CN111961278A - Large-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulation material for electric wires - Google Patents
Large-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulation material for electric wires Download PDFInfo
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Abstract
The invention relates to a high-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulating material for a wire, which comprises the following components in parts by weight: 30-60 parts of ethylene-vinyl acetate copolymer; 5-20 parts of an ethylene-butylene copolymer; 5-10 parts of polyethylene; 3-10 parts of modified polypropylene; 20-30 parts of modified polyethylene; 3-10 parts of anti-shrinkage master batch; 3-5 parts of antioxidant master batch; 1-5 parts of silicon carbide; 1-5 parts of zinc borate; 1-1.8 parts of a silane coupling agent; 0.5-4 parts of a lubricant; 1-3 parts of a crosslinking sensitizer. The invention provides an irradiation crosslinking polyolefin insulating material which is not easy to smoke, foam, yellow and crack under the action of overload large current, does not burn with open fire under the current condition of 100-300A, can effectively prolong the service time of an electric wire when a circuit is short-circuited, and reduces the risk of firing the circuit.
Description
Technical Field
The invention relates to an insulating material, in particular to a high-current irradiation resistant cross-linking low-smoke halogen-free flame-retardant polyolefin insulating material for a cloth wire.
Background
With the improvement of safety and environmental protection requirements, the low-smoke halogen-free flame-retardant polyolefin insulating material replaces the traditional PVC product in a plurality of cable products by virtue of the advantages of low smoke, halogen free and environmental protection, and is widely applied to civil electric wire and cloth products, and compared with thermoplastic products, the irradiation crosslinking low-smoke halogen-free polyolefin insulating material has higher temperature resistance level, so that the irradiation crosslinking low-smoke halogen-free polyolefin insulating material is more favored by cable products.
The conventional low-smoke halogen-free polyolefin insulating material product, whether thermoplastic or radiation crosslinking, needs to meet the standard requirement of GB/T32129-2015. The formula design is more conventional, and the composite material is prepared by taking polyolefin resins such as ethylene-vinyl acetate copolymer, polyethylene, modified polyethylene, polyolefin resin, ethylene propylene diene monomer rubber and the like as base materials, adding a large amount of inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide and the like, adding processing aids such as polyethylene wax, silane coupling agent, silicone master batch, stearate and the like, and carrying out internal mixing and plasticizing, mixing and granulating by a double-stage extruder.
However, with market competition and improvement of the use safety requirements of the wire distribution products, the current market puts forward the destructive test requirements of overload large current on the wire distribution products, so that the large current overload test provides a new main assessment index for the finished wire distribution products. The destructive test mainly examines whether the low-smoke halogen-free flame-retardant polyolefin insulated cloth wire product is fuming, foaming, yellowing and cracking and the time for generating several phenomena under the heating action of 100A or even higher short-circuit current. The cloth wire prepared by the irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin insulating material produced by the conventional formula has the phenomena of fuming, foaming, yellowing and cracking in a short time, and cannot meet the new requirements of the market on high current resistance or overload and non-combustibility of cloth wire products.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a high-current irradiation resistant crosslinking low-smoke halogen-free flame-retardant polyolefin insulating material for a cloth wire, and the invention provides an irradiation crosslinking polyolefin insulating material which is not easy to smoke, foam, yellow and crack under the action of overload high current, does not burn with open fire under the current condition of 140A or even 150A, can effectively prolong the service time of the wire when a circuit short circuit occurs, and reduces the risk of line ignition.
The invention adopts the following technical scheme:
the high-current irradiation-resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulating material for the cloth wire comprises the following components in parts by weight:
wherein the modified polypropylene is copolymerized polypropylene grafted by maleic anhydride; the grafting rate is 0.2-0.6%, and the melt index under the condition of 190 ℃ multiplied by 2.16kg is 0.5-5g/10 min;
the modified polyethylene is one or more of maleic anhydride grafted linear low density polyethylene, metallocene polyethylene and bimodal polyethylene; the grafting rate is 0.4-0.6%, and the melt index under the condition of 190 ℃ multiplied by 2.16kg is 0.5-3 g/10 min;
the anti-shrinkage master batch comprises polymethyl silicone resin and ethylene-vinyl acetate copolymer (EVA), and the mass fraction of the polymethyl silicone resin in the anti-shrinkage master batch is more than 60%;
the antioxidant master batch comprises an antioxidant, linear low-density polyethylene and silicone, wherein the mass ratio of the antioxidant to the linear low-density polyethylene to the silicone is 50:49: 1. The melt index of the linear low-density polyethylene is 1-5 g/10min under the condition of 190 ℃ multiplied by 2.16kg, the siloxane content of the silicone is more than or equal to 70 percent, and the molecular weight is more than or equal to 100 ten thousand.
Further, the high-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulating material for the wire distribution also comprises the following components in parts by weight:
30-180 parts (preferably 100-180 parts) of aluminum hydroxide;
30-180 parts (preferably 100-180 parts) of magnesium hydroxide;
2-5 parts of color master batch.
Aluminum hydroxide and magnesium hydroxide are added to be matched with zinc borate and silicon carbide for use, so that the flame retardant property of the insulating material can be improved. The color master batches with proper colors can be selected according to the color requirements of the electric wires so as to prepare the polyolefin insulation materials with different colors.
Further, the ethylene-vinyl acetate copolymer comprises at least two ethylene-vinyl acetate copolymers with VA content, wherein one ethylene-vinyl acetate copolymer has VA content of not less than 26%, and the other ethylene-vinyl acetate copolymer has VA content of not less than 14%.
Further, the ethylene-vinyl acetate copolymer comprises a first ethylene-vinyl acetate copolymer and a second ethylene-vinyl acetate copolymer, wherein the VA content of the first ethylene-vinyl acetate copolymer is more than or equal to 26%, and the melt index is more than or equal to 4g/10min under the condition of 190 ℃ multiplied by 2.16 kg; the VA content of the second ethylene-vinyl acetate copolymer is more than or equal to 14 percent, and the melt index is more than or equal to 2g/10min under the condition of 190 ℃ multiplied by 2.16 kg.
Further, the melt index of the ethylene-butylene copolymer at 190 ℃ is multiplied by 2.16kg for 1.0-5.0 g/10min, and the Vicat softening point is more than or equal to 70 ℃.
Further, the polyethylene is one or more of linear low density polyethylene, metallocene polyethylene and bimodal polyethylene, and the melt index of the polyethylene is 0.5-5g/10min under the condition of 190 ℃ multiplied by 2.16 kg.
Further, the silane coupling agent is vinyltris (β -methoxyethoxy) silane and/or vinyltrimethoxysilane.
Further, the lubricant is one or more of silicone master batch, polyethylene wax, calcium stearate, zinc stearate, oleamide and stearic acid.
Further, the crosslinking sensitizer is triallyl isocyanurate and/or trimethylolpropane trimethacrylate.
Further, the antioxidant is at least three of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], dilauryl thiodipropionate, 4' -thiobis (6-tert-butyl-3-methylphenol and tris [2, 4-di-tert-butylphenyl ] phosphite
Further, particle size selection D of aluminum hydroxide50：1.2～2.0μm。
Particle size selection of magnesium hydroxide D50：1.2～2.0μm。
Further, particle size selection D of silicon carbide50：3～5μm。
Further, the particle diameter of zinc borate is D50：1～3μm
Further, the color master batch is a high-temperature resistant color master batch of the polyethylene base material.
Further, the preparation method of the antioxidant masterbatch comprises the following steps:
weighing the antioxidant, the linear low-density polyethylene and the silicone master batch according to the proportion, adding the weighed materials into a high-speed mixer, uniformly mixing the materials for 5 minutes at a low speed, mixing the materials for 2 minutes at a high speed, controlling the temperature of the materials to be 60-80 ℃, and then plasticizing, extruding and granulating the uniformly mixed powder. Preferably, plasticizing extrusion granulation is carried out by adopting a Booth machine, and the Booth machine has an excellent extrusion shearing dispersion function compared with a traditional extruder, so that the antioxidant is prevented from agglomerating and is uniformly dispersed.
Further, the preparation method of the high-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulating material for the wire distribution comprises the following steps:
the weighed components are plasticized and mixed in an internal mixer, and are extruded and granulated through a double-stage extruder set after being uniformly mixed.
Wherein the banburying temperature is 155-160 ℃;
the feeding temperature is 130 ℃;
the twin-screw process temperature of the double-stage machine is as follows: 110 ℃, 115 ℃, 115 ℃, 120 ℃, 125 ℃, 125 ℃, 120 ℃, 115 ℃ and 110 ℃;
the process temperature of the double-stage machine single screw is as follows: 110 deg.C, 120 deg.C, 130 deg.C.
Head temperature: 135 ℃ is adopted.
In the present invention, "large current" in the case of large current resistance means that the current is 100 to 300A.
By the scheme, the invention at least has the following advantages:
1. the invention provides a high-current irradiation-resistant crosslinking low-smoke halogen-free flame-retardant polyolefin insulating material for a wire distribution, which is prepared by taking an ethylene-vinyl acetate copolymer, an ethylene-butylene copolymer, polyethylene, modified polyethylene and modified polypropylene resin as base materials, adding zinc borate and a silicon carbide inorganic flame-retardant filler to endow the insulating material with good flame retardance, adding shrinkage-resistant master batches and antioxidant master batches to improve the heat aging resistance and heat resistance of the material, improving the melting time of the polyolefin insulating material under high current after the wire distribution is prepared, and adding a certain amount of functional additives such as a lubricant, a silane coupling agent and the like to improve the compatibility of each component.
2. The high-current irradiation resistant crosslinking low-smoke halogen-free flame-retardant polyolefin insulating material for the electric wire comprises the antioxidant master batch instead of directly mixing the antioxidant with other components, the antioxidant is mixed with linear low-density polyethylene and silicone in advance to prepare the antioxidant master batch, the antioxidant can not agglomerate, and can be uniformly dispersed in the insulating material after being mixed with other components, so that the product has good heat-resistant aging resistance, the product decomposition time is prolonged, the decomposition temperature is increased, and the fuming, foaming and yellowing time is prolonged. In the antioxidant master batch, the linear low-density polyethylene is used as a carrier, so that the antioxidant can be dispersed, and extrusion granulation and molding are facilitated, and the silicone is used as a lubricant, so that the extrusion granulation is facilitated, and the production efficiency is improved.
3. The high-current irradiation-resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulating material for the electric wires comprises the anti-shrinkage master batch, the main component of the anti-shrinkage master batch is polymethyl silicone resin, and the polymethyl silicone resin is mixed with other components in the form of the master batch, so that the dispersity of the polymethyl silicone resin can be improved, the heat resistance of the polyolefin insulating material can be effectively improved, and the melting time of the electric wires in a high-current test can be prolonged.
4. The modified polyethylene added in the invention is maleic anhydride grafted polyethylene, the addition amount is large, the grafted polyethylene is used for replacing conventional polyethylene resin, and the modified polypropylene (maleic anhydride grafted polypropylene) is used in cooperation, the temperature resistance grade of the product can be greatly improved by adding the maleic anhydride grafted polyethylene and the polypropylene resin, and the initial time of foaming, yellowing and cracking of the product in a high-current resistance test is delayed.
5. When a large current resistant test is carried out on a distribution wire prepared by using the large current irradiation resistant cross-linking low-smoke halogen-free flame-retardant polyolefin insulating material for the distribution wire, for example, the distribution wire with the specification of WDZA-BYJR 1 multiplied by 4, the starting fuming time is not less than 150s, the foaming time is not less than 180s, even no foaming, the yellowing time is not less than 200s, and the cracking time is not less than 300s under the current condition of 140A. And the insulating layer is directly carbonized, open fire combustion does not occur, the service time of the electric wire can be effectively prolonged when a circuit short circuit occurs, and the danger of line fire is reduced.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a preferred embodiment of the present invention and is described in detail below.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the following embodiments of the present invention, the preparation method of the cable is as follows:
the weighed components are added into an internal mixer in sequence according to the flame retardant, the lubricant, the antioxidant master batch, the anti-shrinkage master batch, the matrix material, the master batch and the coupling agent for plasticizing and mixing. After being uniformly mixed, the mixture is extruded and granulated by an 75/180 double-stage extruder set. Wherein:
the banburying temperature is 155-160 ℃;
the feeding temperature is as follows: 130 ℃;
the twin-screw process temperature of the double-stage machine is as follows: 110 ℃, 115 ℃, 115 ℃, 120 ℃, 125 ℃, 125 ℃, 120 ℃, 115 ℃ and 110 ℃;
the process temperature of the double-stage machine single screw is as follows: 110 ℃, 120 ℃ and 130 ℃;
head temperature: 135 ℃ is adopted.
The preparation method of the antioxidant master batch comprises the following steps:
weighing the antioxidant, the polyethylene resin and the silicone master batch according to the proportion, adding the mixture into a high-speed mixer, uniformly mixing the mixture for 5 minutes at a low speed, mixing the mixture for 2 minutes at a high speed, controlling the temperature of the material to be 60-80 ℃, and not agglomerating the material, then adding the uniformly mixed powder into a feeding hopper of a booth machine, and plasticizing, extruding and granulating the powder by using the booth machine. The master batch comprises the following materials in percentage by mass:
antioxidant: 50 percent of
Polyethylene resin: 49 percent of
Silicone master batch: 1 percent;
the antioxidant is three of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, 4' -thiobis (6-tert-butyl-3-methylphenol and tris [2, 4-di-tert-butylphenyl ] phosphite in a ratio of 3:1: 1.
The polyethylene resin is powdery linear low-density polyethylene, the melt index of the polyethylene resin is 2g/10min under the condition of 190 ℃ multiplied by 2.16kg,
the silicone master batch has the siloxane content of 75 percent and the molecular weight of 120 ten thousand.
The anti-shrinkage master batch consists of polymethyl silicone resin and EVA, wherein the mass fraction of the polymethyl silicone resin is 70%.
The low-smoke halogen-free flame-retardant polyolefin insulating material is prepared according to the formula in table 1, a cable is prepared, and then the product after irradiation crosslinking is tested, and the result is shown in table 1. The cable specifications in Table 1 are WDZA-BYJ R1X 4, and the test currents are 140A-150A. The amounts of the respective substances in Table 1 are in parts by weight.
TABLE 1 formulation and Performance test results for different low-smoke halogen-free flame-retardant polyolefin insulating materials
In Table 1, the ethylene-vinyl acetate copolymer was composed of a first ethylene-vinyl acetate copolymer having a VA content of 28%, a melt index of 5g/10min under 190 ℃ X2.16 kg, and a second ethylene-vinyl acetate copolymer having a VA content of 18%, a melt index of 2.5g/10min under 190 ℃ X2.16 kg.
The ethylene-butene copolymer had a melt index of 4.5g/10min at 190 ℃ X2.16 kg and a Vicat softening point of 80 ℃.
The polyethylene was a bimodal polyethylene or a linear low density polyethylene having a melt index of 1.0g/10min at 190 ℃ under 2.16 kg.
The modified polyethylene is maleic anhydride grafted bimodal polyethylene, the grafting rate of the modified polyethylene is 0.5%, and the melt index under the condition of 190 ℃ multiplied by 2.16kg is 2g/10 min.
The modified polypropylene is copolymerized polypropylene grafted by maleic anhydride; the grafting ratio was 0.5%, and the melt index under 190 ℃ X2.16 kg was 1.5g/10 min.
The flame retardant is aluminum hydroxide (D)50: 1.2 to 2.0 μm) and magnesium hydroxide (D)50：1.2～2.0μm)。
The lubricant is silicone master batch and calcium stearate.
The antioxidants used in comparative examples 1 and 2 were pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and dilauryl thiodipropionate.
The silane coupling agent is vinyl trimethoxy silane.
The crosslinking sensitizer is a mixture of triallyl isocyanurate and trimethylolpropane trimethacrylate.
The results in table 1 show that compared with the conventional products in the market, the cloth wire prepared by using the irradiation crosslinking low-smoke halogen-free flame-retardant polyolefin insulating material has better heat resistance, and when a large current resistance test is carried out, the time from electrifying to starting fuming is long, the fuming amount is small, the foaming time is long, more importantly, the foaming is small and less, even the foaming is not carried out, and the yellowing time and the cracking time are long.
In addition, in order to confirm the effect of characteristic parameters such as VA content, melt index, etc. of the resin matrix on the performance of the polyolefin insulation, comparative examples 3 to 5 were provided below, and the performance thereof was tested under the same test conditions as in Table 1, and the results are shown in Table 2. In comparison with the results in Table 1, it can be seen that comparative examples 3 to 5 are inferior to examples 1 to 3 in the large current resistance.
TABLE 2 formulation and Performance test results for different low-smoke halogen-free flame-retardant polyolefin insulating materials
In Table 2, the ethylene-vinyl acetate copolymer had a VA content of 40% and a melt index of 8g/10min at 190 ℃ under 2.16 kg.
The ethylene-butene copolymer had a melt index of 18g/10min at 190 ℃ under 2.16 kg.
The polyethylene has a melt index of 10g/10min at 190 ℃ multiplied by 2.16 kg.
The modified polyethylene maleic anhydride grafted linear low-density polyethylene has the grafting rate of 0.5 percent and the melt index of 7g/10min under the condition of 190 ℃ multiplied by 2.16 kg.
The modified polypropylene is maleic anhydride grafted homo-polypropylene, the grafting ratio is 0.4%, and the melt index is 6g/10min under the condition of 190 ℃ multiplied by 2.16 kg.
The flame retardant is aluminum hydroxide (D)50: 1.2 to 2.0 μm) and magnesium hydroxide (D)50：1.2～2.0μm)。
The lubricant is silicone master batch and polyethylene wax.
The antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and dilauryl thiodipropionate.
The silane coupling agent is vinyl trimethoxy silane.
The crosslinking sensitizer is trimethylolpropane trimethacrylate.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The high-current irradiation-resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulating material for the cloth wire is characterized in that the high current is 100-300A, and the insulating material comprises the following components in parts by weight:
wherein the modified polypropylene is copolymerized polypropylene grafted by maleic anhydride; the grafting rate is 0.2-0.6%, and the melt index under the condition of 190 ℃ multiplied by 2.16kg is 0.5-5g/10 min;
the modified polyethylene is one or more of maleic anhydride grafted linear low-density polyethylene, metallocene polyethylene and bimodal polyethylene; the grafting rate is 0.4-0.6%, and the melt index under the condition of 190 ℃ multiplied by 2.16kg is 0.5-3 g/10 min;
the anti-shrinkage master batch comprises polymethyl silicone resin and ethylene-vinyl acetate copolymer, and the mass fraction of the polymethyl silicone resin in the anti-shrinkage master batch is more than 60%;
the antioxidant master batch comprises an antioxidant, linear low-density polyethylene and silicone, wherein the mass ratio of the antioxidant to the linear low-density polyethylene to the silicone is 50:49: 1.
2. The high-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulation material for the electric wires according to claim 1, which is characterized by further comprising the following components in parts by weight:
30-180 parts of aluminum hydroxide;
30-180 parts of magnesium hydroxide;
2-5 parts of color master batch.
3. The high-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulation material for the electric wires according to claim 1 or 2, which is characterized in that: the ethylene-vinyl acetate copolymer comprises at least two ethylene-vinyl acetate copolymers with VA content, wherein the VA content of one ethylene-vinyl acetate copolymer is not less than 26%, and the VA content of the other ethylene-vinyl acetate copolymer is not less than 14%.
4. The high-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulation material for the electric wires according to claim 1 or 2, which is characterized in that: the ethylene-vinyl acetate copolymer comprises a first ethylene-vinyl acetate copolymer and a second ethylene-vinyl acetate copolymer, wherein the VA content of the first ethylene-vinyl acetate copolymer is more than or equal to 26%, and the melt index is more than or equal to 4g/10min under the condition of 190 ℃ multiplied by 2.16 kg; the VA content of the second ethylene-vinyl acetate copolymer is more than or equal to 14 percent, and the melt index is more than or equal to 2g/10min under the condition of 190 ℃ multiplied by 2.16 kg.
5. The high-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulation material for the electric wires according to claim 1 or 2, which is characterized in that: the melt index of the ethylene-butene copolymer is 1.0-5.0 g/10min under the condition of 190 ℃ multiplied by 2.16kg, and the Vicat softening point is more than or equal to 70 ℃.
6. The high-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulation material for the electric wires according to claim 1 or 2, which is characterized in that: the polyethylene is one or more of linear low density polyethylene, metallocene polyethylene and bimodal polyethylene, and the melt index of the polyethylene is 0.5-5g/10min under the condition of 190 ℃ multiplied by 2.16 kg.
7. The high-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulation material for the electric wires according to claim 1 or 2, which is characterized in that: the silane coupling agent is vinyl tri (beta-methoxyethoxy) silane and/or vinyl trimethoxy silane.
8. The high-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulation material for the electric wires according to claim 1 or 2, which is characterized in that: the lubricant is one or more of silicone master batch, polyethylene wax, calcium stearate, zinc stearate, oleamide and stearic acid.
9. The high-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulation material for the electric wires according to claim 1 or 2, which is characterized in that: the crosslinking sensitizer is triallyl isocyanurate and/or trimethylolpropane trimethacrylate.
10. The high-current irradiation resistant cross-linked low-smoke halogen-free flame-retardant polyolefin insulation material for the electric wires according to claim 1 or 2, which is characterized in that: the antioxidant is at least three of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], dilauryl thiodipropionate, 4' -thiobis (6-tert-butyl-3-methylphenol and tris [2, 4-di-tert-butylphenyl ] phosphite.
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