CN101165088A - Middle and high pressure oil-resisting rubber semiconduction shielded cable material and preparation - Google Patents
Middle and high pressure oil-resisting rubber semiconduction shielded cable material and preparation Download PDFInfo
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- CN101165088A CN101165088A CNA2006100969824A CN200610096982A CN101165088A CN 101165088 A CN101165088 A CN 101165088A CN A2006100969824 A CNA2006100969824 A CN A2006100969824A CN 200610096982 A CN200610096982 A CN 200610096982A CN 101165088 A CN101165088 A CN 101165088A
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Abstract
The improved oil resistant semi-conductive cable shielding material consists of butadiene-acrylonitrile rubber or hydrogenated butadiene-acrylonitrile rubber 100 weight portions, conducting carbon black 50-80 weight portions, graphite powder 15-30 weight portions, plasticizer 15-20 weight portions, dithio tetramethyl thiram and alphatic polysulfide 1.0-3.0 weight portions, dibenzothiazole disulfide and zinc diethyl dithio amino formate 1.0-2.0 weight portions, zinc oxide and stearic acid 8.0-10.0 weight portions. Compared with available technology, the present invention has the advantages of excellent conductivity, volume resistivity not greater than 50 ohm.cm, high tensile strength up to 18 MPa, high oil resistance and other advantages.
Description
Technical field
The present invention relates to a kind of mesohigh Plastic-sheathed Cable, conductor and insulation fuel-resistant rubber semi-conductive shielding CABLE MATERIALS, especially a kind of fuel-resistant rubber semi-conductive shielding CABLE MATERIALS of easily peeling off.
Background technology
Mesohigh (for example voltage range＞6000 volt) Plastic-sheathed Cable, conductor and insulation rubber semi-conductive shielding material, the basic rubber of prior art all adopts terpolymer EP rubber or other non-polar rubber.As semiconductive polyolefine as external shielding material of cable as described in the Chinese patent 97115236.5, its composition (weight): base resin terpolymer EP rubber 10-30 part, modified resin chloroprene rubber 70-90 part, Shawinigan black 15-25 part, vulcanization system 18-23 part, antioxidant 1010＜0.5 part, stearic acid+white oil 4-6 part, DOP 10-15 part.The Chinese patent 200410089024.5 described middle guttapercha cables of pressing expect that with shielding component is: 100 parts of terpolymer EP rubbers, 50～100 parts of graphitized carbon blacks, 1～3 part of protective agent, 2～4 parts of organo-peroxides, 1～2 part of coupling agent, 2～8 parts in wax, 5～20 parts of treated oils.Because it is nonpolar forming semi-conductive screen rubber, thereby not anti-non-polar oil (for example mineral oil, oil fuel), in use meet polar oil and can produce the distortion expansion, cause physical and mechanical properties sharply to descend, influence is normally used; Secondly, be the semi-conductive screen CABLE MATERIALS that basic rubber is made with Ethylene Propylene Terpolymer, resistance ratio is higher, common volume specific resistance＞100 Ω .cm, conductivity is relatively poor, and shield effectiveness is bad; Besides, the employed vulcanization system of terpolymer EP rubber adopts the organic peroxy compound basically, production process and lay after can bulk storage go out unpleasant, pungent peculiar smell, do not meet the environmental requirement that improves day by day.And with the terpolymer EP rubber is the semi-conductive screen CABLE MATERIALS of base-material, also exists to tear to peel off difficulty, and peeling off to construction makes troubles, and with insulation layer color can take place and move mutually, influences the cable outward appearance, causes deficiencies such as insulated electro performance decline.
Though prior art has the nitrile rubber of employing to be used for insulation or sheath report, because of insulation, sheath and semiconductive shieldin material belong to two generic request differing materials.Nitrile rubber mooney viscosity height need not add electro-conductive material when being used for insulation or sheath, only fills lime carbonate or the talcum powder with low mooney viscosity, thereby mixes good manufacturability easily; And need to add a large amount of electro-conductive materials as shielding material, and and the electro-conductive material mooney viscosity is higher equally, causes both to be difficult to thorough mixing, and the manufacturability extreme difference, institute is not so that all have report before the present invention, adopts the fine or hydrogenation nitrile rubber of fourth to make the semi-conductive screen base-material.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, provide a kind of oil-proofness good, high conductance electricity, free from extraneous odour produces, and the mesohigh fuel-resistant rubber semi-conductive shielding CABLE MATERIALS of easily peeling off.
Another object of the present invention is to provide a kind of preparation of above-mentioned semi-conductive screen CABLE MATERIALS.
The present invention's first purpose realizes, the main improvement is to adopt polar fourth fine (NBR) or hydrogenation nitrile rubber (HBNR) to make basic rubber, select suitable tasteless vulcanization system, and increase the adding Graphite Powder 99, thereby make the rubber semi-conductive screen CABLE MATERIALS of composition, both oil resistant, has high conductivity again, and the free from extraneous odour generation, and easily peel off, thereby realize the object of the invention.Specifically, mesohigh fuel-resistant rubber semi-conductive shielding CABLE MATERIALS of the present invention basic composition is (weight):
100 parts of the fine or hydrogenation nitrile rubbers of fourth
Conductive carbon black 50-80 part
Graphite Powder 99 15-30 part
Softening agent 15-20 part
Two sulphur tetra methylthiurams and aliphatics polysulfide 1.0-3.0 part
Curing Dibenzo thiazole and zinc diethyldithiocarbamate 1.0-2.0 part
Zinc oxide and stearic acid 8.0-10.0 part.
Among the present invention
Fine or the hydrogenation nitrile rubber of fourth is semi-conductive screen basis rubber, because of belonging to polar material, and can anti-non-polar oil.
Conductive carbon black, main effect increases the conductivity of shielded cable material, and the present invention's add-on preferably is 50-60 part.
Graphite Powder 99, a kind of electro-conductive material mainly plays and improves the conductivity effect; Graphite Powder 99 also has lubricity simultaneously, thereby also has lubricant in the present composition, helps improving the easy separability and the workability of semiconductive shieldin material.Select to adopt Graphite Powder 99 to be used for the present invention, both made conductive additive, use as lubricant again, it realizes that double effects is the present invention's one invention characteristics.Test shows that add-on preferably is 15-20 part.
Softening agent mainly has been a plastification, improves the complete processing of rubber mass, and the softening agent that uses in any rubber all can use, but from economic considerations, the present invention better adopts dioctyl ester and/or Vaseline to make softening agent.
Two sulphur tetra methylthiurams and aliphatics polysulfide as the fine or hydrogenation nitrile rubber vulcanizing agent of fourth, not only have intermiscibility preferably with rubber, and vulcanization rate is fast, the production efficiency height, and also free from extraneous odour produces.Test shows that both are preferably 40-70 at ratio of mixture: 30-60, adopt this ratio of mixture, and it is long to have a time of scorch, sulfuration safety.
Curing Dibenzo thiazole and zinc diethyldithiocarbamate are for cooperating vulcanization accelerator with vulcanizing agent.Test shows that both ratio of mixture are preferably near the equivalent proportioning, adopts same-size ratio, and it is good to have a sulfuration security.
Zinc oxide and stearic acid are the promoting agent of accelerated cure.Both mix use, and ratio of mixture is 4-5 preferably: 1, and this ratio is more conducive to vulcanize safety, and can play the optimum activity effect to vulcanizing agent and promotor.Vulcanizing agent, vulcanization accelerator and promoting agent three constitute rubber vulcanization system of the present invention jointly.
In addition, can also add some other functional agent as common semi-conductive screen among the present invention, for example have the anti-aging agent of anti-aging function, the weighting agent that reduces cost is to realize corresponding function.
For further improving its tearing property, strengthen the construction process rippability, and improve material plasticity and improve manufacturability, the various lubricants that can also add lubricate in the rubber production among the present invention, wherein the present invention preferably adopts A-16 type release agent (Shanghai bodyguard minister commerce and trade company limited product) and Vaseline.
The present invention better consists of (weight) like this:
100 parts of the fine or hydrogenation nitrile rubbers of fourth
Conductive carbon black 50-60 part
Graphite Powder 99 15-20 part
Softening agent 15-20 part
Two sulphur tetra methylthiurams and aliphatics polysulfide 1.0-3.0 part
Curing Dibenzo thiazole and zinc diethyldithiocarbamate 1.0-2.0 part
Zinc oxide and stearic acid 8.0-10.0 part
Anti-aging agent 1.0-1.5 part
Lubricant 1.0-1.5 part.
Mesohigh fuel-resistant rubber semi-conductive shielding CABLE MATERIALS of the present invention preparation: comprise required material mixingly, it is characterized in that earlier fine or hydrogenation nitrile rubber mastication reduces viscosity with fourth; Add other outer mixing ingredients of sulphur removal agent at least and promotor again, mixing back adds the vulcanization system batch mixes, opens bar slice or granulation.
The present invention test shows, when fourth is fine or hydrogenation nitrile rubber mastication to plasticity value 0.4-0.5, can be better and other add the fully mixing of pan feeding, the while is again a less expensive.
Decompose or roll banding for avoiding high temperature to produce, mastication temperature of the present invention better is to be not more than 60 ℃; And mastication is preferably at interval and carries out, and after promptly a mastication is finished, places the time, and cooling treats that molecule carries out mastication next time after stable again, and for example two minor ticks were greater than 4 hours.For avoiding adding the pyrolytic decomposition or the roll banding of pan feeding, melting temperature of the present invention better is to be not more than 90 ℃.The time of placing after mastication is finished treats that molecule is stable for example more than 8 hours, carries out mixing again.
Mastication of the present invention and mixing can adopt common compounding rubber mill, Banbury mixer or mixing extruder.
The present invention is because the fourth of the anti-non-polar oil of employing is fine or the hydrogenation nitrile rubber is made base-material, and select to cooperate with it, the vulcanization system that produces of free from extraneous odour again, and the Graphite Powder 99 that adds conduction, lubricates, thereby overcome mesohigh Plastic-sheathed Cable conductor and insulation shielding material that prior art can not prepare anti-mineral oil or oil fuel, and had the taste and volume specific resistance is higher, the deficiency of tearing property difference (performance comparison sees Table) of being pungent.Mesohigh fuel-resistant rubber semi-conductive shielding CABLE MATERIALS of the present invention has than prior art: conductivity is good, utmost point low insulation resistance, volume specific resistance only is original about 1/2, generally be not more than 50 Ω .cm, improved the inside and outside electromagnetic radiation of isolation cable, antistatic coupling, electromagnetic induction and interfered with each other ability, the cable shield performance is better; The tensile strength height can reach more than the 18Mpa; Anti-mineral oil, oil fuel do not expand; There is not pungent peculiar smell; With the not migration mutually of insulation color, appearance luster is good, can't reduce insulating property; Shielding and conductor, shielding and insulation rippability are good, construction, easy to use.The Ethylene Propylene Terpolymer base-material be can substitute fully and medium and high voltage cable conductor and insulating shielding are used for.The inventive method owing to adopt before mixing, fine or hydrogenation nitrile rubber mastication reduces mooney viscosity with fourth earlier, thereby the remarkable fine or hydrogenation nitrile rubber of fourth that improved as the semi-conductive screen production technique, enable reality and be used for actual production.Semi-conductive screen of the present invention, anti-mineral oil that it is good and oil fuel performance, there is not pungent peculiar smell, high-tensile, low insulation resistance is the important difference that is different from other rubber semi-conductive screens, and because of adopting the fine or hydrogenation nitrile rubber of fourth, contain vinyl cyanide in the molecular structure, this is again that the present invention distinguishes the differential point with other semi-conductive screen CABLE MATERIALS.
Below in conjunction with several embodiments, further specify the present invention.
Embodiment:
Embodiment: the embodiment proportioning sees Table two.Prepare, take by weighing each by table two embodiment proportioning and expect, earlier with basic rubber mastication in little mill, bowl temperature is less than 60 ℃, and mastication secondary, each mastication draw and approach tube 8-10 time, and twice mastication interval is more than 4 hours, and the plasticity value that mastication finishes rubber is 0.4-0.5.Place more than 8 hours, again that mastication is good rubber mixing bag roller or at mixer mixing 1-2 minute in mill, add graphitized carbon black, Graphite Powder 99, promoting agent (also can then add), and after slowly adding softening agent, lubricant, the mixing 4-5 of anti-aging agent minute, melting temperature is less than 90 ℃, add vulcanizing agent and promotor at last, through 1-1.5 minute mixing evenly after, it is standby to pull into 1.00mm thickness sheet or 4mm3 cube grain.
Get a certain amount of sheet stock or pellet, through 160 ℃ * 30 minutes, pressure was about 15-18Mpa on vulcanizing press, was pressed into the test piece that thickness is 1-2mm, carried out performance test (the results are shown in Table two).
Table one the present invention and Ethylene Propylene Terpolymer semi-conductive screen performance comparison sheet
Table two Example formulations and performance
Illustrate: numerical value among the embodiment, front are umber, are weight in the bracket.
Among the embodiment: example 1,2 adopts nitrile rubber (NBR), and example 3 adopts hydrogenation nitrile rubber (HNBR); Promoting agent adopts respectively: 4: 1,5: 1,5: 1 zinc oxide and stearic acid; Anti-aging agent, example 1 is 2-thiol group and imidazoles, example 2 is 2,2,4-trimethylammonium-1,2-hydrogenated quinoline polymer, example 3 is two kinds of 1: 1 balanced mix; Lubricant was respectively 3: 1, and 2: 1,2: 1 Vaseline and A-16 release agent (Shanghai bodyguard minister commerce and trade company limited); Softening agent is a dioctyl phthalate (DOP); Graphitized carbon black adopts Korea S to produce graphitized carbon black 420B, homemade graphitized carbon black XF-72 respectively, and use at 1: 1; Vulcanizing agent was respectively 3: 7, and 6: 4, blue and nurse aliphatics polysulfide of 5: 5 two sulphur tetramethyl-autumns; Promotor is 1: 1 zinc diethyldithiocarbamate and curing Dibenzo thiazole; Weighting agent is respectively lime carbonate, potter's clay powder, talcum powder.
Claims (10)
1. mesohigh fuel-resistant rubber semi-conductive shielding CABLE MATERIALS basic composition is (weight):
100 parts of the fine or hydrogenation nitrile rubbers of fourth
Conductive carbon black 50-80 part
Graphite Powder 99 15-30 part
Softening agent 15-20 part
Two sulphur tetra methylthiurams and aliphatics polysulfide 1.0-3.0 part
Curing Dibenzo thiazole and zinc diethyldithiocarbamate 1.0-2.0 part
Zinc oxide and stearic acid 8.0-10.0 part.
2. according to the described mesohigh fuel-resistant rubber semi-conductive shielding of claim 1 CABLE MATERIALS, it is characterized in that consisting of (weight):
100 parts of the fine or hydrogenation nitrile rubbers of fourth
Conductive carbon black 50-60 part
Graphite Powder 99 15-20 part
Softening agent 15-20 part
Two sulphur tetra methylthiurams and aliphatics polysulfide 1.0-3.0 part
Curing Dibenzo thiazole and zinc diethyldithiocarbamate 1.0-2.0 part
Zinc oxide and stearic acid 8.0-10.0 part
Anti-aging agent 1.0-1.5 part
Lubricant 1.0-1.5 part.
3. according to claim 1 or 2 described mesohigh fuel-resistant rubber semi-conductive shielding CABLE MATERIALS, it is characterized in that two sulphur tetra methylthiurams and aliphatics polysulfide ratio of mixture are 40-70: 30-60.
4. according to claim 1 or 2 described mesohigh fuel-resistant rubber semi-conductive shielding CABLE MATERIALS, it is characterized in that curing Dibenzo thiazole and zinc diethyldithiocarbamate ratio of mixture are near same-size ratio.
5. according to claim 1 or 2 described mesohigh fuel-resistant rubber semi-conductive shielding CABLE MATERIALS, it is characterized in that zinc oxide and stearic acid ratio of mixture are 4-5: 1.
6. one kind as high pressure fuel-resistant rubber semi-conductive shielding CABLE MATERIALS preparation as described in arbitrary claim among the claim 1-5: comprise required material mixingly, it is characterized in that earlier fine or hydrogenation nitrile rubber mastication reduces viscosity with fourth; Add other outer mixing ingredients of sulphur removal agent at least and promotor again, mixing back adds the vulcanization system batch mixes, opens bar slice or granulation.
7. according to the preparation of the described mesohigh fuel-resistant rubber semi-conductive shielding of claim 6 CABLE MATERIALS, it is characterized in that mastication is to plasticity value 0.4-0.5.
8. according to the preparation of the described mesohigh fuel-resistant rubber semi-conductive shielding of claim 6 CABLE MATERIALS, it is characterized in that the mastication temperature is not more than 60 ℃.
9. according to claim 6,7 or 8 described mesohigh fuel-resistant rubber semi-conductive shielding CABLE MATERIALS preparations, it is characterized in that mastication carries out at interval.
10. according to the preparation of the described mesohigh fuel-resistant rubber semi-conductive shielding of claim 9 CABLE MATERIALS, it is characterized in that melting temperature is not more than 90 ℃.
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| CN101440186B (en) * | 2008-12-24 | 2010-11-10 | 四川明星电缆股份有限公司 | Medium and low voltage fuel-resistant rubber semi-conductive shielding material for cable and preparation thereof |
| CN102097176A (en) * | 2011-03-04 | 2011-06-15 | 沈勇 | Shielded power cable |
| CN103113635A (en) * | 2013-01-15 | 2013-05-22 | 安徽华宇电缆集团有限公司 | Oil-resistant power cable material and preparation method thereof |
| CN103122085A (en) * | 2013-02-06 | 2013-05-29 | 上海驰程化工工贸有限公司 | Strippable semiconductive shielding rubber for rubber insulation and preparation method thereof |
| CN103554571A (en) * | 2013-10-25 | 2014-02-05 | 安徽文峰电子科技集团有限公司 | Oil-resistant and ozone-resistant nitrile rubber cable material |
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| CN106566175A (en) * | 2016-10-20 | 2017-04-19 | 成都新柯力化工科技有限公司 | Special semiconductive shielded graphene masterbatch for electric cables, and a preparation method thereof |
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| CN101834030A (en) * | 2010-05-05 | 2010-09-15 | 天津天缆集团有限公司北辰工厂 | High-temperature submersible electric pump cable |
| CN101834030B (en) * | 2010-05-05 | 2011-09-28 | 天津天缆集团有限公司北辰工厂 | High-temperature submersible electric pump cable |
| CN102097176A (en) * | 2011-03-04 | 2011-06-15 | 沈勇 | Shielded power cable |
| CN103113635A (en) * | 2013-01-15 | 2013-05-22 | 安徽华宇电缆集团有限公司 | Oil-resistant power cable material and preparation method thereof |
| CN103122085A (en) * | 2013-02-06 | 2013-05-29 | 上海驰程化工工贸有限公司 | Strippable semiconductive shielding rubber for rubber insulation and preparation method thereof |
| CN103122085B (en) * | 2013-02-06 | 2015-09-23 | 上海驰程化工工贸有限公司 | A kind of rubber insulation strippable semi-conductive shielding rubber and preparation method thereof |
| CN104119689A (en) * | 2013-04-28 | 2014-10-29 | 扬州大学 | Regenerated oil-resistant low-smoke halogen-free cable material and preparation method thereof |
| CN103554571A (en) * | 2013-10-25 | 2014-02-05 | 安徽文峰电子科技集团有限公司 | Oil-resistant and ozone-resistant nitrile rubber cable material |
| CN103897231A (en) * | 2014-03-01 | 2014-07-02 | 安徽省定兴电缆有限公司 | Heat-resistant anti-aging cable sheath material and preparation method thereof |
| CN103897231B (en) * | 2014-03-01 | 2016-05-18 | 安徽省定兴电缆有限公司 | Aging cable sheath material of a kind of heat-resistant and preparation method thereof |
| CN105524320A (en) * | 2016-01-22 | 2016-04-27 | 安徽慧艺线缆集团有限公司 | Shielding material for rubber cable |
| CN106566175A (en) * | 2016-10-20 | 2017-04-19 | 成都新柯力化工科技有限公司 | Special semiconductive shielded graphene masterbatch for electric cables, and a preparation method thereof |
| CN107286455A (en) * | 2017-07-19 | 2017-10-24 | 安徽国电电缆集团有限公司 | A kind of preparation method of middle-high voltage power cable shield semiconductors layer sizing |
| CN107383451A (en) * | 2017-08-31 | 2017-11-24 | 安徽华海特种电缆集团有限公司 | The mobile grease proofing cold-resistant voltage-resistant flat electric cable material of one kind |
| CN110556713A (en) * | 2018-06-01 | 2019-12-10 | 中国电力科学研究院有限公司 | anti-seismic structure for pillar type electrical equipment |
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Open date: 20080423 |