CN1186381C - Silicon rubber/conductive ethylene propylene terpolymer and its preparing method - Google Patents
Silicon rubber/conductive ethylene propylene terpolymer and its preparing method Download PDFInfo
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- CN1186381C CN1186381C CN 03112434 CN03112434A CN1186381C CN 1186381 C CN1186381 C CN 1186381C CN 03112434 CN03112434 CN 03112434 CN 03112434 A CN03112434 A CN 03112434A CN 1186381 C CN1186381 C CN 1186381C
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Abstract
The present invention relates to silicon rubber/ ethylene propylene terpolymer combination conductive rubber and a preparation method, and belongs to the technical field of macromolecular conductive composite material. The silicon rubber/ ethylene propylene terpolymer rubber is made from raw ethylene propylene terpolymer, raw silastic, silane coupling agents, organic peroxides, black carbon and white carbon black. The preparation method has the steps that an open type double-roller rubber mixing machine is used for machining, the raw rubber are rolled, the white carbon black is added to be blended, the black carbon is added to be blended, the sizing with uniform blending carries out tight milling, the silane coupling agents are added to be blended, and the organic peroxides are added to carry out tight milling, rolling and sheet discharging. The method of the present invention can obtain combination conductive rubber with good mechanical property, the preparation method is simple and easy to implement, the cost is low, and the product quality is good.
Description
(1) technical field
The present invention relates to a kind of novel conductive rubber, belong to the conductive polymer composite technical field.
(2) background technology
Conductive filler material (carbon black, carbon fiber, metal-powder etc.) is filled into the compound conductive silicon rubber that obtains in the silicon rubber, because do not contain tenderizer, softening agent or the vulcanization accelerator etc. of treated oil and dibutyl phthalate, dioctyl phthalate (DOP) and so on, therefore can not haze and cause environmental pollution because of leakage, it is only electronic unit material, the weathering resistance of silicon rubber inherent excellence and high and low temperature resistance make conductive silicon rubber become the conductive rubber of present consumption maximum in addition.The biggest market of conductive silicon rubber is the key contactor material, and with regard to the wearing quality of keyboard, desk-top computer is about 1,000,000 times, and terminal then requires more than ten million time.But the kinetic characteristic of silicon rubber is bad, in the loaded repeatedly uses of need such as keyboard, needs to improve its intensity and weather resistance.In addition, the cost of silicon rubber is higher, also is to make one of reason that its use is restricted.With the synthetic rubber and the usefulness of silicon rubber and other kind, be an effective way that improves the conductive silicon rubber mechanical property and reduce cost.
Terpolymer EP rubber (EPDM) has good winter hardiness, thermotolerance, ozone resistance, resistance to acids and bases, electric insulating quality and higher physical strength etc., and price is cheaper in addition, thereby has obtained widespread use at many industrial sectors.The silicon rubber solubility parameter is 7.3, and the EPDM solubility parameter is 8.0, and both polarity are close, makes and with becoming possibility.Silicon rubber/EPDM blended rubber can reduce the cost of silicon rubber, and effectively improves the physical strength of silicon rubber, the electric property after dynamic fatigue characteristic, water-fast steam, hot water resistance and the immersion.
Japan chemical company of SHIN-ETSU HANTOTAI makes silicon rubber and EPDM form network structure with special silane coupling agent, takes the lead in having developed silicon rubber/EPDM blended rubber.The JSR JENIX E2170 blended rubber that Japan SYnthetic Rubber Co. Ltd releases, no matter tensile strength, tear strength, tensile yield, or thermotolerance, water tolerance all are better than silicon rubber greatly.Relevant report is seen Marvin's stone, " development and application of silicon rubber blended rubber ", rubber industry, 1998,45,630.Generally speaking, it is best that the compatibilizing and co-mixing method is adopted in silicon rubber and EPDM blend.Functional Organic Polysiloxane and reinforced type silicon-dioxide paralled system, ethylene-propylene rubber(EPR) (EPR) grafted silane, polyethylene acrylate, ethylene-vinyl acetate copolymer, polycthylene grafted silane etc. are made compatilizer, make silicon rubber/EPDM also be significantly increased than the simple blend product with rubber physicals, aging resistance, thermal stability.The visible Cole of relevant report waits " chemical interaction is also used rubber performance to silicon rubber-Ethylene Propylene Terpolymer influence ", polymkeric substance, 1995,36 (17), 3273.(Kole S, Roy S and BhowmickA K, Polymer, 1995,36 (17), 3273.); Wang Dizhen, Xu Xiaodan, Li Hang etc., " EPDM/ methyl vinyl silicone rubber blending technology, China Synthetic Rubber Industry, 1996,19 (3), 171.Above macromole compatilizer though the performance that improves blended rubber is had remarkable effect, does not have ready-made product can support utilization.So, can consider to use silane coupling agent to make compatilizer.In fact, it can effectively strengthen between white carbon black and the polymkeric substance and terpolymer EP rubber and silicon rubber between combine, thereby increase substantially the mechanical property and the thermotolerance of blended rubber, referring to the loose people of good fortune, Wang Yilu, " organosilicon synthesis technique and product application ", Chemical Industry Press, Beijing, 1999, P687.
Existing silicon rubber/EPDM paralled system is non-conductive.
(3) summary of the invention
The present invention is directed to the shortcomings such as cost height, intensity and poor durability of conductive silicon rubber, a kind of silicon rubber/Ethylene Propylene Terpolymer is provided and uses conductive rubber and preparation method thereof, by conductive silicon rubber and EPDM and usefulness, obtain mechanical property and be better than the conduction of conductive silicon rubber greatly and use rubber.
Silicon rubber/Ethylene Propylene Terpolymer of the present invention is also as follows with the conductive rubber material component, is weight part:
66～90 parts of terpolymer EP rubber (EPDM) rubbers
10～34 parts of raw-silastic continuouslies
5.0～8.8 parts/100 parts rubbers of silane coupling agent (EPDM and raw-silastic continuously total amount, down together)
4.4～10.0 parts/100 parts rubbers of organo-peroxide
30～60 parts/100 parts rubbers of carbon black
0～30 part/100 parts rubbers of white carbon black
The 3rd monomer of described EPDM is dicyclopentadiene (DCPD), or 5-ethylidene-2-norbornylene (ENB), iodine number 15～24.
Described silicon rubber is methyl vinyl silicone rubber, and vinyl molar content 0.05%～0.50%, or methyl phenyl vinyl silicone rubber, phenyl molar content are 5%～10%.
Described silane coupling agent is γ-(methacryloxy) propyl group trimethoxy silane (A-174), or two (3-triethoxysilylpropyltetrasulfide) tetrasulfides (Si69).
Described organo-peroxide is 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane (two 2,5), or dicumyl peroxide (DCP).
Described carbon black is Shawinigan black (Qingzhou chemical industry company limited product), high wear-resistant carbon black HAF N-330 (Qingzhou chemical industry company limited product), VXC-72 graphitized carbon black (Cabot Shanghai branch office product) or BP2000 superconduction carbon black (Cabot Shanghai branch office product).
Described white carbon black is 4# thermal silica (a Cabot Shanghai branch office product).
Silicon rubber/EPDM of the present invention is also as follows with the conductive rubber preparation method:
Adopt the processing of open type dual-roller rubber mixing machine, bowl temperature is a room temperature.At first 66～90 parts of EPDM rubbers and raw-silastic continuously are added on the cylinder for 10～34 parts, machine, make its bag roller after, add 0～30 part/100 parts rubbers of white carbon black earlier, mixingly add 30～60 parts/100 parts rubbers of carbon black again after evenly.The mixing operating time is relevant with amount of filler, generally at 25～60 minutes.Mixing uniform sizing material adds 5.0～8.8 parts of silane coupling agent/100 part rubbers after 8～10 thin-passes, after mixing 1～5 minute, add 4.4～10.0 parts/100 parts rubbers of organo-peroxide, thin-pass 10 times, sheet under the clot.On vulcanizing press, carry out one step cure.The one step cure condition is: under the 10MPa pressure, and 160 ℃ * 60 minutes; Post vulcanization carries out in the baking oven of tape drum wind, and condition is: 160 ℃ * 120 minutes.
Excellent results compared with prior art of the present invention is:
1. obtain a kind of mechanical property good and use conductive rubber, mainly mechanical property and electrical performance indexes are as follows: hardness: 71～77 (Shore A); Tensile strength: 7.04～17.37MPa; Tear strength: 23.69～50.1kN/m; Elongation at break: 189.2～383.6%; Volume specific resistance: ∞～87.3 Ω cm.
2. the preparation method is simple and easy to do.Cost is low, good product quality.
(4) embodiment
Embodiment 1: silicon rubber/Ethylene Propylene Terpolymer is also as follows with the conductive rubber material component, is weight part:
Terpolymer EP rubber (EPDM) rubber, the 3rd monomer are 75 parts of 5-ethylidenes-2-norbornylene (ENB)
Methyl vinyl silicon kautschuk, molecular weight 580,000, vinyl molar content 0.05%～0.50% 25 part
8.4 parts of two (3-triethoxysilylpropyltetrasulfide) tetrasulfides (Si69)
7.9 parts of dicumyl peroxides (DCP)
40 parts of VXC-72 graphitized carbon blacks
20 parts of 4# thermal silicas.
The preparation method is as follows:
Earlier that EPDM rubber and raw-silastic continuously is mixing to the hard-pressed bale preliminary roller in mill together, add white carbon black, mixing even back adds graphitized carbon black, mixing even, add two (3-triethoxysilylpropyltetrasulfide) tetrasulfides (Si69) of coupling agent and dicumyl peroxide (DCP) successively, thin-pass 10 times obtains and uses conductive rubber behind one step cure, the post vulcanization.Its hardness is: 75 (Shore A), and tensile strength is: 13.51MPa, tear strength is: 37.4kN/m, elongation at break is: 306.9%, volume specific resistance is: 6.57 * 10
2Ω cm.
Embodiment 2: silicon rubber/Ethylene Propylene Terpolymer is also as follows with the conductive rubber material component, is weight part:
Terpolymer EP rubber (EPDM) rubber, the 3rd monomer are 66 parts of 5-ethylidenes-2-norbornylene (ENB)
Methyl vinyl silicon kautschuk, molecular weight 580,000, vinyl molar content 0.05%～0.50% 34 part
7.8 parts of γ-(methacryloxy) propyl group trimethoxy silane (A-174)
2,5-dimethyl-2,6.7 parts of 5-two (t-butyl peroxy) hexanes (two 2,5)
40 parts of VXC-72 graphitized carbon blacks
20 parts of 4# thermal silicas.
The preparation method is as follows:
Earlier that EPDM rubber and raw-silastic continuously is mixing to the hard-pressed bale preliminary roller in mill together, add white carbon black, mixing even back adds graphitized carbon black, mixing even, add coupling agent Si69 and dicumyl peroxide DCP successively, thin-pass 10 times obtains and uses conductive rubber behind one step cure, the post vulcanization.Its hardness is: 75 (Shore A), and tensile strength is: 9.36MPa, tear strength is: 23.96kN/m, elongation at break is: 270.4%, volume specific resistance is: 9.31 * 10
2Ω cm.
Embodiment 3: silicon rubber/Ethylene Propylene Terpolymer is also as follows with the conductive rubber material component, is weight part:
Terpolymer EP rubber (EPDM) rubber, the 3rd monomer are 90 parts of 5-ethylidenes-2-norbornylene (ENB)
Methyl vinyl silicon kautschuk, molecular weight 580,000, vinyl molar content 0.05%～0.50% 10 part
7.8 parts of two (3-triethoxysilylpropyltetrasulfide) tetrasulfides (Si69)
6.7 parts of dicumyl peroxides (DCP)
40 parts of VXC-72 graphitized carbon blacks
20 parts of 4# thermal silicas.
The preparation method is as follows:
Earlier that EPDM rubber and raw-silastic continuously is mixing to the hard-pressed bale preliminary roller in mill together, add white carbon black, mixing even back adds graphitized carbon black, mixing even, add coupling agent γ-(methacryloxy) propyl group trimethoxy silane (A-174) and organo-peroxide 2 successively, 5-dimethyl-2,5-two (t-butyl peroxy) hexane (two 2,5), thin-pass 10 times obtains and uses conductive rubber behind one step cure, the post vulcanization.Its hardness is: 77 (Shore A), and tensile strength is: 17.37MPa, tear strength is: 50.1kN/m, elongation at break is: 383.6%, volume specific resistance is: 1.09 * 10
8Ω cm.
Claims (3)
1. silicon rubber/Ethylene Propylene Terpolymer is also used conductive rubber, it is characterized in that material component is as follows, is weight part:
66～90 parts of terpolymer EP rubber rubbers
10～34 parts of raw-silastic continuouslies
5.0～8.8 parts/100 parts rubbers of silane coupling agent
4.4～10.0 parts/100 parts rubbers of organo-peroxide
30～60 parts/100 parts rubbers of carbon black
0～30 part/100 parts rubbers of white carbon black;
The 3rd monomer of described terpolymer EP rubber is a dicyclopentadiene, or 5-ethylidene-2-norbornylene, iodine number 15～24;
Described silicon rubber is methyl vinyl silicone rubber, and vinyl molar content 0.05%～0.50%, or methyl phenyl vinyl silicone rubber, phenyl molar content are 5%～10%;
Described silane coupling agent is γ-(methacryloxy) propyl group trimethoxy silane, or two (3-triethoxysilylpropyltetrasulfide) tetrasulfide;
Described organo-peroxide is 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, or dicumyl peroxide.
2. silicon rubber/Ethylene Propylene Terpolymer as claimed in claim 1 is also used conductive rubber, it is characterized in that described carbon black is a Shawinigan black, high wear-resistant carbon black HAF N-330, VXC-72 graphitized carbon black or BP2000 superconduction carbon black.
3. the described silicon rubber/Ethylene Propylene Terpolymer of claim 1 comprises that also with the preparation method of conductive rubber step is as follows:
Adopt the processing of open type dual-roller rubber mixing machine, bowl temperature is a room temperature, at first 66～90 parts of terpolymer EP rubber rubber rubbers and raw-silastic continuously are added on the cylinder for 10～34 parts, machine, after making its bag roller, add 0～30 part/100 parts rubbers of white carbon black earlier, mixingly add 30～60 parts/100 parts rubbers of carbon black again after evenly, 25～60 minutes mixing operating times, mixing uniform sizing material adds 5.0～8.8 parts of silane coupling agent/100 part rubbers after 8～10 thin-passes, after mixing 1～5 minute, add 4.4～10.0 parts/100 parts rubbers of organo-peroxide, thin-pass 10 times, sheet under the clot; Carry out one step cure on vulcanizing press, condition is: under the 10MPa pressure, and 160 ℃ * 60 minutes; Post vulcanization carries out in the baking oven of tape drum wind, and condition is: 160 ℃ * 120 minutes.
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| CN102061038B (en) * | 2010-12-18 | 2013-02-27 | 福建省工研苑塑胶技术研发有限公司 | Silicon rubber and EPDM mixed rubber and preparation method thereof |
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Assignee: MINDAR CHINA CO., LTD. Assignor: Shandong University Contract fulfillment period: 2008.7.21 to 2013.7.20 contract change Contract record no.: 2009110000158 Denomination of invention: Silicon rubber/conductive ethylene propylene terpolymer and its preparing method Granted publication date: 20050126 License type: Exclusive license Record date: 2009.7.30 |
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