CN113817256A - High-service-life copper damage irradiation-resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulating material and preparation method thereof - Google Patents
High-service-life copper damage irradiation-resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulating material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a long-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulating material and a preparation method thereof, and the raw materials of the long-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulating material comprise: 10-50 parts of modified linear low-density polyethylene, 30-80 parts of ethylene-vinyl acetate copolymer, 30-80 parts of ethylene-butyl acrylate copolymer, 5-20 parts of maleic anhydride grafted copolymer elastomer, 3-15 parts of silicone master batch, 30-80 parts of aluminum hydroxide, 30-80 parts of magnesium hydroxide, 30-80 parts of zinc borate, 3-5 parts of composite antioxidant, 2-5 parts of composite copper resisting agent, 1-2 parts of lubricant, 2-5 parts of coupling agent and 1-2 parts of crosslinking sensitizer, wherein the parts are parts by weight. According to the invention, the composite antioxidant, the composite copper-resistant agent and the composite flame retardant with specific compositions are compounded with other raw materials, so that the insulating material with long service life, copper harm resistance and flame retardance is obtained, and meanwhile, the mechanical property and the insulating property are excellent; the preparation method is simple and easy to operate.
Description
Technical Field
The invention relates to a long-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulating material and a preparation method thereof, belonging to the technical field of cables.
Background
Polyolefin materials are extremely sensitive to copper ions, which can accelerate degradation and aging of polyolefin materials. After the polyolefin insulating material is contacted with the copper conductor, the aging speed is accelerated by 3 times, and the service life of the cable is greatly reduced, so that the problem of copper harm of the polyolefin insulating material is a problem to be solved urgently. The low-smoke halogen-free polyolefin insulating material not only needs to have excellent mechanical properties and insulating properties, but also needs to have excellent flame retardant properties, but the improvement of the flame retardant properties of the material inevitably reduces the mechanical properties and the insulating properties of the material, so that the flame retardant properties, the mechanical properties and the like are difficult to simultaneously consider.
Disclosure of Invention
The invention provides a high-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulating material and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a long-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulating material comprises the following raw materials: 10-50 parts of modified linear low-density polyethylene, 30-80 parts of ethylene-vinyl acetate copolymer, 30-80 parts of ethylene-butyl acrylate copolymer, 5-20 parts of maleic anhydride grafted copolymer elastomer, 3-15 parts of silicone master batch, 30-80 parts of aluminum hydroxide, 30-80 parts of magnesium hydroxide, 30-80 parts of zinc borate, 3-5 parts of composite antioxidant, 2-5 parts of composite copper resisting agent, 1-2 parts of lubricant, 2-5 parts of coupling agent and 1-2 parts of crosslinking sensitizer, wherein the composite antioxidant is antioxidant 1010, antioxidant 168, antioxidant DLTDP, antioxidant 412s and antioxidant 445, and the mass ratio of the antioxidant 1010 to the antioxidant 445 is 2: (0.5-2): (0.5-2): (0.5-2): (0.5-2), wherein the composite copper resisting agent is a mixture of a copper resisting agent 1024, a copper resisting agent 2115 and benzotriazole, and the mass ratio of the copper resisting agent to the benzotriazole is 2: (1-2): (0.5-1.5), wherein the parts are parts by weight.
The applicant finds through research and development practices that the antioxidant or the copper resisting agent is difficult to have an obvious copper harm resisting effect when used alone, in order to prolong the service life of the cable, the high-efficiency antioxidant and the copper resisting agent need to be added into the insulating material, but the single-component use effect of the antioxidant and the copper resisting agent is very limited, in order to ensure that the material has excellent aging performance, the composite antioxidant is adopted, and through selection of the components of the antioxidant 1010, the antioxidant 168, the antioxidant DLTDP, the antioxidant 412s, the antioxidant 445 and the dosage of the antioxidant, the synergistic effect among the components is brought into play to the best, so that the aging performance of the material is ensured; in order to ensure that the material has excellent copper resistance, the composite copper resistant agent is adopted, and the synergistic effect among the components is brought into play to the best by selecting the components of the copper resistant agent 1024, the copper resistant agent 2115, benzotriazole and the dosage of the components, so that the copper resistance of the material is ensured; in order to ensure that the material has excellent flame retardant performance, the flame retardant is compounded and flame-retardant by adopting a plurality of flame retardants, the synergistic effect among the components is exerted to the best by selecting the components of aluminum hydroxide, magnesium hydroxide, zinc borate and the dosage of the aluminum hydroxide, the magnesium hydroxide, the zinc borate and the dosage of the zinc hydroxide, the flame retardant performance of the material is ensured, and the mechanical performance and the insulating performance of the product are ensured by combining the selection of the base resin and the dosage of the base resin.
In order to take both the resistance performance and the mechanical performance into consideration, the aluminum hydroxide, the magnesium hydroxide and the zinc borate are all coated by organic resin, and the particle sizes are all 1-2 mu m.
In order to further promote the synergistic effect among the components, enhance the flame retardant effect and improve the mechanical property, the mass ratio of the aluminum hydroxide, the magnesium hydroxide and the zinc borate is (1-2): (1-2): 1.
in order to improve the mechanical property of the product, the addition amount of the coupling agent is 1.2-1.5% of the total amount of the aluminum hydroxide, the magnesium hydroxide and the zinc borate.
In order to improve the uniformity of material mixing and promote the synergistic promotion among materials, the preparation of the composite antioxidant comprises the following steps: placing the antioxidant 1010, the antioxidant 168, the antioxidant DLTDP, the antioxidant 412s and the antioxidant 445 in a high-speed mixer, and mixing for 5 +/-1 min at the rotating speed of 1000 +/-50 r/min to obtain the composite antioxidant. That is, the antioxidant is required to be mixed first and then mixed with other materials, so that the uniformity of the mixing of the materials can be ensured, the mutual cooperation among the antioxidants can be promoted, and the improvement of the oxidation resistance can be promoted.
In order to improve the uniformity of material mixing and promote the synergistic promotion among materials, the preparation of the composite copper resisting agent comprises the following steps: and (3) placing the copper resisting agent 1024, the copper resisting agent 2115 and the copper resisting agent benzotriazole into a high-speed mixer, and mixing for 5 +/-1 min at the rotating speed of 1000 +/-50 r/min to obtain the composite copper resisting agent. That is, the application needs to mix the copper resisting agents firstly and then mix the copper resisting agents with other materials, so that the uniformity of the mixing of the materials can be ensured, the mutual cooperation among the copper resisting agents can be promoted, and the improvement of the copper harm resisting performance is promoted.
The applicant finds that interaction effects of raw materials of different manufacturers and brands and other components are different in practice research and development, and in order to further ensure the insulating property and the mechanical property of the insulating material, the modified linear low-density polyethylene is SP0540 produced by the three-well chemical production; the ethylene-vinyl acetate copolymer is KA-31 produced by Singapore polyolefin; the ethylene-butyl acrylate copolymer was 1715 from spanish lyocell. Researches show that SP0540 produced by the three-well chemical production can further promote the coordination effect among the components, so that the obtained cable has excellent electrical property and mechanical property, the performance of the filling powder is excellent, and the dilemma of poor mechanical property and poor electrical property caused by excessive addition of the filler in a formula system is solved.
To further promote the synergistic effect between the components, the maleic anhydride graft copolymer elastomer is a shanghai long-polymerizing compatibilizer JCP 1000.
In order to improve the processability of the material, the lubricant is polyethylene wax.
In order to make the cable more even, wherein the powder composition can be better the dispersion in order to exert its material advantage, promote the synergistic effect between each component, this application anti copper harm irradiation cross-linking halogen-free low smoke flame retardant polyolefin insulating material of long-life adopts earlier to carry out antioxidant, anti copper agent mixture, carries out weightlessness balance automatic weighing again, and the mixing of reciprocating engine combines single screw granulation, specifically includes following step:
A. placing the antioxidant 1010, the antioxidant 168, the antioxidant DLTDP, the antioxidant 412s, the antioxidant 445 and the lubricant in a high-speed mixer, and mixing for 5 +/-1 min at the rotating speed of 1000 +/-50 r/min to obtain the composite antioxidant; placing the copper resisting agent 1024, the copper resisting agent 2115 and benzotriazole into a high-speed mixer, and mixing for 5 +/-1 min at the rotating speed of 1000 +/-50 r/min to obtain a composite copper resisting agent;
B. accurately weighing and mixing the modified linear low-density polyethylene, the ethylene-vinyl acetate copolymer, the maleic anhydride graft copolymer elastomer and the silicone master batch by using an automatic mixer to obtain a mixed base material.
C. Accurately weighing the mixed base material, the composite antioxidant, the composite copper-resistant agent, the aluminum hydroxide, the magnesium hydroxide and the zinc borate by using a weightlessness scale, adding the weighed materials into a reciprocating machine through forced feeding, accurately weighing the crosslinking sensitizer and the coupling agent by using the weightlessness scale, injecting the weighed materials into the reciprocating machine through a liquid gun, mixing the mixed base material, the composite antioxidant, the composite copper-resistant agent, the aluminum hydroxide, the magnesium hydroxide, the zinc borate, the crosslinking sensitizer and the coupling agent in the reciprocating machine, extruding and granulating by a single screw rod, and cooling by wind to obtain the long-life copper harm irradiation-resistant crosslinked halogen-free low-smoke flame-retardant polyolefin insulating material.
The raw materials are weighed by a weightless scale, mixed by a reciprocating machine and extruded and granulated by a single screw, so that not only is automatic batch production realized, but also the error caused by human factors is reduced, the uniformity of the insulating material is improved, and the material quality is ensured.
Preferably, in the step C, the discharge temperature of the reciprocating machine is 120-160 ℃, and the single-screw extrusion granulation temperature is 120-160 ℃.
The prior art is referred to in the art for techniques not mentioned in the present invention.
According to the high-life copper harm irradiation-resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulating material, the composite antioxidant, the composite copper harm-resistant agent and the composite flame retardant which are specially composed are compounded with other raw materials, so that the insulating material with high life, copper harm resistance and flame retardance is obtained, and meanwhile, the mechanical property and the insulating property are excellent; the preparation method is simple, easy to operate and low in cost; the preparation method adopts the steps of mixing the composite antioxidant and the composite copper resisting agent in advance, then carrying out weightlessness balance automatic weighing, and mixing by a reciprocating machine and combining single screw granulation, thereby realizing automatic and batch production and obtaining a product with good uniformity and excellent performance.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In each example, the mass ratio of the antioxidant 1010 (Tianjin Li Sheng), the antioxidant 168 (Tianjin Li Sheng), the antioxidant DLTDP (Tianjin Li Sheng), the antioxidant 445 (Ke Pi) and the antioxidant 412S (Ke Li) is 2: 1: 1: 1: 1, and the composite antioxidant is prepared by the following steps: and (3) proportionally placing the antioxidant 1010, the antioxidant 168, the antioxidant DLTDP, the antioxidant 445 and the antioxidant 412S into a high-speed mixer, and mixing for 5min at the rotating speed of 1000r/min to obtain the composite antioxidant.
The composite copper-resistant agent is prepared by mixing 1024 (basf) copper-resistant agent, 2115 (Weihai Huaen rubber and plastic new material Co., Ltd.) and benzotriazole (Nanjing Guangxi Jun chemical industry) copper-resistant agent in a mass ratio of 2: 1.5: 1, the specific preparation of the composite copper resisting agent is as follows: and (3) proportionally placing the anti-copper agent 1024, the anti-copper agent 2115 and the anti-copper agent benzotriazole into a high-speed mixer to be mixed for 5min under the condition that the rotating speed is 1000r/min, thus obtaining the composite anti-copper agent.
The maleic anhydride graft copolymer elastomer is a compatible agent JCP1000 for Shanghai long-term polymerization; the modified linear low density polyethylene is SP0540 produced by the three-well chemical industry; the ethylene-vinyl acetate copolymer is KA-31 produced by Singapore polyolefin; the ethylene-butyl acrylate copolymer was 1715 from spanish lyocell; the silicone master batch is AF-15 silicone master batch (Shanghai Wujiang new material Co., Ltd.), and the lubricant is polyethylene wax (Changzhou successful lubricant); the aluminum hydroxide is WF-1 produced by the aluminum industry in China, the particle size is 1-2 mu m, and the magnesium hydroxide is H5 produced by American Yabao; the zinc borate is HT-207 of Thaxin; the crosslinking sensitizer is TAIC (Koley in Hangzhou state), and the coupling agent is Degussa A172.
Example 1
A long-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulating material comprises the following raw materials in parts by weight: 35 parts of modified linear low-density polyethylene SP0540 (Mitsui chemical), 40 parts of ethylene-vinyl acetate copolymer KA-31 (Singapore polyolefin), 45 parts of ethylene-butyl acrylate copolymer 1715 (Lepusoler), 10 parts of maleic anhydride graft copolymer elastomer JCP1000 (Shanghai Jiuyi poly), 5 parts of silicone master batch AF-15 (Shanghai Wujiang river), 50 parts of aluminum hydroxide, 50 parts of magnesium hydroxide, 50 parts of zinc borate, 3 parts of composite antioxidant, 2 parts of composite copper resisting agent, 2 parts of polyethylene wax (successful in match), 2 parts of crosslinking sensitizer TAIC (Hangzhou Keli) and 2 parts of coupling agent.
The preparation method of the long-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulating material comprises the following steps:
A. placing the antioxidant 1010, the antioxidant 168, the antioxidant DLTDP, the antioxidant 412s and the antioxidant 445 in a high-speed mixer, mixing for 5min at the rotating speed of 1000r/min to obtain the composite antioxidant, placing the copper resisting agent 1024, the copper resisting agent 2115 and the copper resisting agent benzotriazole in the high-speed mixer, and mixing for 5min at the rotating speed of 1000r/min to obtain the composite copper resisting agent.
B. Accurately weighing and mixing the modified linear low-density polyethylene, the ethylene-vinyl acetate copolymer, the maleic anhydride graft copolymer elastomer and the silicone master batch by using an automatic mixer to obtain a mixed base material.
C. Accurately weighing the mixed base material, the composite antioxidant, the composite copper-resistant agent, the aluminum hydroxide, the magnesium hydroxide and the zinc borate by using a weightlessness scale, adding the weighed materials into a reciprocating machine through forced feeding, accurately weighing the crosslinking sensitizer and the coupling agent by using the weightlessness scale, injecting the weighed materials into the reciprocating machine through a liquid gun, mixing the mixed base material, the composite antioxidant, the composite copper-resistant agent, the aluminum hydroxide, the magnesium hydroxide, the zinc borate, the crosslinking sensitizer and the coupling agent in the reciprocating machine, extruding and granulating by using a single screw rod, and finally cooling by wind to obtain the long-life copper harm irradiation-resistant crosslinked halogen-free low-smoke flame-retardant polyolefin insulating material.
The indexes of the high-life copper damage irradiation-resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulating material are shown in table 1 after detection.
Example 2
The weight composition of the long-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulating material is as follows: 50 parts of modified linear low-density polyethylene SP0540 (Mitsui chemical), 30 parts of ethylene-vinyl acetate copolymer KA-31 (Singapore polyolefin), 55 parts of ethylene-butyl acrylate copolymer 1715 (Lepusoler), 10 parts of maleic anhydride graft copolymer elastomer JCP1000 (Shanghai Jiyun), 5 parts of silicone master batch AF-15 (Shanghai Wujiang river), 50 parts of aluminum hydroxide, 50 parts of magnesium hydroxide, 50 parts of zinc borate, 3 parts of composite antioxidant, 2 parts of polyethylene wax (successful in competition), 2 parts of crosslinking sensitizer TAIC (Kolie in Hangzhou), and 2 parts of coupling agent.
Referring to example 1, the preparation method of the long-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulation material is shown in table 1 by detecting various indexes.
Example 3
The weight composition of the long-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulating material is as follows: 35 parts of modified linear low-density polyethylene SP0540 (Mitsui chemical), 40 parts of ethylene-vinyl acetate copolymer KA-31 (Singapore polyolefin), 40 parts of ethylene-butyl acrylate copolymer 1715 (Lyprisol), 10 parts of maleic anhydride graft copolymer elastomer JCP1000 (Shanghai Jiyun), 5 parts of silicone master batch AF-15 (Shanghai Wujiang river), 60 parts of aluminum hydroxide, 60 parts of magnesium hydroxide, 30 parts of zinc borate, 3 parts of composite antioxidant, 2 parts of polyethylene wax (successful in competition), 2 parts of crosslinking sensitizer TAIC (Hangzhou Keli) and 2 parts of coupling agent.
Referring to example 1, the preparation method of the long-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulation material is shown in table 1 by detecting various indexes.
Comparative example 1
All antioxidants were 1010, and the rest were as in example 1.
Comparative example 2
The copper-resistant agents were all copper-resistant agents 1024, and the rest were referred to example 1.
TABLE 1 Performance Table of the long-life copper damage irradiation resistant crosslinked halogen-free low-smoke flame-retardant polyolefin insulation material
Claims (10)
1. A long-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulating material is characterized in that: the raw materials comprise the following components: 10-50 parts of modified linear low-density polyethylene, 30-80 parts of ethylene-vinyl acetate copolymer, 30-80 parts of ethylene-butyl acrylate copolymer, 5-20 parts of maleic anhydride grafted copolymer elastomer, 3-15 parts of silicone master batch, 30-80 parts of aluminum hydroxide, 30-80 parts of magnesium hydroxide, 30-80 parts of zinc borate, 3-5 parts of composite antioxidant, 2-5 parts of composite copper resisting agent, 1-2 parts of lubricant, 2-5 parts of coupling agent and 1-2 parts of crosslinking sensitizer, wherein the composite antioxidant is antioxidant 1010, antioxidant 168, antioxidant DLTDP, antioxidant 412s and antioxidant 445, and the mass ratio of the antioxidant 1010 to the antioxidant 445 is 2: (0.5-2): (0.5-2): (0.5-2): (0.5-2), wherein the composite copper resisting agent is a mixture of a copper resisting agent 1024, a copper resisting agent 2115 and benzotriazole, and the mass ratio of the copper resisting agent to the benzotriazole is 2: (1-2): (0.5-1.5), wherein the parts are parts by weight.
2. The long-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulation material as claimed in claim 1, characterized in that: the aluminum hydroxide, the magnesium hydroxide and the zinc borate are all coated by organic resin, and the particle sizes are all 1-2 mu m.
3. The high-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulation material as claimed in claim 1 or 2, characterized in that: the mass ratio of the aluminum hydroxide to the magnesium hydroxide to the zinc borate is (1-2): (1-2): 1.
4. the high-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulation material as claimed in claim 1 or 2, characterized in that: the addition amount of the coupling agent is 1.2-1.5% of the total amount of the aluminum hydroxide, the magnesium hydroxide and the zinc borate.
5. The high-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulation material as claimed in claim 1 or 2, characterized in that: the preparation of the composite antioxidant comprises the following steps: placing the antioxidant 1010, the antioxidant 168, the antioxidant DLTDP, the antioxidant 412s and the antioxidant 445 in a high-speed mixer, and mixing for 5 +/-1 min at the rotating speed of 1000 +/-50 r/min to obtain the composite antioxidant.
6. The high-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulation material as claimed in claim 1 or 2, characterized in that: the preparation of the composite copper resisting agent comprises the following steps: and (3) placing the copper resisting agent 1024, the copper resisting agent 2115 and the copper resisting agent benzotriazole into a high-speed mixer, and mixing for 5 +/-1 min at the rotating speed of 1000 +/-50 r/min to obtain the composite copper resisting agent.
7. The high-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulation material as claimed in claim 1 or 2, characterized in that: the modified linear low density polyethylene is SP0540 produced by the three-well chemical industry; the ethylene-vinyl acetate copolymer is KA-31 produced by Singapore polyolefin; the ethylene-butyl acrylate copolymer was 1715 from spanish lyocell.
8. The high-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulation material as claimed in claim 1 or 2, characterized in that: the maleic anhydride graft copolymer elastomer is a compatible agent JCP1000 for Shanghai long-term polymerization; the lubricant is polyethylene wax.
9. The preparation method of the long-life copper damage irradiation resistant cross-linked halogen-free low-smoke flame-retardant polyolefin insulation material according to any one of claims 1 to 8, characterized by comprising the following steps: the method comprises the following steps:
A. placing the antioxidant 1010, the antioxidant 168, the antioxidant DLTDP, the antioxidant 412s, the antioxidant 445 and the lubricant in a high-speed mixer, and mixing for 5 +/-1 min at the rotating speed of 1000 +/-50 r/min to obtain the composite antioxidant; placing the copper resisting agent 1024, the copper resisting agent 2115 and benzotriazole into a high-speed mixer, and mixing for 5 +/-1 min at the rotating speed of 1000 +/-50 r/min to obtain a composite copper resisting agent;
B. accurately weighing and mixing the modified linear low-density polyethylene, the ethylene-vinyl acetate copolymer, the maleic anhydride graft copolymer elastomer, the ethylene-butyl acrylate copolymer and the silicone master batch by using an automatic mixer to obtain a mixed base material;
C. accurately weighing the mixed base material, the composite antioxidant, the composite copper-resistant agent, the aluminum hydroxide, the magnesium hydroxide and the zinc borate by using a weightlessness scale, adding the weighed materials into a reciprocating machine through forced feeding, accurately weighing the crosslinking sensitizer and the coupling agent by using the weightlessness scale, injecting the weighed materials into the reciprocating machine through a liquid gun, mixing the mixed base material, the composite antioxidant, the composite copper-resistant agent, the aluminum hydroxide, the magnesium hydroxide, the zinc borate, the crosslinking sensitizer and the coupling agent in the reciprocating machine, extruding and granulating by a single screw rod, and cooling by wind to obtain the long-life copper harm irradiation-resistant crosslinked halogen-free low-smoke flame-retardant polyolefin insulating material.
10. The method of claim 9, wherein: in the step C, the discharge temperature of the reciprocating machine is 120-160 ℃, and the extrusion granulation temperature of the single screw is 120-160 ℃.
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