CN114249937B - Irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for thin-wall ship cable, and preparation method and application thereof - Google Patents
Irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for thin-wall ship cable, and preparation method and application thereof Download PDFInfo
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- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
Abstract
The invention relates to an irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for a thin-wall ship cable, and a preparation method and application thereof, wherein the irradiation crosslinking low-smoke halogen-free flame-retardant insulating material comprises the following raw materials in parts by weight: 40-60 parts of ultra-high molecular weight polyethylene, 10-30 parts of polyolefin elastomer, 10-30 parts of processing modified resin, 10-30 parts of polyolefin grafted maleic anhydride, 120-160 parts of inorganic flame retardant, 10-30 parts of flame retardant synergist, 1-3 parts of composite antioxidant, 0.5-2 parts of lubricant and 0.5-2.5 parts of irradiation crosslinking auxiliary agent; the inorganic flame retardant is prepared by mixing magnesium hydroxide and aluminum hydroxide according to the mass ratio of (4-7) to (1-3); the flame retardant synergist is non-metal ore or metal oxide. The insulating material disclosed by the invention has excellent scratch and wear resistance and long-term heat aging resistance after being subjected to irradiation crosslinking, can be subjected to long-term aging at 105 ℃ for 2000 hours to achieve the effect of no cracking, and has excellent flame retardant property and mechanical property.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for a thin-wall ship cable, a preparation method and application thereof.
Background
Modern ships have higher and higher requirements on digitalization and informatization of ships, and the ships are required to be equipped with a large number of communication wires and cables. The space utilization ratio of the effective space of the ship can be increased by the limitation of the space and the bearing of the sea fight, so that the outer diameter of the cable is reduced, the weight of the cable is lightened, the space utilization ratio can be improved, the dead weight of the ship is reduced, the effective load is increased, and the maneuvering performance is enhanced, thereby having great significance for enhancing the fight force of the ship.
At present, most of the cables for ships in China are of a general structure, the dead weight of the cables is relatively large, the outer diameter of the cables is large, the development needs of novel ships cannot be met, and the cables for ships are developed towards the directions of low smoke, low toxicity, thin wall and light weight.
The development direction of halogen-free thin wall light weight of ship cable inevitably puts new performance requirements on the cable materials used. The thickness of the insulation wall of the thin-wall cable is only 0.2-0.3mm, which puts higher requirements on the scratch and abrasion resistance of the insulation material; in addition, considering the use condition, the cable is required to resist long-term heat aging, and the cable is not broken down and does not crack after being aged at 105 ℃ for 20000 hours; low smoke, no halogen, flame retardance and no toxicity; the solvent resistance is good, and the paint can be kept in the environment of mineral oil and fuel oil.
Therefore, there is an urgent need in the art to develop an insulating material for low-smoke halogen-free thin-wall ship cables, which has excellent performance and relatively low price.
Disclosure of Invention
In order to solve the technical problems of poor scraping performance and poor thermal aging resistance of the insulating material for the thin-wall ship cable, the irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for the thin-wall ship cable and the preparation method and application thereof are provided. The insulating material disclosed by the invention can completely meet the technical requirements in DNVGL-CP-0400 in performance after irradiation crosslinking, has excellent scratch and wear resistance and long-term heat aging resistance, can resist long-term aging at 105 ℃ for 2000 hours, achieves the effect of no cracking, and is excellent in flame retardance, electrical property and mechanical property, good in processability and suitable for high-speed extrusion.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
the irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for the thin-wall ship cable comprises the following raw materials in parts by weight:
40 to 60 parts of ultra-high molecular weight polyethylene,
10 to 30 parts of polyolefin elastomer,
10 to 30 parts of processing modified resin,
10 to 30 parts of polyolefin grafted maleic anhydride,
120-160 parts of inorganic flame retardant,
10 to 30 parts of flame retardant synergist,
1 to 3 parts of composite antioxidant,
0.5 to 2 parts of lubricant,
0.5 to 2.5 portions of irradiation crosslinking auxiliary agent;
the inorganic flame retardant is prepared by mixing magnesium hydroxide and aluminum hydroxide according to the mass ratio of (4-7) to (1-3);
the flame retardant synergist is nonmetal ore or metal oxide;
the composite antioxidant is prepared by mixing an antioxidant and an anti-copper agent according to the mass ratio of (1-5) to (0.2-1).
Further, the relative molecular mass of the ultra-high molecular weight polyethylene is 300-500 ten thousand g/mol.
Further, the processing modified resin is a mixture of LDPE and HDPE according to any ratio; the melt index of the LDPE and the HDPE is 10g/10 min-100 g/10min.
Further, the polyolefin elastomer is one of ethylene-octene copolymer, ethylene-hexene copolymer and ethylene-propylene copolymer; the polyolefin elastomer had a density of 0.866g/cm 3 ～0.900g/cm 3 。
Further, the polyolefin grafted maleic anhydride is one or more of low-density polyethylene grafted maleic anhydride, linear low-density polyethylene grafted maleic anhydride and ethylene-octyl copolymer grafted maleic anhydride; the grafting rate of the maleic anhydride in the polyolefin grafted maleic anhydride is 0.5-2 wt%.
Further, the nonmetallic ore is one of nano attapulgite, nano montmorillonite and nano mica powder; the metal oxide is nano zinc oxide.
Further, the antioxidant is a mixture of at least two of 1010, DLTP, 168, 1098, DSTP, 1790, 412S; the copper inhibitor is one or more of N, N ' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, (3, 5-di-tert-butyl-4-hydroxyphenyl) oxalyl propionate (diimino-2, 1-ethylene ester), N ' -di (beta-naphthyl) p-phenylenediamine and N-phenyl-N ' -isopropyl p-phenylenediamine.
Further, the lubricant is one or more of polyethylene wax, microcrystalline paraffin, zinc stearate and silicone master batch; the cross-linking auxiliary agent is one or more of triallyl hydroxyurea, triallyl isocyanurate, trimethylol propane trimethacrylate and 1, 2-polybutadiene.
The invention also provides a preparation method of the irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for the thin-wall ship cable, which comprises the following steps: premixing the raw materials, banburying into master batch, and finally extruding and granulating to obtain the irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for the thin-wall ship cable; the temperature of each extruded section is as follows: the feeding section is 210-220 ℃, the conveying section is 190-200 ℃, the hot melting section is 180-190 ℃, and the head section is 170-180 ℃.
The invention provides a final aspect that the insulating material is applied to preparing thin wall type ship cable, when in application, the insulating material is coated outside a conductor by screw extrusion to be used as an insulating layer, and after the electron accelerator is irradiated and crosslinked (the irradiation dose is controlled by thermal extension, and the thermal extension is controlled within 100 percent), the thin wall type ship cable is prepared, and the wall thickness of the insulating layer of the cable is 0.2 mm-0.3 mm.
The beneficial technical effects are as follows:
the invention adopts high-fluidity polyethylene processing resin with high melt index and ultra-high molecular weight polyethylene as matrix resin, can well balance manufacturability and scratch and abrasion resistance during high-speed thin-wall extrusion, simultaneously adds inorganic flame retardant, flame retardant synergist, antioxidant, lubricant and other auxiliary agents, adopts banburying extrusion to obtain the irradiation crosslinking low-smoke halogen-free flame retardant insulating material, and is applied to preparing thin-wall ship cables as an insulating layer outside the conductors.
The insulating material disclosed by the invention can completely meet the technical requirements in DNVGL-CP-0400 in performance after irradiation crosslinking, has excellent scratch and wear resistance and long-term heat aging resistance, can resist long-term aging at 105 ℃ for 2000 hours, achieves the effect of no cracking, and is excellent in flame retardance, electrical property and mechanical property, good in processability and suitable for high-speed extrusion.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The numerical values set forth in these examples do not limit the scope of the present invention unless specifically stated otherwise. Techniques, methods known to those of ordinary skill in the relevant art may not be discussed in detail, but should be considered part of the specification where appropriate. In all examples shown and discussed herein, any specific values should be construed as merely illustrative, and not a limitation. Thus, other examples of the exemplary embodiments may have different values.
The experimental methods in the following examples, for which specific conditions are not noted, are generally determined according to national standards; if the national standard is not corresponding, the method is carried out according to the general international standard or the standard requirements set by related enterprises. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Examples 1 to 6
The formulations of the irradiation crosslinking low smoke halogen-free flame retardant insulating materials for the thin wall type ship cables of examples 1 to 6 are shown in Table 1. The meaning of the english abbreviations or brands in the examples below:
UHMWPE ultra-high molecular weight polyethylene;
POE ethylene-octene copolymer;
LDPE low density polyethylene, HDPE high density polyethylene; the melt index is 20g/10 min-50 g/10min.
LLDPE-g-MAH linear low density polyethylene grafted maleic anhydride,
LDPE-g-MAH low density polyethylene grafted maleic anhydride,
POE-g-MAH ethylene-octyl copolymer grafted maleic anhydride;
MH magnesium hydroxide, AH aluminum hydroxide;
Nano-MT montmorillonite, nano-ZnO Nano-zinc oxide, nano-AT Nano attapulgite;
1010 pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ],
DLTP dilauryl thiodipropionate,
168 tris (2, 4-di-tert-butylphenyl) phosphite,
1098N, N' -bis- (3- (35-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine,
distearyl DSTP thiodipropionate,
1790 1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione,
412S pentaerythritol tetrakis (3-laurylthiopropionate);
1024N, N' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine,
XL-1 (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid oxalyl (diimino-2, 1-ethylene ester),
4010NA N-phenyl-N' -isopropyl-p-phenylenediamine;
PE wax polyethylene wax, znSt zinc stearate, siMb silicone master batch;
TAIC triallyl isocyanurate, TMTPMA trimethylolpropane trimethacrylate.
TABLE 1 formulations (by weight Kg) of insulation materials of examples 1-6
Comparative example 1
The formulation of the insulating material of this comparative example was the same as in example 1, except that: the processing modified resins LDPE and HDPE were not added and the POE weight was increased to 40Kg.
Comparative example 2
The formulation of the insulating material of this comparative example was the same as in example 3, except that: no flame retardant synergist nano zinc oxide is added.
Comparative example 3
The formulation of the insulating material of this comparative example was the same as in example 3, except that: no ultra-high molecular weight polyethylene, 40Kg of POE, 20Kg of LDPE, 20Kg of HDPE, 20Kg of LDPE-g-MAH, was added.
Example 7
The preparation method of the irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for the thin-wall ship cable comprises the following steps: the preparation method comprises the steps of mixing ultrahigh molecular weight polyethylene, polyolefin elastomer, processing modified resin, compatilizer, inorganic flame retardant, flame retardant synergist, composite antioxidant, lubricant and crosslinking auxiliary agent according to the proportion of each embodiment in table 1, putting into a high-speed mixer for premixing, stirring for 3-5 minutes at room temperature, mixing uniformly, then adding into an internal mixer for banburying to obtain master batch, adding into a double-screw extrusion granulating by a double-cone forced feeder, wherein the temperatures of each section of screw are as follows: 200-210 ℃ of the feeding section, 190-200 ℃ of the conveying section, 180-190 ℃ of the melting section and 170-180 ℃ of the machine head.
Comparative examples 1 to 3 insulating materials were prepared in the same manner as in this example.
Example 8
The irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for the thin-wall ship cable corresponding to the proportions of examples 1-6, obtained by the preparation method of example 7, is extruded and coated outside a conductor to be used as an insulating layer by a single screw extruder, and is subjected to irradiation crosslinking by an electron accelerator (irradiation dose is controlled by thermal extension, and the thermal extension is controlled within 100 percent), so that the thin-wall ship cable (or called an insulating wire core) with the insulating layers of different proportions is obtained.
The method for producing the cable using the insulating materials of comparative examples 1 to 3 as the insulating layer was the same as in this example.
Example 9
The cable products prepared in examples 1 to 6 and comparative examples 1 to 3 above were subjected to performance tests comprising:
(1) Tensile property test: testing tensile properties according to GB/T1040-2008 standard;
(2) Oxygen index test: oxygen index was tested according to GB/T2406-93 standard;
(3) Cable single vertical combustion experiment: testing the flame retardant property of the cable according to GB/T18380.12-2008 standard;
(4) Thermal aging test: testing the aging performance of the cable according to EN 50306 standard;
(5) Thermal extension test: the thermal elongation performance was tested according to GB/T2951.21-2008 standard;
(6) Scratch and abrasion resistance test: the cable was tested for scratch resistance according to EN 50305 standard.
The test results are shown in Table 2.
Table 2 results of performance of examples and comparative examples
As shown in Table 2, the irradiation crosslinking low-smoke halogen-free flame retardant insulating material for the thin-wall ship cable prepared by the invention not only meets the requirements in DNVGL-CP-0400, but also has excellent mechanical property, flame retardant property, long-term aging resistance, scratch and abrasion resistance and other properties. Can be used for the application of the insulation of the thin-wall ship cable and has wide application prospect. The irradiation crosslinking low smoke halogen-free flame retardant insulating material for the thin wall type ship cable has oxygen index higher than 32%, and has better flame retardant property, because the introduced layered or spherical nano particles can migrate to the surface through a resin matrix which is in a molten state under the action of heat released by combustion, and part of nano particles are softened into a glassy structure to form a barrier layer, so that oxygen, heat and polymer decomposition micromolecule fuel are effectively isolated, and the combustion element is interrupted or greatly weakened, thereby the material surface is rapidly self-quenched, and under the action, the nano particles can improve the water molecules released by the magnesium hydroxide and aluminum hydroxide inorganic flame retardant, and the cooling effect is realized. The multi-mechanism improves the flame-retardant effect of the condensed phase in the combustion process, reduces the ablative diffusion, heat and smoke release amount of materials and cables, and passes the severe flame-retardant test.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (7)
1. The irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for the thin-wall ship cable is characterized by comprising the following raw materials in parts by weight:
40 to 60 parts of ultra-high molecular weight polyethylene,
10-20 parts of POE,
15-30 parts of processing modified resin,
10 to 15 parts of polyolefin grafted maleic anhydride,
120-160 parts of inorganic flame retardant,
10 to 30 parts of flame retardant synergist,
1 to 3 parts of composite antioxidant,
0.5 to 2 parts of lubricant,
0.5 to 2.5 portions of irradiation crosslinking auxiliary agent;
the inorganic flame retardant is prepared by mixing magnesium hydroxide and aluminum hydroxide according to the mass ratio of (4-7) to (1-3);
the flame retardant synergist is nonmetal ore or metal oxide, and the nonmetal ore is one of nano attapulgite, nano montmorillonite and nano mica powder; the metal oxide is nano zinc oxide;
the composite antioxidant is prepared by mixing an antioxidant and an anti-copper agent according to the mass ratio of (1-5) (0.2-1);
the relative molecular mass of the ultra-high molecular weight polyethylene is 300-500 ten thousand g/mol;
the processing modified resin is a mixture of LDPE and HDPE, the melt index of the LDPE and the HDPE is 20g/10 min-50 g/10min, and the mass ratio of the LDPE to the HDPE is 1:1 or 2:1.
2. The irradiation crosslinking low smoke zero halogen flame retardant insulating material for thin wall type ship cable as claimed in claim 1, wherein the POE has a density of 0.866g/cm 3 ～0.900g/cm 3 。
3. The irradiation crosslinking low smoke zero halogen flame-retardant insulating material for the thin wall type ship cable according to claim 1, wherein the polyolefin grafted maleic anhydride is one or more of low density polyethylene grafted maleic anhydride, linear low density polyethylene grafted maleic anhydride and ethylene-octyl copolymer grafted maleic anhydride; the grafting rate of the maleic anhydride in the polyolefin grafted maleic anhydride is 0.5-2 wt%.
4. The irradiation crosslinking low smoke zero halogen flame retardant insulating material for the thin wall type ship cable of claim 1, wherein the antioxidant is a mixture of at least two of 1010, DLTP, 168, 1098, DSTP, 1790, 412S; the copper inhibitor is one or more of N, N ' -bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, (3, 5-di-tert-butyl-4-hydroxyphenyl) oxalyl propionate (diimino-2, 1-ethylene ester), N ' -di (beta-naphthyl) p-phenylenediamine and N-phenyl-N ' -isopropyl p-phenylenediamine.
5. The irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for the thin-wall ship cable according to claim 1, wherein the lubricant is one or more of polyethylene wax, microcrystalline paraffin, zinc stearate and silicone master batch; the cross-linking auxiliary agent is one or more of triallyl hydroxyurea, triallyl isocyanurate, trimethylol propane trimethacrylate and 1, 2-polybutadiene.
6. The method for preparing the irradiation crosslinking low-smoke halogen-free flame retardant insulating material for the thin-wall ship cable according to any one of claims 1 to 5, which is characterized by comprising the following steps: premixing the raw materials, banburying into master batch, and finally extruding and granulating to obtain the irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for the thin-wall ship cable; the temperature of each extruded section is as follows: the feeding section is 210-220 ℃, the conveying section is 190-200 ℃, the hot melting section is 180-190 ℃, and the head section is 170-180 ℃.
7. The application of the irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for the thin-wall ship cable according to any one of claims 1 to 5, wherein the insulating material is applied to the preparation of the thin-wall ship cable, the insulating material is extruded and coated outside a conductor to be used as an insulating layer by a screw rod during the application, and the thin-wall ship cable is prepared after irradiation crosslinking, and the wall thickness of the insulating layer of the cable is 0.2mm to 0.3mm.
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| CN202011027017.8A CN114249937B (en) | 2020-09-25 | 2020-09-25 | Irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for thin-wall ship cable, and preparation method and application thereof |
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| CN202011027017.8A CN114249937B (en) | 2020-09-25 | 2020-09-25 | Irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for thin-wall ship cable, and preparation method and application thereof |
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| CN114249937B true CN114249937B (en) | 2023-10-17 |
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| CN202011027017.8A Active CN114249937B (en) | 2020-09-25 | 2020-09-25 | Irradiation crosslinking low-smoke halogen-free flame-retardant insulating material for thin-wall ship cable, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104194139A (en) * | 2014-08-26 | 2014-12-10 | 无锡杰科塑业有限公司 | High-wear-resistance irradiation crosslinking halogen-free flame-retardant polyolefin material for automobile thin-wall electric wire and preparation method thereof |
| CN105440412A (en) * | 2015-12-21 | 2016-03-30 | 中广核三角洲（苏州）高聚物有限公司 | 125 DEG C irradiation-crosslinked high-wear-resistant halogen-free flame-retardant insulation material used for thin-wall locomotive cables |
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| US10497491B2 (en) * | 2017-03-30 | 2019-12-03 | Ls Cable & System Ltd. | Halogen-free flame-retardant polyolefin insulation composition and cable having an insulating layer formed from the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104194139A (en) * | 2014-08-26 | 2014-12-10 | 无锡杰科塑业有限公司 | High-wear-resistance irradiation crosslinking halogen-free flame-retardant polyolefin material for automobile thin-wall electric wire and preparation method thereof |
| CN105440412A (en) * | 2015-12-21 | 2016-03-30 | 中广核三角洲（苏州）高聚物有限公司 | 125 DEG C irradiation-crosslinked high-wear-resistant halogen-free flame-retardant insulation material used for thin-wall locomotive cables |
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