some characteristic such as solvent and physiological inertia resistance to, be widely used in space flight, aviation, electronics, electrically, machinery, automobile, daily sealing, the national economy such as health care and people's lives every field, also play an important role in defence and military, hi-tech industry.
The white carbon black of the reinforced filling being adapted to high-temperature silicon disulfide rubber mainly high fineness, the particle diameter, specific surface area, chemical composition, surface chemical property etc. of reinforcing effect and white carbon black are closely related.According to method for making classification, white carbon black has vapor phase process and the precipitator method two kinds.Wherein precipitated silica is from water glass, under agitation adds hydrochloric acid and sulfuric acid neutralization reaction, obtains SiO
2precipitation, after filtration, dry, grinding forms.Precipitated silica, with its low price, obtains high-temperature silicon disulfide rubber good processability, and the goods rebound resilience after sulfuration, permanent compression set are excellent, are widely used in the silastic products such as button, rubber roll, oil resistant gasket.
But the water content of precipitated silica is high and be easy to water suction, when the high-temperature silicon disulfide rubber of conventional precipitated silica reinforcement is used for extrusion moulding, easily produces bubble, has a strong impact on the quality and performance of goods.This problem unresolved, JP-A-133356 proposes the method for thermal treatment silicon rubber under 200 DEG C or higher temperature, but this method needs specific step, and economy is poor, and easily causes the degraded of silicon rubber; In addition, also have patent to propose to use the precipitated silica of hydrophobic treatment, but this white carbon black is expensive, and the generation of bubble when can not suppress extrusion moulding completely, there is larger limitation; 50 hazes are real wait people by Selection radio surface-area (CTAB method)/specific surface area (BET method) for 1.0-1.3 and water-content lower than 4% precipitated silica as reinforced filling, be aided with Methyl-ethylenvinyl gum and appropriate solidifying agent, even if obtain the high-temperature silicon disulfide rubber that also can not foam in hot-air vulcanization.This preparation method reduces the range of choices of precipitated silica on the one hand, and on the other hand in order to remove the moisture contained in precipitated silica, preparation process needs high vacuum, high-temperature, economical lower.
Summary of the invention
The object of this invention is to provide the preparation method of the high-temperature silicon disulfide rubber that a kind of extrusion moulding precipitated silica strengthens, be there is by mixing the high-temperature silicon disulfide rubber of the organopolysiloxane of the vinyl of at least two silicon bondings, precipitated silica, softening agent, after adding vulcanizing agent, long quality-guarantee period can be obtained, even if the high-temperature silicon disulfide rubber goods that sulfuration also can not be foamed in warm air.
The preparation method of the high-temperature silicon disulfide rubber that a kind of extrusion moulding precipitated silica strengthens, concrete grammar is: after using kneader that organopolysiloxane, precipitated silica, polydimethylsiloxane, releasing agent are kneaded into homogeneous phase high-temperature silicon disulfide rubber sizing material, add solidifying agent and mix, to obtain final product.
Described mediate time temperature be room temperature to 100 DEG C, preferred room temperature to 80 DEG C, especially preferably 30 DEG C-60 DEG C.
The polymerization degree of described organopolysiloxane is more than or equal to 100, preferably from 1000 to 80000, especially preferred from 5000 to 20000.When the polymerization degree is too low, the high-temperature silicon disulfide rubber of gained does not have enough physical strengths; When the polymerization degree is too high, precipitated silica not easily mixes with organopolysiloxane.
Described organopolysiloxane at least has the vinyl of two silicon bondings, and an average group accepted way of doing sth is: R2
asiO
(4-a)/2
Wherein a is the positive number of 1.95-2.05.
Wherein R2 can be identical or different, and the monovalent hydrocarbon representing unsubstituted respectively or replace, this alkyl preferably has 1-12 carbon atom, more preferably there is 1-8 carbon atom, comprise alkyl, cycloalkyl, thiazolinyl, aryl, aralkyl, group part or all of hydrogen atom by halogen atom or cyano group etc. replace and formed group.
Wherein alkyl comprises ethyl, propyl group, butyl, base and octyl group; Cycloalkyl comprises cyclopentyl and cyclohexyl; Thiazolinyl comprises vinyl, allyl group, propenyl and cycloalkenyl group; Aryl comprises phenyl and tolyl; Aralkyl comprises benzyl and 2-styroyl; The group that the part or all of hydrogen atom of group is replaced by halogen atom or cyano group etc. and formed comprises trifluoro propyl.
Wherein R2 preferable methyl, vinyl, phenyl and trifluoro propyl, more preferably methyl and vinyl, the particularly preferably methyl of at least 80mol%, the especially preferably methyl of at least 90mol%.
Described organopolysiloxane comprises the organopolysiloxane be made up of dimethyl siloxane units, especially the diphenylsiloxane unit with phenyl, vinyl, trifluoro propyl is comprised, methyl vinyl siloxane unit, the organopolysiloxane of the dimethylsiloxane backbones of methyl-trifluoropropyl siloxane unit.
Each molecule of described organopolysiloxane has two or more vinyl, and preferred vinyl content is 0.01-20mol% organopolysiloxane, and particularly preferably contents of ethylene is the organopolysiloxane of 0.02-10mol%.
Its medium vinyl is one or more of chain end-vinyl and chain medium vinyl.
The specific surface area of described precipitated silica is greater than 50m
2/ g, preferred 100m
2/ g-400m
2/ g, more preferably 120m
2/ g-300m
2/ g.When the specific surface area of precipitated silica is less than 50m
2during/g, the high-temperature silicon disulfide rubber obtained there is no enough physical strengths; When specific surface area is higher than 400m
2during/g, precipitated silica not easily mixes with organopolysiloxane.
Relative to the organopolysiloxane of 100 weight parts, the content of precipitated silica is 3-120 weight part, preferred 10-90 weight part, more preferably 20-70 weight part.When the content of precipitated silica is less than 3 weight part, add-on is too little, the high-temperature silicon disulfide rubber obtained there is no enough physical strengths; When the content of precipitated silica is greater than 120 parts, precipitated silica not easily mixes with organopolysiloxane, and the high-temperature silicon disulfide rubber obtained is processed, mechanical property is poor.
In the present invention, because releasing agent can improve the processability in the processing characteristics of high-temperature silicon disulfide rubber and extruding-out process, preferably in high-temperature silicon disulfide rubber, add releasing agent.
One or more in the ester that described releasing agent is higher fatty acid, the metal-salt of higher fatty acid, higher fatty acid and alcohol synthesize.
Its Fatty Acids comprises stearic acid, palmitinic acid, oleic acid, lauric acid; The metal-salt of higher fatty acid comprises Zinic stearas, zinc oleate, calcium oleate; The ester that higher fatty acid and alcohol synthesize comprises Stearic ethyl stearate, Unister M 9676, ethyl oleate, butyl oleate.
Relative to the organopolysiloxane of 100 weight parts, the content of releasing agent is generally 0-3 weight part, preferred 0.01-2 weight part, particularly preferably 0.05-1 weight part.When the content of releasing agent is too large, the permanent compression set of high-temperature silicon disulfide rubber may be reduced, and affect the outward appearance of high-temperature silicon disulfide rubber after sulfuration.
The polydimethylsiloxane of described polydimethylsiloxane to be molecule chain end be hydroxyl or methoxy group, molecule chain end are hydroxyl or methoxy group and side base contains the polydimethylsiloxane of phenyl or vinyl, can be one or several mixture of above several polydimethylsiloxane.
Relative to the organopolysiloxane of 100 weight parts, the content of polydimethylsiloxane is generally 0-20 weight part, preferred 0.1-15 weight part, particularly preferably 0.5-10 weight part.When the content of polydimethylsiloxane is too large, roll banding and the sticking to mould of high-temperature silicon disulfide rubber masterbatch may be caused, thus reduce processing characteristics; When the content of polydimethylsiloxane is too little, high-temperature silicon disulfide rubber masterbatch is easy to structurizing, is unfavorable for its processing characteristics equally.
Described solidifying agent comprises benzoyl peroxide, 2,4-dichlorobenzoperoxide, peroxidation face toluyl, dicumyl peroxide, 2 to toluyl, peroxidation, 5-dimethyl-2, the superoxide such as 5-exane-tert-butyl peroxide, di-t-butyl peroxide, also comprise the platinum curing system be made up of platinum complex compound and containing hydrogen silicone oil mixture.When using the solidifying agent of peroxide, can be wherein a kind of, also can be above more than two or three snperoxiaized combination.
Relative to the high-temperature silicon disulfide rubber sizing material of 100 weight parts, the amount of the superoxide added is 0.1-15 weight part, preferred 0.3-10 weight part, especially preferably 0.5-6 weight part.When using platinum curing system, relative to the high-temperature silicon disulfide rubber sizing material of 100 weight parts, in platinum curing system, the addition of the mixture of platinum complex compound and polysiloxane is 0.1-15 weight part, preferred 0.2-10, especially preferably 0.4-5; In platinum curing system, the addition of the mixture of containing hydrogen silicone oil and white carbon black is 0.1-20 weight part, preferred 0.2-15, especially preferably 0.4-8.
Advantage of the present invention is provide a kind of method of high-temperature silicon disulfide rubber product preparing long quality-guarantee period, the bubble-free precipitated silica reinforcement of extrusion moulding.
Embodiment
Embodiment 1
Utilize kneader by the dimethyl siloxane units with 99.85mol% of 100 weight parts, 0.15mol% methyl vinyl siloxane unit, and mean polymerisation degree be 7000 organopolysiloxane and 50 parts of specific surface areas be 180m
2the precipitated silica YX-900A (being produced by Fujian Yuanxiang Chemical Co., Ltd.) of/g and 6 parts of each molecule chain ends contain silanol groups and the polydimethylsiloxane that viscosity is 25cSt (25 DEG C) is mixed into homogeneous phase high-temperature silicon disulfide rubber sizing material, control mixing temperature not higher than 60 DEG C.
To in 100 parts of high-temperature silicon disulfide rubber sizing materials obtained, add 1.25 part of 2,4-dichlorobenzoperoxide and mix.The uniform mixture obtained is solidified 8min at 115 DEG C, for the preparation of the thin slice of Performance Detection, then regelate 4h at 200 DEG C.Evaluate its physicals, the visible table 1 of result.The result of the bubble experiment of hot-air vulcanization also shows table 1.
Embodiment 2
Except using, there is the dimethyl siloxane units of 99.96mol%, 0.04mol% methyl vinyl siloxane unit, mean polymerisation degree are the organopolysiloxane of 7000 and have the dimethyl siloxane units of 99.78mol%, 0.22mol% methyl vinyl siloxane unit, mean polymerisation degree be except the mixture of the organopolysiloxane of 7000, according to the thin slice of mode identical in embodiment 1 for the preparation of Performance Detection, and evaluate its physicals, the visible table 1 of result.The result of the bubble experiment of hot-air vulcanization also shows table 1.
Embodiment 3
Produce except using Zhejiang Ying Luohua silicon materials company limited of precipitated silica ZH-909(Hengdian Group) except, according to the thin slice of mode identical in embodiment 1 for the preparation of Performance Detection, and evaluate its physicals, the visible table 1 of result.The result of the bubble experiment of hot-air vulcanization also shows table 1.
Embodiment 4
Produce except using precipitated silica 523(Wanzai County Hui Ming Chemical Co., Ltd.) except, according to the thin slice of mode identical in embodiment 1 for the preparation of Performance Detection, and evaluate its physicals, the visible table 1 of result.The result of the bubble experiment of hot-air vulcanization also shows table 1.
Embodiment 5
Be 180m except using 60 parts of specific surface areas
2the precipitated silica YX-900A (being produced by Fujian Yuanxiang Chemical Co., Ltd.) of/g and 7.5 parts of each molecule chain ends contain silanol groups and viscosity is outside the polydimethylsiloxane of 25cSt (25 DEG C), according to the thin slice of mode identical in embodiment 1 for the preparation of Performance Detection, and evaluate its physicals, the visible table 1 of result.The result of the bubble experiment of hot-air vulcanization also shows table 1.
Embodiment 6
Except adding the stearic acid of 3 weight parts as except releasing agent, according to the thin slice of mode identical in embodiment 1 for the preparation of Performance Detection, and evaluate its physicals, the visible table 1 of result.The result of the bubble experiment of hot-air vulcanization also shows table 1.
Embodiment 7
Except using the YX-900A at 105 DEG C after dry 2 hours and replacing the YX-900A of non-drying treatment, according to the thin slice of mode identical in embodiment 1 for the preparation of Performance Detection, and evaluate its physicals, the visible table 1 of result.The result of the bubble experiment of hot-air vulcanization also shows table 1.
Embodiment 8
Except not controlling to mediate temperature final product temperature reaches except 120 DEG C, according to the thin slice of mode identical in embodiment 1 for the preparation of Performance Detection, and evaluate its physicals, the visible table 1 of result.The result of the bubble experiment of hot-air vulcanization also shows table 1.
Embodiment 9
Except be 160 DEG C in temperature, vacuum tightness is carried out except thermal treatment under the condition of-0.09MPa, according to the thin slice of mode identical in embodiment 1 for the preparation of Performance Detection, and evaluates its physicals, the visible table 1 of result.The result of the bubble experiment of hot-air vulcanization also shows table 1.
Note: +++ represent almost without any bubble, ++ indicate a small amount of small bubbles ,+indicate a large amount of bubbles.
As can be seen from the data results of table 1, the high-temperature silicon disulfide rubber that embodiments of the invention 1-7 obtains has stronger tensile strength, elongation at break and tear strength, and bubble is less, and the high-temperature silicon disulfide rubber elongation at break that the embodiment 8 not controlling to mediate temperature and the embodiment 9 that do not control thermal treatment temp obtain and tear strength more weak, bubble is also more simultaneously, visible the present invention strictly controls to mediate temperature, is improved effect to the performance of obtained high-temperature silicon disulfide rubber.
Claims (10)
1. the preparation method of high-temperature silicon disulfide rubber that strengthens with precipitated silica of an extrusion moulding, it is characterized by: concrete grammar is: after using kneader that organopolysiloxane, precipitated silica, polydimethylsiloxane, releasing agent are kneaded into homogeneous phase high-temperature silicon disulfide rubber sizing material, add solidifying agent and mix, to obtain final product;
Temperature during kneading be room temperature to 100 DEG C, preferred room temperature to 80 DEG C, especially preferably 30 DEG C-60 DEG C;
The polymerization degree of organopolysiloxane is more than or equal to 100, preferably from 1000 to 80000, especially preferred from 5000 to 20000.
2. the preparation method of the high-temperature silicon disulfide rubber of a kind of extrusion moulding precipitated silica enhancing as claimed in claim 1, it is characterized by: described organopolysiloxane at least has the vinyl of two silicon bondings, an average group accepted way of doing sth is: R2
asiO
(4-a)/2;
Wherein a is the positive number of 1.95-2.05;
Wherein R2 can be identical or different, and the monovalent hydrocarbon representing unsubstituted respectively or replace, this alkyl preferably has 1-12 carbon atom, more preferably there is 1-8 carbon atom, comprise alkyl, cycloalkyl, thiazolinyl, aryl, aralkyl, group part or all of hydrogen atom by halogen atom or cyano group etc. replace and formed group;
Wherein alkyl comprises ethyl, propyl group, butyl, base and octyl group; Cycloalkyl comprises cyclopentyl and cyclohexyl; Thiazolinyl comprises vinyl, allyl group, propenyl and cycloalkenyl group; Aryl comprises phenyl and tolyl; Aralkyl comprises benzyl and 2-styroyl; The group that the part or all of hydrogen atom of group is replaced by halogen atom or cyano group etc. and formed comprises trifluoro propyl;
Wherein R2 preferable methyl, vinyl, phenyl and trifluoro propyl, more preferably methyl and vinyl, the particularly preferably methyl of at least 80mol%, the especially preferably methyl of at least 90mol%.
3. the preparation method of the high-temperature silicon disulfide rubber of a kind of extrusion moulding precipitated silica enhancing as claimed in claim 1, it is characterized by: described organopolysiloxane comprises the organopolysiloxane be made up of dimethyl siloxane units, especially the diphenylsiloxane unit with phenyl, vinyl, trifluoro propyl is comprised, methyl vinyl siloxane unit, the organopolysiloxane of the dimethylsiloxane backbones of methyl-trifluoropropyl siloxane unit;
Each molecule of described organopolysiloxane has two or more vinyl, and preferred vinyl content is 0.01-20mol% organopolysiloxane, and particularly preferably contents of ethylene is the organopolysiloxane of 0.02-10mol%;
Its medium vinyl is one or more of chain end-vinyl and chain medium vinyl.
4. the preparation method of the high-temperature silicon disulfide rubber of a kind of extrusion moulding precipitated silica enhancing as claimed in claim 1, is characterized by: the specific surface area of precipitated silica is greater than 50m
2/ g, preferred 100m
2/ g-400m
2/ g, more preferably 120m
2/ g-300m
2/ g.
5. the preparation method of the high-temperature silicon disulfide rubber of a kind of extrusion moulding precipitated silica enhancing as claimed in claim 4, it is characterized by: relative to the organopolysiloxane of 100 weight parts, the content of precipitated silica is 3-120 weight part, preferred 10-90 weight part, more preferably 20-70 weight part.
6. the preparation method of high-temperature silicon disulfide rubber that strengthens of a kind of extrusion moulding precipitated silica as claimed in claim 1, is characterized by: one or more in the ester that described releasing agent is higher fatty acid, the metal-salt of higher fatty acid, higher fatty acid and alcohol synthesize;
Its Fatty Acids comprises stearic acid, palmitinic acid, oleic acid, lauric acid; The metal-salt of higher fatty acid comprises Zinic stearas, zinc oleate, calcium oleate; The ester that higher fatty acid and alcohol synthesize comprises Stearic ethyl stearate, Unister M 9676, ethyl oleate, butyl oleate.
7. the preparation method of the high-temperature silicon disulfide rubber of a kind of extrusion moulding precipitated silica enhancing as claimed in claim 6, it is characterized by: relative to the organopolysiloxane of 100 weight parts, the content of releasing agent is generally 0-3 weight part, preferred 0.01-2 weight part, particularly preferably 0.05-1 weight part;
When the content of releasing agent is too large, the permanent compression set of high-temperature silicon disulfide rubber may be reduced, and affect the outward appearance of high-temperature silicon disulfide rubber after sulfuration.
8. the preparation method of the high-temperature silicon disulfide rubber of a kind of extrusion moulding precipitated silica enhancing as claimed in claim 1, it is characterized by: the polydimethylsiloxane of described polydimethylsiloxane to be molecule chain end be hydroxyl or methoxy group, molecule chain end are hydroxyl or methoxy group and side base contains the polydimethylsiloxane of phenyl or vinyl, can be one or several mixture of above several polydimethylsiloxane;
Relative to the organopolysiloxane of 100 weight parts, the content of polydimethylsiloxane is generally 0-20 weight part, preferred 0.1-15 weight part, particularly preferably 0.5-10 weight part.
9. the preparation method of the high-temperature silicon disulfide rubber of a kind of extrusion moulding precipitated silica enhancing as claimed in claim 1, it is characterized by: described solidifying agent comprises benzoyl peroxide, 2,4-dichlorobenzoperoxide, peroxidation face toluyl, dicumyl peroxide, 2 to toluyl, peroxidation, 5-dimethyl-2, the superoxide such as 5-exane-tert-butyl peroxide, di-t-butyl peroxide, also comprise the platinum curing system be made up of platinum complex compound and containing hydrogen silicone oil mixture;
When using the solidifying agent of peroxide, can be wherein a kind of, also can be above more than two or three snperoxiaized combination.
10. the preparation method of the high-temperature silicon disulfide rubber of a kind of extrusion moulding precipitated silica enhancing as claimed in claim 9, it is characterized by: relative to the high-temperature silicon disulfide rubber sizing material of 100 weight parts, the amount of the superoxide added is 0.1-15 weight part, preferred 0.3-10 weight part, especially preferably 0.5-6 weight part;
When using platinum curing system, relative to the high-temperature silicon disulfide rubber sizing material of 100 weight parts, in platinum curing system, the addition of the mixture of platinum complex compound and polysiloxane is 0.1-15 weight part, preferred 0.2-10, especially preferably 0.4-5; In platinum curing system, the addition of the mixture of containing hydrogen silicone oil and white carbon black is 0.1-20 weight part, preferred 0.2-15, especially preferably 0.4-8.
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| CN107964247A (en) * | 2017-12-13 | 2018-04-27 | 江西蓝星星火有机硅有限公司 | A kind of preparation method of the Conductive high-temperature silicon sulfide rubber of good mechanical performance |
| CN109337375A (en) * | 2018-10-24 | 2019-02-15 | 合盛硅业股份有限公司 | Low compression set silastic material and preparation method thereof |
| CN109679351A (en) * | 2018-12-26 | 2019-04-26 | 上海应用技术大学 | A kind of high-strength silicone rubber composite material and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107964247A (en) * | 2017-12-13 | 2018-04-27 | 江西蓝星星火有机硅有限公司 | A kind of preparation method of the Conductive high-temperature silicon sulfide rubber of good mechanical performance |
| CN107964247B (en) * | 2017-12-13 | 2020-11-24 | 江西蓝星星火有机硅有限公司 | Preparation method of conductive high-temperature vulcanized silicone rubber with excellent mechanical properties |
| CN109337375A (en) * | 2018-10-24 | 2019-02-15 | 合盛硅业股份有限公司 | Low compression set silastic material and preparation method thereof |
| CN109679351A (en) * | 2018-12-26 | 2019-04-26 | 上海应用技术大学 | A kind of high-strength silicone rubber composite material and preparation method |
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| CN105400209B (en) | 2019-01-25 |
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