CN107236182A - The oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material - Google Patents

The oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material Download PDF

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CN107236182A
CN107236182A CN201710301895.6A CN201710301895A CN107236182A CN 107236182 A CN107236182 A CN 107236182A CN 201710301895 A CN201710301895 A CN 201710301895A CN 107236182 A CN107236182 A CN 107236182A
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vinyl acetate
retardant
resistance
flame
ethylene
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CN107236182B (en
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高晓慧
曾光新
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Zhongguang Nuclear High-tech Nuclear Material Technology (Suzhou) Co., Ltd.
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China Guangdong Nuclear Material Ltd Co Of Group Of High
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Abstract

A kind of oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material of the present invention, is made up of the material of following parts by weight：Ethylene-vinyl acetate copolymer, ethylene-vinyl acetate carbon monoxide terpolymer, high density polyethylene (HDPE), the copolymer of Research of Grafting Malaic Anhydride Onto Polyethylene, carbon black, aluminium hydroxide fire retardant, flame retardant of magnesium hydroxide, coupling agent, crosslinking sensitizer, antioxidant, silicone, lubricant；Wherein, the vinyl acetate VA contents in the ethylene-vinyl acetate copolymer are 33%, and the melt index (MI) of this ethylene-vinyl acetate copolymer is 0.2g/10min；The crosslinking sensitizer be front three for allyl iso cyanurate TMAIC prepolymers, polymerization degree n is 2~10, monomer be front three for allyl iso cyanurate TMAIC, molecular weight is 291.35.LSZH of the present invention, commission irradiation processing are easy, improve the mechanical performance of the compatibility and material of filler and base material in intermingling material.

Description

The oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material
Technical field
The present invention relates to fireproofing cable material without halide field, more particularly to a kind of oil resistant irradiation cross-linking flame-retardant of resistance to mud electricity Cable material.
Background technology
With Chinese seat of honour autonomous Design, " the 6th generation deep water semi-submersible drilling platform " offshore oil built in 2012 981 formally spud in, indicates that the deep water strategy of Chinese Offshore Oil Industry has stepped substantial paces, the country builds large-scale The technology of deep water platform is ripe, while used for oil platform it is also proposed higher technical requirements with cable to matched. Special cable used for oil platform, because of the particularity of its use environment, it is desirable to which it has oil resistant, resistance to mud, high temperature resistant, resistance to low The performances such as warm, wear-resisting, high mechanical properties, Halogen, low cigarette.For cable used for oil platform, harsher oil resistant requirement and oil resistant Mud requirement is always the main bugbear of cable industry research.
The domestic producer for not only producing special cable used for oil platform is few at present, and possesses the material of resistance to shape mud sheath production The producer of ability is even more few, and very unstable in terms of resistance to mud property, so cable and material are depended on Import.
The domestic disclosed relevant cable of resistance to mud patent used for oil platform, only proposes that sheath uses low smoke and zero halogen mostly Resistance to mud materials, the technology of preparing of material is not pointed out.Smoke amount is big when how to solve cost height, burning, equipment investment is big, The cumbersome technical problem of technique, the direction made great efforts as those of ordinary skill in the art.
The content of the invention
It is an object of the invention to provide a kind of oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material, the resistance to mud irradiation of the oil resistant Cross-linked fire-resistant cable material LSZH, commission irradiation processing are easy, input cost is low, and can produce and meet Norway The halogen-free flameproof material of resistance to shape mud sheath of NEK606 offshore platforms Halogen/anti-mud cable standard.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of oil resistant irradiation cross-linking flame-retardant of resistance to mud Cable material, composition of raw materials is made up of the material of following parts by weight：25~45 parts of ethylene-vinyl acetate copolymer, ethyl vinyl acetate 12~18 parts of ethylenecarbon monoxide terpolymer, 30~45 parts of high density polyethylene (HDPE), the copolymerization of Research of Grafting Malaic Anhydride Onto Polyethylene 5~15 parts of thing, 8 ~ 10 parts of carbon black, 115 parts of aluminium hydroxide fire retardant, 35 parts of flame retardant of magnesium hydroxide, 0.7 ~ 1.8 part of coupling agent, 1.5 ~ 3 parts of crosslinking sensitizer, 1.4 ~ 2.4 parts of antioxidant, 3~4 parts of silicone, 0.5~1 part of lubricant；
The resistance to flame-proof cable material of cross-linking radiation is obtained by following steps：
The first step：By the ethylene-vinyl acetate copolymer EVA measured by formulation weight, ethene-vinyl acetate-carbon monoxide ternary The copolymer of copolymer, polyethylene and Research of Grafting Malaic Anhydride Onto Polyethylene is mixed 30 seconds in high-speed mixer high speed, Ran Houjing Dual-screw pelletizer mixing plasticizing is granulated, and processing temperature is：120~130 DEG C of transportation section, 140~155 DEG C of melt zone, mixing section 160~170 DEG C, 155~165 DEG C of exhaust section, 155~165 DEG C of homogenizing zone, 160~170 DEG C of head；
Second step：Above-mentioned material is added into the carbon black measured by formulation weight, aluminium hydroxide fire retardant, magnesium hydroxide flame retardant Agent, silane coupler, crosslinking sensitizer front three are for allyl iso cyanurate TMAIC prepolymers, antioxidant 1010, antioxidant DLTP, silicone master batch and lubricant, are mixed 30 seconds in high-speed mixer, then kneading plasticizing granulation, double ranks in double rank machines The processing temperature of machine including twin-screw is：100~115 DEG C of transportation section, 120~135 DEG C of melt zone, 140~150 DEG C of mixing section, 145~155 DEG C of exhaust section, 145~155 DEG C of homogenizing zone, 150~160 DEG C of head, including single screw rod temperature are：First area 120~ 135 DEG C, the second 120~135 DEG C of area, the 3rd 120~135 DEG C of area, 130~145 DEG C of head is packed after pelletizing is air-cooled；
3rd step：Second step resulting materials are squeezed on line machine production line in electric wire, in 110~120 DEG C of an area, two areas 120 ~140 DEG C, three 135~155 DEG C of areas, four 135~155 DEG C of areas extrude at a temperature of 130~150 DEG C of head, are coated on conductor lines On core, then irradiation processing is carried out, heat extension 15%~25% after irradiation；
Wherein, the vinyl acetate VA contents in the ethylene-vinyl acetate copolymer are 33%, this ethylene-vinyl acetate copolymer Melt index (MI) is 0.2g/10min；
Carbon monoxide content is 8~12% in the ethene-vinyl acetate-carbon monoxide terpolymer, and ethylene-vinyl acetate is common Vinyl acetate VA contents in polymers EVA are 24~30%, the melt of the ethene-vinyl acetate-carbon monoxide terpolymer Index is 35g/10min；
The polyethylene is high density polyethylene (HDPE), and melt index (MI) is 0.08g/10min；
The grafting rate of the copolymer of the Research of Grafting Malaic Anhydride Onto Polyethylene is 0.6%~1.2%；
The carbon black is the carbon black that oven process is generated, and particle diameter is 12~30nm, and oil factor is 50~80cc/100g；
The halogen-free flame retardants is aluminium hydroxide and magnesium hydroxide according to 2 ~ 3：1 mass ratio compounds the mixture to be formed, and it is flat Equal particle diameter is all 0.8~1.5 μm；
The coupling agent is silane coupling A -172 or Z-6173；
The crosslinking sensitizer be front three for allyl iso cyanurate TMAIC prepolymers, molecular structure is shown below, the degree of polymerization N be 2~10, monomer be front three for allyl iso cyanurate TMAIC, molecular weight is 291.35；
The antioxidant is 1010 and DLTP according to 0.8 ~ 1：The mixture of 1 ~ 1.2 mass ratio compounding.
The further improved technical scheme of above-mentioned technical proposal is as follows：
1. in such scheme, the mass content of active ingredient silicone is 50% in the silicone master batch.
2. in such scheme, the lubricant is at least one of PE waxes, EVA waxes, calcium stearate or zinc stearate.
3. in such scheme, the aluminium hydroxide fire retardant average grain diameter is 0.8 ~ 1.5 μm.
4. in such scheme, the flame retardant of magnesium hydroxide average grain diameter is 0.8 ~ 1.5 μm.
Due to the utilization of above-mentioned technical proposal, the present invention has following advantages compared with prior art：
1. the oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material of the present invention, from ethylene-vinyl acetate copolymer EVA, ethene-vinegar The copolymer of sour ethylenecarbon monoxide terpolymer, polyethylene and Research of Grafting Malaic Anhydride Onto Polyethylene is used as substrate resin, addition Aluminium hydroxide and flame retardant of magnesium hydroxide, and furnace black, and in silane coupler, crosslinking sensitizer TMAIC prepolymers and resist Using double rank machines under the promoter effects such as oxygen agent, i.e., the equipment being made up of twin-screw and single screw rod, through two-step mode technique, can be improved The compatibility of filler and base material in intermingling material, improves the mechanical performance of material；Put down at the final obtained Norway NEK606 seas that meet Platform turns into oil with the halogen-free flame-retardant sheath material of the cable of resistance to mud of Halogen/anti-mud cable standard after irradiated processing The platform cross-linking radiation low-smoke halogen-free inflaming-retarding cable of resistance to mud.
2. the oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material of the present invention, base material is aoxidized from ethene-vinyl acetate-one Carbon terpolymer is one of features of the present invention, and the copolymer can be in the case where keeping VA contents relatively low, oil resistance Equivalent to the EVM of high VA contents；Carried out with EVA copolymer, high density polyethylene (HDPE) and PE grafted maleics anhydride copolymer rationally multiple Match somebody with somebody, not only eliminate the shortcomings of high VA contents EVM has tacky, caking in process of production, maintain gratifying heat-resisting Property and cryogenic property；Importantly, in furnace black（3.3%~3.5% ratio）Strengthening action under, achieve superior height Oil resistance and resistance to mud property, after irradiation, pass through the resistance to mud property requirement of Norske standard NEK606 oil resistant.
3. the oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material of the present invention, using front three for allyl iso cyanurate TMAIC Prepolymer is another big feature of the present invention, after TMAIC prepolymers are used in formula, significantly carried as crosslinking sensitizer The high cross-linking radiation effect of product, in identical hot elongation percentage（10%）Requirement under, irradiation dose is reduced from original 25Mrad To current 15Mrad, the difficulty of processing and processing cost of irradiation are greatly reduced, it is ensured that it easily reaches the resistance to mud of high oil resistant The cross-linking radiation requirement of required low-heat elongation percentage, further contributes to the realization of the resistance to mud scheme of high oil resistant.
4. the oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material of the present invention, using aluminium hydroxide, magnesium hydroxide, assigns production Product halogen-free flame retardant feature, is used cooperatively with lubricant silicone master batch, with obvious synergistic effect, can improve composite flame-proof body The flame retardant effects such as the crusting of system, resistance to drippage.Add silane coupler simultaneously to be modified inorganic filler, it is possible to increase inorganic resistance The compatibility between agent and base-material is fired, is all beneficial for improving material aging performance, oil resistivity and resistance to mud property so 's.Antioxidant system is by the way of antioxidant 1010 and DLTP are used cooperatively, with obvious synergy so that product is bright While aobvious reduction antioxidant consumption, certain ageing properties requirement, i.e., after certain high temperature ageing, material knot can be still met Structure and performance have certain retentivity, while also ensure that the oil resistivity and resistance to mud property of product；To conventional low smoke and zero halogen The formula of fire-resistant cable material carries out technological improvement, is mended by adding ethene-vinyl acetate-carbon monoxide terpolymer with carbon black It is strong to coordinate, and efficient promotion of the crosslinking sensitizer TMAIC prepolymers to cross-linking effect, it is effectively improved halogen-free flameproof shield The oil resistance of jacking and resistance to mud property, Norway NEK606 offshore platforms Halogen/anti-mud may finally be met well The requirement of cable standard.
Embodiment
With reference to embodiment, the invention will be further described：
Embodiment：A kind of oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material, material prescription：
Preparation technology
The first step：By the ethylene-vinyl acetate copolymer EVA measured by formulation weight, ethene-vinyl acetate-carbon monoxide ternary The copolymer of copolymer, polyethylene and Research of Grafting Malaic Anhydride Onto Polyethylene is mixed 30 seconds in high-speed mixer high speed, Ran Houjing Dual-screw pelletizer mixing plasticizing is granulated, and processing temperature is：120~130 DEG C of transportation section, 140~155 DEG C of melt zone, mixing section 160~170 DEG C, 155~165 DEG C of exhaust section, 155~165 DEG C of homogenizing zone, 160~170 DEG C of head.
Second step：Above-mentioned material is added into the carbon black measured by formulation weight, aluminium hydroxide fire retardant, magnesium hydroxide resistance Agent, silane coupler, crosslinking sensitizer front three are fired for allyl iso cyanurate TMAIC prepolymers, antioxidant 1010, antioxidant DLTP, silicone master batch and lubricant, are mixed 30 seconds in high-speed mixer, then kneading plasticizing granulation, double ranks in double rank machines The processing temperature of machine including twin-screw is：100~115 DEG C of transportation section, 120~135 DEG C of melt zone, 140~150 DEG C of mixing section, 145~155 DEG C of exhaust section, 145~155 DEG C of homogenizing zone, 150~160 DEG C of head, including single screw rod temperature are：First area 120~ 135 DEG C, the second 120~135 DEG C of area, the 3rd 120~135 DEG C of area, 130~145 DEG C of head is packed after pelletizing is air-cooled.
3rd step：Second step resulting materials are squeezed on line machine production line in electric wire, in 110~120 DEG C of an area, 2nd area 120~140 DEG C, three 135~155 DEG C of areas, four 135~155 DEG C of areas extrude at a temperature of 130~150 DEG C of head, are coated on and lead On body core, then irradiation processing is carried out, heat extension 15%~25%, becomes and meet Norway NEK606 offshore platform nothings after irradiation Indices are detected by the cable of halogen/anti-mud cable standard according to cable standard.
2nd, technical indicator
As can be seen from the above-described embodiment, the present invention in material prescription by adding ethene-vinyl acetate-carbon monoxide ternary Copolymer and efficient crosslinking sensitizer TMAIC prepolymers so that more full and uniform effective cross-linking reaction can occur for material, both And with higher oil resistivity and resistance to mud property；Norway NEK606 seas can be met using product made from the cable jacket material The requirement of upper mounting plate Halogen/anti-mud cable standard.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.

Claims (5)

1. a kind of oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material, it is characterised in that：Composition of raw materials by following parts by weight material Material composition：25~45 parts of ethylene-vinyl acetate copolymer, 12~18 parts of ethene-vinyl acetate-carbon monoxide terpolymer, height 8 ~ 10 parts of 5~15 parts of copolymer, carbon black, the aluminium hydroxide flame-retardant of 30~45 parts of density polyethylene, Research of Grafting Malaic Anhydride Onto Polyethylene 115 parts of agent, 35 parts of flame retardant of magnesium hydroxide, 0.7 ~ 1.8 part of coupling agent, 1.5 ~ 3 parts of crosslinking sensitizer, antioxidant 1.4 ~ 2.4 Part, 3~4 parts of silicone, 0.5~1 part of lubricant；
The resistance to flame-proof cable material of cross-linking radiation is obtained by following steps：
The first step：By the ethylene-vinyl acetate copolymer EVA measured by formulation weight, ethene-vinyl acetate-carbon monoxide ternary The copolymer of copolymer, polyethylene and Research of Grafting Malaic Anhydride Onto Polyethylene is mixed 30 seconds in high-speed mixer high speed, Ran Houjing Dual-screw pelletizer mixing plasticizing is granulated, and processing temperature is：120~130 DEG C of transportation section, 140~155 DEG C of melt zone, mixing section 160~170 DEG C, 155~165 DEG C of exhaust section, 155~165 DEG C of homogenizing zone, 160~170 DEG C of head；
Second step：Above-mentioned material is added into the carbon black measured by formulation weight, aluminium hydroxide fire retardant, magnesium hydroxide flame retardant Agent, silane coupler, crosslinking sensitizer front three are for allyl iso cyanurate TMAIC prepolymers, antioxidant 1010, antioxidant DLTP, silicone master batch and lubricant, are mixed 30 seconds in high-speed mixer, then kneading plasticizing granulation, double ranks in double rank machines The processing temperature of machine including twin-screw is：100~115 DEG C of transportation section, 120~135 DEG C of melt zone, 140~150 DEG C of mixing section, 145~155 DEG C of exhaust section, 145~155 DEG C of homogenizing zone, 150~160 DEG C of head, including single screw rod temperature are：First area 120~ 135 DEG C, the second 120~135 DEG C of area, the 3rd 120~135 DEG C of area, 130~145 DEG C of head is packed after pelletizing is air-cooled；
3rd step：Second step resulting materials are squeezed on line machine production line in electric wire, in 110~120 DEG C of an area, two areas 120 ~140 DEG C, three 135~155 DEG C of areas, four 135~155 DEG C of areas extrude at a temperature of 130~150 DEG C of head, are coated on conductor lines On core, then irradiation processing is carried out, heat extension 15%~25% after irradiation；
Wherein, the vinyl acetate VA contents in the ethylene-vinyl acetate copolymer are 33%, this ethylene-vinyl acetate copolymer Melt index (MI) is 0.2g/10min；
Carbon monoxide content is 8~12% in the ethene-vinyl acetate-carbon monoxide terpolymer, and ethylene-vinyl acetate is common Vinyl acetate VA contents in polymers EVA are 24~30%, the melt of the ethene-vinyl acetate-carbon monoxide terpolymer Index is 35g/10min；
The polyethylene is high density polyethylene (HDPE), and melt index (MI) is 0.08g/10min；
The grafting rate of the copolymer of the Research of Grafting Malaic Anhydride Onto Polyethylene is 0.6%~1.2%；
The carbon black is the carbon black that oven process is generated, and particle diameter is 12~30nm, and oil factor is 50~80cc/100g；
The halogen-free flame retardants is aluminium hydroxide and magnesium hydroxide according to 2 ~ 3：1 mass ratio compounds the mixture to be formed；
The coupling agent is silane coupling A -172 or Z-6173；
The crosslinking sensitizer be front three for allyl iso cyanurate TMAIC prepolymers, molecular structure is shown below, the degree of polymerization N be 2~10, monomer be front three for allyl iso cyanurate TMAIC, molecular weight is 291.35；
The antioxidant is 1010 and DLTP according to 0.8 ~ 1：The mixture of 1 ~ 1.2 mass ratio compounding.
2. the oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material according to claim 1, it is characterised in that：The silicone is female The mass content of active ingredient silicone is 50% in grain.
3. the oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material according to claim 1, it is characterised in that：The lubricant For at least one of PE waxes, EVA waxes, calcium stearate or zinc stearate.
4. the oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material according to claim 1, it is characterised in that：The hydroxide Aluminium fire retardant average grain diameter is 0.8 ~ 1.5 μm.
5. the oil resistant irradiation cross-linking flame-retardant of resistance to mud cable material according to claim 1, it is characterised in that：The hydroxide Magnesium fire retardant average grain diameter is 0.8 ~ 1.5 μm.
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