CN107236182B - Oil-resistant and mud-resistant radiation cross-linked flame-retardant cable material - Google Patents
Oil-resistant and mud-resistant radiation cross-linked flame-retardant cable material Download PDFInfo
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Abstract
The invention relates to an oil-resistant and mud-resistant radiation-crosslinked flame-retardant cable material which is prepared from the following materials in parts by weight: ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide terpolymer, high-density polyethylene, copolymer of polyethylene grafted maleic anhydride, carbon black, aluminum hydroxide flame retardant, magnesium hydroxide flame retardant, coupling agent, crosslinking sensitizer, antioxidant, silicone and lubricant; wherein the content of vinyl acetate VA in the ethylene-vinyl acetate copolymer is 33 percent, and the melt index of the ethylene-vinyl acetate copolymer is 0.2g/10 min; the crosslinking sensitizer is TMAIC prepolymer, the polymerization degree n is 2-10, the monomer is TMAIC, and the molecular weight is 291.35. The invention has low smoke, no toxicity and simple and convenient entrusted irradiation processing, and improves the compatibility of the filler and the base material in the blending material and the mechanical property of the material.
Description
Technical Field
The invention relates to the field of low-smoke halogen-free flame-retardant cable materials, in particular to an oil-resistant mud-irradiation-resistant crosslinked flame-retardant cable material.
Background
With the formal drilling of the offshore oil 981 of the 'sixth-generation deepwater semi-submersible drilling platform' which is independently designed and built in the first place in 2012, the deepwater strategy of the offshore oil industry in China is marked to take a substantial step, the technology for building large-scale deepwater platforms in China is mature, and meanwhile, higher technical requirements are provided for the supporting cables for the oil platforms. Due to the particularity of the use environment, the special cable for the oil platform is required to have the performances of oil resistance, slurry resistance, high temperature resistance, low temperature resistance, wear resistance, high mechanical strength, no halogen, low smoke and the like. For the cable used in the oil platform, the more rigorous oil resistance requirement and oil sludge resistance requirement are always the main problems of the research of the cable industry.
At present, not only are few manufacturers for producing special cables for oil platforms in China, but also few manufacturers with the production capacity of slurry-resistant sheath materials are few and unstable in slurry resistance, so that the cables and the materials mainly depend on import.
The mud-resistant cable patents for the petroleum platform published in China mostly only propose that the sheath adopts a low-smoke halogen-free mud-resistant material, and do not indicate the preparation technology of the material. How to solve the technical problems of high cost, large smoke generation amount during combustion, large equipment investment and complex process becomes the direction of efforts of ordinary technicians in the field.
Disclosure of Invention
The invention aims to provide an oil-resistant and slurry-resistant irradiation crosslinking flame-retardant cable material which is low-smoke and nontoxic, convenient to entrust irradiation processing and low in investment cost, and can be used for producing a halogen-free flame-retardant slurry-resistant sheath material meeting the standards of halogen-free/slurry-resistant cables for Norwegian NEK606 offshore platforms.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: an oil-resistant and mud-resistant radiation-crosslinked flame-retardant cable material comprises the following raw materials in parts by weight: 25-45 parts of ethylene-vinyl acetate copolymer, 12-18 parts of ethylene-vinyl acetate-carbon monoxide terpolymer, 30-45 parts of high-density polyethylene, 5-15 parts of copolymer of polyethylene grafted maleic anhydride, 8-10 parts of carbon black, 115 parts of aluminum hydroxide flame retardant, 35 parts of magnesium hydroxide flame retardant, 0.7-1.8 parts of coupling agent, 1.5-3 parts of crosslinking sensitizer, 1.4-2.4 parts of antioxidant, 3-4 parts of silicone and 0.5-1 part of lubricant;
the irradiation crosslinking flame-retardant cable material is obtained through the following steps:
the first step is as follows: ethylene vinyl acetate copolymer EVA, ethylene-vinyl acetate-carbon monoxide terpolymer and polyethylene grafted maleic anhydride copolymer which are measured according to the weight of the formula are mixed in a high-speed mixer at high speed for 30 seconds, and then are mixed, plasticized and granulated by a double-screw granulator, and the processing temperature is as follows: the conveying section is 120-130 ℃, the melting section is 140-155 ℃, the mixing section is 160-170 ℃, the exhaust section is 155-165 ℃, the homogenizing section is 155-165 ℃ and the machine head is 160-170 ℃;
the second step is that: adding carbon black, an aluminum hydroxide flame retardant, a magnesium hydroxide flame retardant, a silane coupling agent, a crosslinking sensitizer TMAIC prepolymer, an antioxidant 1010, an antioxidant DLTP, silicone master batches and a lubricant which are measured according to the weight of the formula into the materials, mixing the materials in a high-speed mixer for 30 seconds, and kneading, plasticizing and granulating the materials in a double-stage machine, wherein the double-stage machine comprises double screws, and the processing temperature is as follows: the temperature of the conveying section is 100-115 ℃, the temperature of the melting section is 120-135 ℃, the temperature of the mixing section is 140-150 ℃, the temperature of the exhaust section is 145-155 ℃, the temperature of the homogenizing section is 145-155 ℃, and the temperature of the machine head is 150-160 ℃, wherein the temperature of a single screw is: the temperature of the first zone is 120-135 ℃, the temperature of the second zone is 120-135 ℃, the temperature of the third zone is 120-135 ℃, the temperature of the machine head is 130-145 ℃, and the material is cut into particles, cooled by air and packaged;
the third step: extruding the material obtained in the second step on a production line of a wire and cable extruding machine at the temperature of 110-120 ℃ in a first area, 120-140 ℃ in a second area, 135-155 ℃ in a third area, 135-155 ℃ in a fourth area and 130-150 ℃ of a machine head, coating the material on a conductor wire core, and then performing irradiation processing, wherein the thermal extension is 15-25% after irradiation;
wherein the content of vinyl acetate VA in the ethylene-vinyl acetate copolymer is 33 percent, and the melt index of the ethylene-vinyl acetate copolymer is 0.2g/10 min;
the content of carbon monoxide in the ethylene-vinyl acetate-carbon monoxide terpolymer is 8-12%, the content of vinyl acetate VA in the ethylene-vinyl acetate copolymer EVA is 24-30%, and the melt index of the ethylene-vinyl acetate-carbon monoxide terpolymer is 35g/10 min;
the polyethylene is high-density polyethylene, and the melt index is 0.08g/10 min;
the grafting rate of the copolymer of polyethylene grafted maleic anhydride is 0.6-1.2%;
the carbon black is generated by a furnace method, the particle size is 12-30 nm, and the oil absorption value is 50-80 cc/100 g;
the halogen-free flame retardant is prepared by mixing aluminum hydroxide and magnesium hydroxide according to the weight ratio of 2-3: 1 mass ratio of the mixture to be compounded, and the average grain diameter of the mixture is 0.8-1.5 mu m;
the coupling agent is silane coupling agent A-172 or Z-6173;
the crosslinking sensitizer is a TMAIC prepolymer, the molecular structure is shown in the following formula, the polymerization degree n is 2-10, the monomer is TMAIC, and the molecular weight is 291.35;
the antioxidant is 1010 and DLTP according to the ratio of 0.8-1: 1-1.2 by mass ratio.
The technical scheme of the further improvement of the technical scheme is as follows:
1. in the scheme, the mass content of the effective component silicone in the silicone master batch is 50%.
2. In the above scheme, the lubricant is at least one of PE wax, EVA wax, calcium stearate, or zinc stearate.
3. In the scheme, the average particle size of the aluminum hydroxide flame retardant is 0.8-1.5 mu m.
4. In the scheme, the average particle size of the magnesium hydroxide flame retardant is 0.8-1.5 mu m.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the oil-resistant and mud-resistant radiation-crosslinked flame-retardant cable material selects ethylene-vinyl acetate copolymer EVA, ethylene-vinyl acetate-carbon monoxide terpolymer, polyethylene and polyethylene-grafted maleic anhydride copolymer as base material resin, aluminum hydroxide and magnesium hydroxide flame retardant and furnace carbon black are added, a double-stage machine, namely equipment consisting of double screws and single screws, is adopted under the action of silane coupling agent, crosslinking sensitizer TMAIC prepolymer, antioxidant and other auxiliaries, and the compatibility of a filler and the base material in a blended material can be improved and the mechanical property of the material is improved by a two-step technology; finally, the halogen-free flame-retardant sheath material for the slurry-resistant cable, which meets the standards of the halogen-free/slurry-resistant cable for the Norwegian NEK606 offshore platform, is prepared, and is subjected to irradiation processing to form the irradiation crosslinking slurry-resistant low-smoke halogen-free flame-retardant cable for the oil platform.
2. According to the oil-resistant and mud-resistant radiation-crosslinked flame-retardant cable material, the ethylene-vinyl acetate-carbon monoxide terpolymer is selected as the base material, and the oil resistance of the ethylene-vinyl acetate-carbon monoxide terpolymer is equivalent to that of EVM with high VA content under the condition that the VA content is kept low; the EVA copolymer, the high-density polyethylene and the PE grafted maleic anhydride copolymer are reasonably compounded, so that the defects of stickiness, caking and the like in the production process of the high VA content EVM are eliminated, and satisfactory heat resistance and low-temperature performance are maintained; more importantly, under the reinforcing effect of furnace carbon black (3.3-3.5 percent), excellent high oil resistance and slurry resistance are obtained, and after irradiation, the requirements of Norwegian standard NEK606 on oil resistance and slurry resistance are met.
3. The oil-resistant and mud-resistant radiation crosslinking flame-retardant cable material adopts TMAIC prepolymer as a crosslinking sensitizer, and has the other great characteristic that after the TMAIC prepolymer is used in a formula, the radiation crosslinking effect of the product is greatly improved, the radiation dose is reduced from the original 25Mrad to the current 15Mrad under the requirement of the same thermal elongation (10%), the processing difficulty and the processing cost of radiation are greatly reduced, the radiation crosslinking requirement of low thermal elongation required by high oil-resistant and mud-resistant is ensured to be easily met, and the realization of a scheme of high oil-resistant and mud-resistant is further promoted.
4. The oil-resistant and mud-resistant radiation-crosslinked flame-retardant cable material uses aluminum hydroxide and magnesium hydroxide to endow the product with halogen-free flame-retardant property, has obvious synergistic effect when used together with the lubricant silicone master batch, and can improve the flame-retardant effects of crusting, dripping resistance and the like of a composite flame-retardant system. Meanwhile, the silane coupling agent is added to modify the inorganic filler, so that the compatibility between the inorganic flame retardant and the base material can be improved, and the material is beneficial to improving the aging property, oil resistance and mud resistance of the material. The antioxidant system adopts a mode of matching antioxidant 1010 and DLTP, has obvious synergistic effect, so that the product can still meet certain aging performance requirements while obviously reducing the using amount of the antioxidant, namely, after certain high-temperature aging, the material structure and performance have certain retentivity, and the oil resistance and slurry resistance of the product are ensured; the formula of the conventional low-smoke halogen-free flame-retardant cable material is technically improved, the ethylene-vinyl acetate-carbon monoxide ternary copolymer is added to be matched with the carbon black in a reinforcing way, and the crosslinking effect of the high-efficiency crosslinking sensitizer TMAIC prepolymer is promoted, so that the oil resistance and the slurry resistance of the halogen-free flame-retardant sheath material are effectively improved, and finally, the requirements of the halogen-free/slurry-proof cable standard for Norwegian NEK606 offshore platforms can be well met.
Detailed Description
The invention is further described below with reference to the following examples:
example (b): an oil-resistant and mud-resistant radiation-crosslinked flame-retardant cable material comprises the following material formula:
preparation process
The first step is as follows: ethylene vinyl acetate copolymer EVA, ethylene-vinyl acetate-carbon monoxide terpolymer and polyethylene grafted maleic anhydride copolymer which are measured according to the weight of the formula are mixed in a high-speed mixer at high speed for 30 seconds, and then are mixed, plasticized and granulated by a double-screw granulator, and the processing temperature is as follows: the conveying section is 120-130 ℃, the melting section is 140-155 ℃, the mixing section is 160-170 ℃, the exhaust section is 155-165 ℃, the homogenizing section is 155-165 ℃ and the machine head is 160-170 ℃.
The second step is that: adding carbon black, an aluminum hydroxide flame retardant, a magnesium hydroxide flame retardant, a silane coupling agent, a crosslinking sensitizer TMAIC prepolymer, an antioxidant 1010, an antioxidant DLTP, silicone master batches and a lubricant which are measured according to the weight of the formula into the materials, mixing the materials in a high-speed mixer for 30 seconds, and kneading, plasticizing and granulating the materials in a double-stage machine, wherein the double-stage machine comprises double screws, and the processing temperature is as follows: the temperature of the conveying section is 100-115 ℃, the temperature of the melting section is 120-135 ℃, the temperature of the mixing section is 140-150 ℃, the temperature of the exhaust section is 145-155 ℃, the temperature of the homogenizing section is 145-155 ℃, and the temperature of the machine head is 150-160 ℃, wherein the temperature of a single screw is: the temperature of the first zone is 120-135 ℃, the temperature of the second zone is 120-135 ℃, the temperature of the third zone is 120-135 ℃, the temperature of the machine head is 130-145 ℃, and the material is cut into particles, cooled by air and packaged.
The third step: extruding the material obtained in the second step on a production line of a wire and cable extruding machine at the temperature of 110-120 ℃ in the first area, 120-140 ℃ in the second area, 135-155 ℃ in the third area, 135-155 ℃ in the fourth area and 130-150 ℃ in a machine head, coating the material on a conductor wire core, performing irradiation processing, and thermally extending for 15-25% after irradiation to obtain the cable meeting the standards of the halogen-free/slurry-proof cable for the Norwegian NEK606 offshore platform, and detecting various indexes according to the cable standards.
2. Technical index
The embodiment shows that the ethylene-vinyl acetate-carbon monoxide terpolymer and the high-efficiency crosslinking sensitizer TMAIC prepolymer are added in the material formula, so that the material can generate more sufficient, uniform and effective crosslinking reaction, and has higher oil resistance and mud resistance; the product prepared by using the cable sheath material can meet the requirements of halogen-free/slurry-proof cable standards for Norwegian NEK606 offshore platforms.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (5)
1. An oil-resistant and mud-resistant radiation-crosslinked flame-retardant cable material is characterized in that: the raw material formula comprises the following materials in parts by weight: 25-45 parts of ethylene-vinyl acetate copolymer, 12-18 parts of ethylene-vinyl acetate-carbon monoxide terpolymer, 30-45 parts of high-density polyethylene, 5-15 parts of copolymer of polyethylene grafted maleic anhydride, 8-10 parts of carbon black, 115 parts of aluminum hydroxide flame retardant, 35 parts of magnesium hydroxide flame retardant, 0.7-1.8 parts of coupling agent, 1.5-3 parts of crosslinking sensitizer, 1.4-2.4 parts of antioxidant, 3-4 parts of silicone and 0.5-1 part of lubricant;
the irradiation crosslinking flame-retardant cable material is obtained through the following steps:
the first step is as follows: ethylene vinyl acetate copolymer EVA, ethylene-vinyl acetate-carbon monoxide terpolymer and polyethylene grafted maleic anhydride copolymer which are measured according to the weight of the formula are mixed in a high-speed mixer at high speed for 30 seconds, and then are mixed, plasticized and granulated by a double-screw granulator, and the processing temperature is as follows: the conveying section is 120-130 ℃, the melting section is 140-155 ℃, the mixing section is 160-170 ℃, the exhaust section is 155-165 ℃, the homogenizing section is 155-165 ℃ and the machine head is 160-170 ℃;
the second step is that: adding carbon black, an aluminum hydroxide flame retardant, a magnesium hydroxide flame retardant, a silane coupling agent, a crosslinking sensitizer TMAIC prepolymer, an antioxidant 1010, an antioxidant DLTP, silicone master batches and a lubricant which are measured according to the weight of the formula into the materials, mixing the materials in a high-speed mixer for 30 seconds, and kneading, plasticizing and granulating the materials in a double-stage machine, wherein the double-stage machine comprises double screws, and the processing temperature is as follows: the temperature of the conveying section is 100-115 ℃, the temperature of the melting section is 120-135 ℃, the temperature of the mixing section is 140-150 ℃, the temperature of the exhaust section is 145-155 ℃, the temperature of the homogenizing section is 145-155 ℃, and the temperature of the machine head is 150-160 ℃, wherein the temperature of a single screw is: the temperature of the first zone is 120-135 ℃, the temperature of the second zone is 120-135 ℃, the temperature of the third zone is 120-135 ℃, the temperature of the machine head is 130-145 ℃, and the material is cut into particles, cooled by air and packaged;
the third step: extruding the material obtained in the second step on a production line of a wire and cable extruding machine at the temperature of 110-120 ℃ in a first area, 120-140 ℃ in a second area, 135-155 ℃ in a third area, 135-155 ℃ in a fourth area and 130-150 ℃ of a machine head, coating the material on a conductor wire core, and then performing irradiation processing, wherein the thermal extension is 15-25% after irradiation;
wherein the content of vinyl acetate VA in the ethylene-vinyl acetate copolymer is 33 percent, and the melt index of the ethylene-vinyl acetate copolymer is 0.2g/10 min;
the content of carbon monoxide in the ethylene-vinyl acetate-carbon monoxide terpolymer is 8-12%, the content of vinyl acetate VA in the ethylene-vinyl acetate copolymer EVA is 24-30%, and the melt index of the ethylene-vinyl acetate-carbon monoxide terpolymer is 35g/10 min;
the melt index of the high-density polyethylene is 0.08g/10 min;
the grafting rate of the copolymer of polyethylene grafted maleic anhydride is 0.6-1.2%;
the carbon black is generated by a furnace method, the particle size is 12-30 nm, and the oil absorption value is 50-80 cc/100 g;
the coupling agent is silane coupling agent A-172 or Z-6173;
the crosslinking sensitizer is a TMAIC prepolymer, the molecular structure is shown in the following formula, the polymerization degree n is 2-10, the monomer is TMAIC, and the molecular weight is 291.35;
the antioxidant is 1010 and DLTP according to the ratio of 0.8-1: 1-1.2 by mass ratio.
2. The oil-resistant mud radiation-resistant crosslinked flame-retardant cable material according to claim 1, characterized in that: the mass content of the effective component silicone in the silicone master batch is 50%.
3. The oil-resistant mud radiation-resistant crosslinked flame-retardant cable material according to claim 1, characterized in that: the lubricant is at least one of PE wax, EVA wax, calcium stearate or zinc stearate.
4. The oil-resistant mud radiation-resistant crosslinked flame-retardant cable material according to claim 1, characterized in that: the average particle size of the aluminum hydroxide flame retardant is 0.8-1.5 mu m.
5. The oil-resistant mud radiation-resistant crosslinked flame-retardant cable material according to claim 1, characterized in that: the average particle size of the magnesium hydroxide flame retardant is 0.8-1.5 mu m.
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| CN201710301895.6A CN107236182B (en) | 2015-05-11 | 2015-05-11 | Oil-resistant and mud-resistant radiation cross-linked flame-retardant cable material |
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| CN201710301895.6A Active CN107236182B (en) | 2015-05-11 | 2015-05-11 | Oil-resistant and mud-resistant radiation cross-linked flame-retardant cable material |
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| CN105400046B (en) * | 2015-12-15 | 2018-09-07 | 中广核三角洲（苏州）高聚物有限公司 | Automotive line 150 DEG C of cross-linking radiation high abrasion non-halogen flame-retardant cables and preparation method thereof |
| CN105469867B (en) * | 2015-12-16 | 2018-04-13 | 江苏亨通线缆科技有限公司 | Wear-resistant special cable used for rolling stock |
| CN105551585B (en) * | 2015-12-16 | 2018-01-09 | 江苏亨通线缆科技有限公司 | High-intensity high combustion locomotive cable |
| CN105462052A (en) * | 2015-12-24 | 2016-04-06 | 上海至正道化高分子材料股份有限公司 | 125 DEG C irradiation crosslinking low-smoke halogen-free cable material for automotive wires and preparation method thereof |
| CN105761781A (en) * | 2015-12-31 | 2016-07-13 | 江苏亨通线缆科技有限公司 | Robot signal cable |
| CN105469884A (en) * | 2015-12-31 | 2016-04-06 | 江苏亨通线缆科技有限公司 | Tensile flexible power cable for robot |
| CN105694518A (en) * | 2016-03-18 | 2016-06-22 | 建湖东方电缆材料有限公司 | Hot material type halogen-free low-smoke flame-retardant sheath material |
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| CN109280256B (en) * | 2018-08-07 | 2020-12-29 | 中广核高新核材科技（苏州）有限公司 | Low-VOC halogen-free flame-retardant polyolefin cable material for locomotive |
| CN112625648B (en) * | 2020-12-17 | 2022-11-01 | 广东长鹿新材料科技有限公司 | High-temperature-resistant oil bath room-temperature curing silicone rubber and preparation method thereof |
| CN113061314B (en) * | 2021-03-25 | 2022-08-23 | 浙江新恒泰新材料有限公司 | IXPE foam material prepared by IXPE foaming leftover material and preparation method thereof |
| CN113773596A (en) * | 2021-09-03 | 2021-12-10 | 会通新材料(上海)有限公司 | High-mechanical-property high-flame-retardant mud-resistant cable sheath material and preparation method thereof |
| CN114149772B (en) * | 2021-11-25 | 2023-04-18 | 广州番禺电缆集团有限公司 | Hot melt adhesive for crosslinked polyethylene cable connector and preparation method thereof |
| CN116396551A (en) * | 2023-03-22 | 2023-07-07 | 金发科技股份有限公司 | Polyethylene composition and preparation method and application thereof |
| CN116589783A (en) * | 2023-06-17 | 2023-08-15 | 上海新上化高分子材料有限公司 | Silane self-crosslinking mud-resistant low-smoke and halogen-free material and preparation method thereof |
| EP4501584A1 (en) * | 2023-08-04 | 2025-02-05 | Ingenia Polymers International S.A. | Poly(vinyl ester) polymer processing aids for polyolefins |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN104927176B (en) | 2018-02-09 |
| CN107236182A (en) | 2017-10-10 |
| CN107236166B (en) | 2020-12-29 |
| CN107236166A (en) | 2017-10-10 |
| CN104927176A (en) | 2015-09-23 |
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