CN1252187C - Dendritic molecular crosslinked peroxide hig temperature silicon sulfide rubber and its preparing method - Google Patents
Dendritic molecular crosslinked peroxide hig temperature silicon sulfide rubber and its preparing method Download PDFInfo
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- CN1252187C CN1252187C CN 200310114640 CN200310114640A CN1252187C CN 1252187 C CN1252187 C CN 1252187C CN 200310114640 CN200310114640 CN 200310114640 CN 200310114640 A CN200310114640 A CN 200310114640A CN 1252187 C CN1252187 C CN 1252187C
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Abstract
The present invention relates to peroxidated high-temperature sulfidated silicone rubber crosslinked with dendritic molecules and a preparation method thereof, which belongs to the field of rubber materials. The silicone rubber contains base adhesive of silicone rubber, pyrogenic white carbon black, silazane, dendritic molecular crosslinking agents containing end allyl and peroxide vulcanizing agents. The molded high-temperature sulfurized silicone rubber of the present invention has the advantages of higher integral mechanical property and long service life, and is especially suitable for being used as high-performance elastic bodies under the conditions that the rubber is in contact with human bodies or the rubber is used at high temperature.
Description
(1) technical field
The present invention relates to crosslinked peroxidation type high-temperature silicon disulfide rubber of a kind of dendrimer and preparation method thereof, belong to field of rubber materials.
(2) background technology
Silicon rubber (Silicone Rubber) is to be basic glue with linear polysiloxane, adds reinforcing filler, linking agent, catalyzer and other Synergist S-421 95, through the elastomerics with flexible network mixing, that sulfuration forms.The polysiloxane molecule main chain alternately is made up of (Si-O-Si-) Siliciumatom and Sauerstoffatom, side chain is be connected with Siliciumatom hydrocarbon or replaces hydrocarbon organic group, these groups can be methyl, unsaturated ethylene thiazolinyl (molar fraction generally is no more than 0.005) or other organic group, so silicon rubber is a kind of macromolecular material that has inorganic and organic character concurrently.
Silicon rubber has excellent specific properties such as high-low temperature resistant, ultraviolet resistance, radiation hardness, weathering resistance, electrical isolation.As high performance elastomerics, since nineteen forty-four by the at first successful synthesizing methyl silicon rubber of U.S. General Electric company since, the basis of silicon rubber and applied research have all obtained deep development, have obtained at aspects such as chemical industry, automobile, aerospace, electronics, electrical equipment, building, weaving, health care, daily lifes using widely.
But because the Si-O-Si chain in the polysiloxane is shielded by organic group, a little less than the macromole interphase interaction power of silicone rubber based glue, molecular chain has the helical molecule configuration, and snappiness is big.These constitutional featuress make the silicon rubber softness and high resilience, but physicals is relatively poor.Intensity is lower after crosslinked, is the deficiency of silicon rubber maximum, has limited its range of application greatly.In addition, compare with organic rubber, the heatproof characteristic is one of the most outstanding premium properties of silicon rubber, so be used for the high temperature occasion more.
High-temperature silicon disulfide rubber is according to the difference of used vulcanizing agent, and sulfuration mechanism is divided into free radical type and silicon hydrogen add-on type, and corresponding cross-linked rubber is called peroxidation type and add-on type high-temperature silicon disulfide rubber.Peroxidation type high-temperature silicon disulfide rubber is to adopt to contain the high molecular polysiloxane (being called vinylsiloxane rubber) of vinyl as basic glue, utilize superoxide under heat effect, to decompose and generate free radical, produce high molecular free radical with the vinyl reaction that contains the vinyl polysiloxane again, two high molecular free radicals take place crosslinked through coupling.
Linking agent has bigger influence to the performance of sulphurated siliastic.Contained vinyl is discrete distribution in the vinylsiloxane rubber in molecular chain, and crosslinked back forms dispersed crosslinked point, i.e. dispersed crosslinked network under peroxidation.The dispersed crosslinked network is done the time spent being subjected to external force, and cross-link bond is fracture one by one easily, so the intensity of cross-linked rubber is lower.If use a certain amount of multi-vinyl silicone oil or other to contain the organism of a plurality of unsaturated groups (vinyl or ethynyl) and silicon compound linking agent as silicon rubber, owing to produce " concentrating cross-linking set " during sulfuration, when material is subjected to external force, by concentrating cross-linking set that stress is distributed on numerous molecular chains equably, the ability of material opposing external force is strengthened.Relevant report is seen " the phenylacetylene base silicon compound is to the influence of high-temperature silicon disulfide rubber; I.1; 3 two (methylbenzene ethynyl vinyl) sily oxide " (Shengyu Feng, Zuodong Du, Effect of Some Phenylethynylsilicon Conpounds on HeatCurable Silicone Rubber.I.1.3-bis (methylphenylethynylvinyl) disiloxane.Journal of AppliedPolymer Science, 1991,43:1323-1326); " the phenylacetylene base silicon compound is to the influence of high-temperature silicon disulfide rubber; II. phenylacetylene base vinyl diethoxy silane " (Shuqi Yu, Shengyu Feng, Shijun Li, Jianhua Chen, Zuodong Du, Effect of Some Phenylethynylsilicon Compounds on Heat Curable SiliconRubber.II.Phenylethynylvinyldiethoxysilane.Journa l of Material Chemistry, 1992,2:529-531); Feng Shengyu, Yu Shuqi, Chen Jianhua, Du Zuodong, the research of high-strength high temperature-resistant peroxidation type high-temperature silicon disulfide rubber, China Synthetic Rubber Industry, 1987,10 (1), 32; " contain the linking agent of vinyl polysiloxane as high-temperature silicon disulfide rubber " (Shigui Zhao and Shengyu Feng.Vinyl-Containing Silicone Resin as the CrosslinkingAgent of Heat-Curable Silicone Rubber.Journal of Applied Polymer Science.2002,83:3123-3126).
Along with the particularly development of national defence and sophisticated technology of science and technology, the thermotolerance of silicon rubber is also had higher requirement.Thereby mechanical property and the use temperature under hot environment and the life-span of improving silicon rubber effectively, widen its range of application, be one of key content of silicon rubber research.
(3) summary of the invention
The present invention is directed to the deficiencies in the prior art, providing a kind of is the peroxidation type high-temperature silicon disulfide rubber and preparation method thereof of linking agent with the dendrimer.
Dendrimer is highly branched, regular macromole.Have as the tree profile, in most of the cases have three-dimensional globosity, almost all have a branch point on each repeating unit, be a class have nanoscale, the extremely narrow polymkeric substance of molecular weight distribution.Owing to there is a large amount of functional groups to be distributed in the outside of globosity thick and fast, during as the linking agent of peroxidation type high-temperature silicon disulfide rubber, resulting silicon rubber has the physical strength and the thermostability of obvious raising than existing silicon rubber.
Technical scheme of the present invention is as follows:
A kind of is the peroxidation type high-temperature silicon disulfide rubber of linking agent with the dendrimer, component is as follows: 100 parts in silicone rubber based glue, gas-phase silica 45-65 part, silazane 6-8 part, contain terminal allyl group dendrimer linking agent 0.10-0.40 part, peroxide vulcanizing agent 1.0-2.0 part, be weight part; Above-mentioned dendrimer is with Ph
2Si, CH
3Si or Si are for nuclear, with CH
3Si is branch point, with CH
2CH
2CH
2Be containing of spacer of terminal allyl group carbon silane type dendrimer.
Above-mentioned silicone rubber based glue is that molecular-weight average is 54～560,000, to contain the vinyl chain link be 0.15% methyl vinyl silicone rubber.Material of the present invention desires to be used in the medical environment that contacts with human body and the common out of use hot environment of organic rubber, and it requires material to have higher stretching, tear strength and long high temperature life, therefore selects for use silicon rubber as basic glue.Silicon rubber has excellent specific properties such as high-low temperature resistant, ultraviolet resistance, radiation hardness, weathering resistance, electrical isolation, physiology inertia.
Above-mentioned contain terminal allyl group dendrimer linking agent, be selected from one of following or its combination:
Be CH
3SiG
1 (Allyl) 6
Be CH
3SiG
2 (Allyl) 12
Be CH
3SiG
3 (Allyl) 24
Be SiG
1 (Allyl) 8
Be SiG
2 (Allyl) 16
Be Ph
2SiG
1 (Allyl) 4
Be Ph
2SiG
2 (Allyl) 8
Be Ph
2SiG
3 (Allyl) 16
It is one of following that above-mentioned peroxide vulcanizing agent is selected from: 2, and 5-dimethyl-2,5-di-t-butyl hexane peroxide, dicumyl peroxide, benzoyl peroxide.
The preparation method of the peroxidation type high-temperature silicon disulfide rubber that above-mentioned dendrimer is crosslinked is as follows:
In mill, 100 parts of raw-silastic continuouslies are plasticated, wait to wrap roller transparent after, add gas-phase silica 45-65 part, silazane 6-8 part, peroxide vulcanizing agent 1.0-2.0 part, contain terminal allyl group dendrimer linking agent 0.10-0.40 part, be weight part; Carry out mixing; Mixing evenly after, sheet under the clot; Whole plasticate and mixing process in, the roller surface temperature remains on 30-45 ℃; One section molded vulcanization carries out on vulcanizing press: curing temperature is 120-170 ℃, and curing time is 15-30 minute, and pressure is 20MPa; Post vulcanization carries out in air oven: 180 ℃ * 2 hours.
The present invention selects for use white carbon black as the reason of filler to be: a little less than the Intermolecular Forces of silicone rubber based glue, the intensity of cross-linked rubber has only about 0.3MPa during not with strengthening agent, add suitable strengthening agent and can make the intensity of silicon rubber vulcanization glue reach 3.9～98MPa, therefore reinforcement is very important to silicon rubber.The filler of silicon rubber has siliceous according to composition and not siliceous two big classes, and as white carbon black, silica powder, diatomite, kaolin, potter's clay, lime carbonate etc., wherein white carbon black is the optimal reinforced filling of silicon rubber.The median size of thermal silica is 5～20nm, and specific surface area is 200～400m
2G
-1, reinforcing effect is better; The median size of precipitated silica is 300～1000nm, and specific surface area is at 30m
2G
-1Below, reinforcing effect is relatively poor.So select for use gas-phase silica as filler.
The performance of material of the present invention is as follows:
| Project | Unit | Performance | Remarks |
| Outward appearance tensile strength 100% tensile modulus tear strength elongation at break hardness | -- MPa MPa KN/m ％ SHA | No significant defect 〉=8.4 〉=1.0 〉=27.5 〉=400≤60 | Visual inspection 12345 |
Annotate: 1. tensile strength: GB528-92;
2.100% tensile modulus: GB528-92;
3. tear strength: GB528-92:
4. elongation at break: GB528-92;
5. hardness: GB531-83.
Compared with the prior art the present invention has following substantive distinguishing features: the comprehensive mechanical performance of this kind material is higher, long service life, be particularly suitable for contacting with human body or hot environment under use.
(4) embodiment
Embodiment 1: by weight, and 100 parts in silicone rubber based glue, 60 parts of gas-phase silicas, 2,5-dimethyl-2,1.0 parts of 5-di-t-butyl hexane peroxides, CH
3SiG
1 (Allyl) 60.28 part, in mill, raw-silastic continuously is plasticated, wait to wrap roller transparent after, add white carbon black, 2,5-dimethyl-2,5-di-t-butyl hexane peroxide, CH
3SiG
1 (Allyl) 6Carry out mixing.Mixing evenly after, sheet under the clot, molded vulcanization on vulcanizing press.Whole plasticate and mixing process in, the roller surface temperature remains on below 45 ℃.The one step cure condition is: 170 ℃ * 30 minutes, pressure was 20MPa.Post vulcanization carries out in air oven: 180 ℃ * 2 hours.
Embodiment 2: with embodiment 1, different is 50 parts of gas-phase silicas, 2, and 5-dimethyl-2,1.8 parts of 5-di-t-butyl hexane peroxides, CH
3SiG
2 (Allyl) 120.10 part, the one step cure condition is: 170 ℃ * 15 minutes.
Embodiment 3: with embodiment 1, different is 50 parts of gas-phase silicas, 2, and 5-dimethyl-2,1.5 parts of 5-di-t-butyl hexane peroxides, CH
3SiG
3 (Allyl) 240.30 part, the one step cure condition is: 170 ℃ * 20 minutes.
Embodiment 4: with embodiment 1, different is 55 parts of gas-phase silicas, 1.0 parts of peroxidation two different interior benzene, 8iG
1 (Allyl) 80.20 part, the one step cure condition is: 170 ℃ * 20 minutes.
Embodiment 5: with embodiment 1, different is 50 parts of gas-phase silicas, 2.0 parts of dicumyl peroxides, SiG
2 (Allyl) 160.32 part, the one step cure condition is: 160 ℃ * 20 minutes.
Embodiment 6: with embodiment 1, different is 50 parts of gas-phase silicas, 2.0 parts of dicumyl peroxides, SiG
3 (Allyl) 320.24 part, the one step cure condition is: 160 ℃ * 20 minutes.
Embodiment 7: with embodiment 1, different is 50 parts of gas-phase silicas, 2.0 parts of benzoyl peroxides, Ph
2SiG
1 (Allyl) 40.32 part, the one step cure condition is: 120 ℃ * 20 minutes.
Embodiment 8: with embodiment 1, different is 45 parts of gas-phase silicas, 2.0 parts of benzoyl peroxides, Ph
2SiG
2 (Allyl) 80.20 part, the one step cure condition is: 120 ℃ * 20 minutes.
Embodiment 9: with embodiment 1, different is 50 parts of gas-phase silicas, 2.0 parts of benzoyl peroxides, Ph
2SiG
3 (Allyl) 160.40 part, the one step cure condition is: 120 ℃ * 20 minutes.
Embodiment 10: with embodiment 1, different is 50 parts of gas-phase silicas, 2.0 parts of dicumyl peroxides, SiG
2 (Allyl) 160.16 part+CH
3SiG
3 (Allyl) 240.30 part, the one step cure condition is: 160 ℃ * 20 minutes.
Embodiment 11: with embodiment 1, different is 50 parts of gas-phase silicas, 2, and 5-dimethyl-2,1.2 parts of 5-di-t-butyl hexane peroxides, SiG
3 (Allyl) 320.24 part+Ph
2SiG
3 (Allyl) 160.16 part, the one step cure condition is: 160 ℃ * 20 minutes.
Embodiment 12: with embodiment 1, different is 50 parts of gas-phase silicas, 2, and 5-dimethyl-2,1.2 parts of 5-di-t-butyl hexane peroxides, SiG
2 (Allyl) 160.16 part+Ph
2SiG
3 (Allyl) 160.16 part, the one step cure condition is: 160 ℃ * 25 minutes.
Claims (4)
1. peroxidation type high-temperature silicon disulfide rubber that dendrimer is crosslinked, it is characterized in that containing 100 parts in silicone rubber based glue, gas-phase silica 45-65 part, silazane 6-8 part, contain terminal allyl group dendrimer linking agent 0.10-0.40 part, peroxide vulcanizing agent 1.0-2.0 part, be weight part;
Describedly contain terminal allyl group dendrimer linking agent, be selected from one of following or its combination:
Be CH
3SiG
3 (Allyl) 24,
Be SiG
2 (Allyl) 16,
Be Ph
2SiG
1 (Allyl) 4,
2. the peroxidation type high-temperature silicon disulfide rubber that dendrimer as claimed in claim 1 is crosslinked is characterized in that described silicone rubber based glue is that molecular-weight average is 54～560,000, to contain the vinyl chain link be 0.15% methyl vinyl silicone rubber.
3. the peroxidation type high-temperature silicon disulfide rubber that dendrimer as claimed in claim 1 is crosslinked, it is characterized in that described peroxide vulcanizing agent selects for use one of following: 2,5-dimethyl-2,5-di-t-butyl hexane peroxide, dicumyl peroxide, benzoyl peroxide.
4. the preparation method of the crosslinked peroxidation type high-temperature silicon disulfide rubber of the described dendrimer of claim 1, it is characterized in that in mill, 100 parts of raw-silastic continuouslies being plasticated, wait to wrap roller transparent after, add gas-phase silica 45-65 part, silazane 6-8 part, peroxide vulcanizing agent 1.0-2.0 part, contain terminal allyl group dendrimer linking agent 0.10-0.40 part, be weight part; Carry out mixing; Mixing evenly after, sheet under the clot; Whole plasticate and mixing process in, the roller surface temperature remains on 30-45 ℃; One section molded vulcanization carries out on vulcanizing press: curing temperature is 120-170 ℃, and curing time is 15-30 minute, and pressure is 20MPa; Post vulcanization carries out in air oven: 180 ℃ * 2 hours.
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| CN113185844B (en) * | 2021-05-18 | 2023-05-12 | 王文雨 | Ultrathin silicon rubber film and preparation method thereof |
| CN113896894B (en) * | 2021-11-03 | 2023-03-28 | 万华化学集团股份有限公司 | Branched cross-linking agent, and preparation method and application thereof |
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Assignee: Maoming City Cheery Silicone Co., Ltd. Assignor: Shandong University Contract record no.: 2010440000781 Denomination of invention: Dendritic molecular crosslinked peroxide hig temperature silicon sulfide rubber and its preparing method Granted publication date: 20060419 License type: Exclusive License Open date: 20041215 Record date: 20100613 |
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