CN112457552A - Weather-resistant low-density polyethylene insulating material and preparation method thereof - Google Patents
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
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Abstract
The invention discloses a weather-resistant low-density polyethylene insulating material and a preparation method thereof. The weather-resistant low-density polyethylene insulating material comprises the following components in parts by weight: 50-70 parts of high-pressure low-density polyethylene, 10-30 parts of high-density polyethylene, 3-10 parts of ethylene-octene copolymer, 2-7 parts of ethylene-vinyl acetate copolymer, 0.1-1 part of ultraviolet absorbent, 0.5-1 part of antioxidant, 0.1-0.5 part of brightener and 1-2 parts of lubricant. The weather-resistant low-density polyethylene insulating material disclosed by the invention is excellent in comprehensive performance, good in flexibility, and greatly superior to a common low-density polyethylene cable material in tensile strength and hardness, and is a novel environment-friendly insulating cable which is cold-resistant, ultraviolet-resistant, resistant to environmental stress cracking, good in processability and suitable for being laid in an overhead environment.
Description
Technical Field
The invention relates to the technical field of cable insulating materials, relates to a polyethylene insulating material and a preparation method thereof, in particular to a weather-resistant low-density polyethylene insulating material and a preparation method thereof, and particularly relates to a weather-resistant low-density polyethylene insulating material for overhead insulated cables of 1KV and below and a preparation method thereof.
Background
The cable insulation material is a cable for power transmission or telecommunication, and comprises a cable core with a plurality of insulated conductors and a polyethylene insulation sheath. The polyethylene jacket has non-impregnated glass fiber bundles embedded therein and distributed coaxially around the core, each glass fiber bundle being sufficiently encased by the jacket material to establish a mechanical bond. Along the longitudinal direction of the cable core, the glass fiber bundles are in a wave shape. Each bundle preferably comprises single or double yarns spun to different thicknesses.
With the cable industry, the cable has an extremely important position in national economy. At present, the production capacity of the existing polyethylene cable in China is about 20 ten thousand tons/year, the demand of the polyethylene cable material in China is about 25 ten thousand tons/year, and a large amount of cable resin, particularly high-pressure-resistant crosslinkable polyethylene resin, is imported in China every year. The rapid development of domestic electric wires and cables enables the cable insulation material to have wide market development prospects in China, and particularly the demand of high-voltage and environment-friendly cable materials is high. The low density polyethylene has excellent electrical performance and processing performance, and after being modified, the product has high mechanical performance, weather resistance and use temperature, and has dielectric strength up to 25kV/mm and work temperature up to 90 deg.c.
CN103540132A discloses a weather-resistant light modified low-density polyethylene cable sheath material, which comprises the following raw materials in parts by weight: 13-17 parts of unsaturated polyester-imide, 4-6 parts of polyacrylonitrile, 42-45 parts of low-density polyethylene, 3-5 parts of ABS high-rubber powder, 3-5 parts of vinyl toluene, 15-18 parts of diallyl phthalate, 1-2 parts of dicumyl peroxide, 3-4 parts of zinc oxide, 1-2 parts of dimethyl tin isooctyl dithioglycolate, 20-22 parts of kaolin powder, 1-2 parts of 3-aminopropyltrimethoxysilane, OD1-2 parts of an anti-aging agent, 15-18 parts of light calcium carbonate, 40101-3 parts of an anti-aging agent, 18-21 parts of tributyl citrate and 14-16 parts of an auxiliary agent; the insulating material combines the advantages of the raw materials such as low-density polyethylene, polyacrylonitrile and the like, and the prepared material is soft in texture, good in mechanical property, resistant to environmental weather cracking, resistant to high-temperature aging, safe and reliable to use, and capable of being widely used for manufacturing various cable sheath insulating materials. But the flexibility and environmental stress crack resistance of the material are to be further improved.
CN103865158A discloses a preparation method of a black weather-resistant polyethylene insulating material for overhead cables, which comprises the following raw materials in percentage by mass: 1-5% of modified polyester, 0.1-0.5% of auxiliary agent, 1-5% of carbon black, 10-40% of modified low-density polyethylene and the balance of silane crosslinked polyethylene. The invention adopts low-temperature carbonization for the rice hull straws, saves the cost on one hand, keeps the original functions of the rice hulls on the other hand, and can be used as an adsorption carrier to play the efficacy of the rice hull straws. However, the process conditions are not well controlled, and the flexibility and environmental stress cracking resistance of the material are also required to be further improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the weather-resistant low-density polyethylene insulating material and the preparation method thereof.
One of the purposes of the invention is to provide a weather-resistant low-density polyethylene insulating material, and in order to achieve the purpose, the invention adopts the following technical scheme:
a weather-resistant low-density polyethylene insulating material comprises the following components in parts by weight:
the weather-resistant low-density polyethylene insulating material is high-density polyethylene which is one of resin base materials in the composition, has the characteristics of good wear resistance (proportional to molecular weight), high strength, impact resistance reaching the maximum when the molecular weight reaches 180 ten thousand, high strength, compensation hardness and the like; the second high-pressure low-density polyethylene of the resin base material has the characteristics of high strength, high toughness, compensation cold resistance and the like; the triethylene-octene copolymer (POE) of the resin base material is used as flexible compensation in a system, so that the POE passes the requirements of an environmental stress cracking resistance test; the adopted resin base material, namely ethylene-vinyl acetate copolymer (EVA), mainly plays a role in connecting low-density polyethylene and high-density polyethylene, prevents layering during processing and plays a role in compatibilization in a system; the high-low density polyethylene and the ethylene-octene copolymer (POE) are taken as base materials, and the ethylene-vinyl acetate resin (EVA) is used as an auxiliary material, so that the impact resistance, the bending fatigue resistance and the low temperature resistance of the product are enhanced; and a proper amount of ultraviolet absorbent, lubricant and brightener are added, so that the product has excellent comprehensive performance, the tensile strength and hardness of the product are greatly superior to those of common low-density polyethylene cable materials, and the cable is a novel environment-friendly insulated cable which is cold-resistant, ultraviolet-resistant, environment stress cracking-resistant, good in processability and suitable for being laid in an overhead environment.
Specifically, the weather-resistant low-density polyethylene insulating material comprises the following components in parts by weight:
50-70 parts of high-pressure low-density polyethylene, for example, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts or 60 parts of high-pressure low-density polyethylene.
10-30 parts of high-density polyethylene, for example, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts or 30 parts of high-density polyethylene.
3-10 parts of ethylene-octene copolymer, for example, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts of ethylene-octene copolymer.
2-7 parts of ethylene-vinyl acetate copolymer, for example, the parts by weight of the ethylene-vinyl acetate copolymer are 2 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts or 7 parts, etc.
0.1 to 1 part of the ultraviolet absorber, for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part by weight of the ultraviolet absorber.
0.5-1 part of antioxidant, for example, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part of antioxidant.
0.1 to 0.5 portion of brightener, for example, 0.1 portion, 0.2 portion, 0.3 portion, 0.4 portion or 0.5 portion of brightener.
1-2 parts of lubricant, for example, 1 part, 1.1 part, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts, etc. by weight of the lubricant.
The density of the high-pressure low-density polyethylene is 0.910-0.935g/cm3For example, the high pressure low density polyethylene has a density of 0.091g/cm3、0.0915g/cm3、0.092g/cm3、0.0925g/cm3、0.093g/cm3、0.0931g/cm3、0.0932g/cm3、0.0933g/cm3、0.0934g/cm3Or 0.0935g/cm3And the like.
The high strength polyethylene has a crystallinity of 80% or more and a weight average molecular weight of more than 150000, such as 00952, Korea 9680 and Kowit equal 6888, and Zilu DGDA-6098.
The ethylene-octene copolymer HAs a melt index of 2g/10min or less, a Shore A hardness of more than 70HA, wherein the Shore A hardness is 1s Shore A hardness, and can be, for example, Dow ethylene-octene copolymer 8150, ethylene-octene copolymer 8100, ethylene-octene copolymer 8452.
The ethylene-vinyl acetate copolymer has a VA content of more than 25%, and can be EVA5110J, EVA00428, EVA7470K and EVA6110M, for example.
The ultraviolet absorbent is any one or mixture of at least two of CHISORB234, CHISORB 326 and UV 531.
The antioxidant is a main antioxidant and an auxiliary antioxidant.
Preferably, the primary antioxidant is a hindered phenol 1010 and/or a hindered phenol 1222.
Preferably, the auxiliary antioxidant is any one or a mixture of at least two of thioester type DSTP, TPL and phosphite ester 168.
The brightener is PPA-FX5924 and/or PPA-8122 of 3M company and is used for improving the surface smoothness and the flowability of the product.
The lubricant is polyethylene wax with the weight-average molecular weight of more than 500000.
The second purpose of the invention is to provide a preparation method of the weather-resistant low-density polyethylene insulating material, which comprises the following steps:
uniformly mixing high-pressure low-density polyethylene, high-density polyethylene, ethylene-octene copolymer and ethylene-vinyl acetate copolymer according to a ratio, adding a lubricant, an antioxidant, a brightener and an ultraviolet absorbent, uniformly mixing, and carrying out mixing, extrusion, cooling, grain cutting and drying to obtain the weather-resistant low-density polyethylene insulating material.
Compared with the prior art, the invention has the beneficial effects that:
the weather-resistant low-density polyethylene insulating material disclosed by the invention is excellent in comprehensive performance, good in flexibility, and greatly superior to a common low-density polyethylene cable material in tensile strength and hardness, and is a novel environment-friendly insulating cable which is cold-resistant, ultraviolet-resistant, resistant to environmental stress cracking, good in processability and suitable for being laid in an overhead environment. Specifically, the tensile strength is more than 30MPa, the low-temperature catalysis temperature can be as low as-76 ℃, the cracking does not occur for 1000h under the environment stress cracking resistance test at 50 ℃, and the volume resistivity is 4.64 x 1014-6.42*1014The dielectric strength is more than 28KV/mm, no cracking is caused after passing UL-1581 ultraviolet 720h test, and the processing temperature is low.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.
Example 1
The weather-resistant low-density polyethylene insulating material comprises the following components in parts by weight:
wherein the density of the high pressure low density polyethylene is 0.930g/cm3The model is FB2310, the high density polyethylene is Korea Korean high density polyethylene 9680, the ethylene-octene copolymer is Dow's ethylene-octene copolymer 8150, the ethylene-vinyl acetate copolymer is EVA5110J, the ultraviolet absorbent is CHISORB234, the antioxidant is a mixture of 0.2 parts of hindered phenols 1010 and 0.3 parts of phosphites 168, the brightener is PPA-FX5924 from 3M company, and the lubricant is polyethylene wax with the weight average molecular weight of 600000.
The preparation method of the weather-resistant low-density polyethylene insulating material of the embodiment is as follows:
taking high-pressure low-density polyethylene, high-density polyethylene, octene-ethylene copolymer (POE) and ethylene-vinyl acetate copolymer (EVA) according to the above proportion, accurately metering and putting into a high-speed mixer kettle, running for 2 minutes at low speed, accurately weighing a lubricant, a main antioxidant, an auxiliary antioxidant, a brightener and an ultraviolet absorbent in a mixing kettle, and mixing for 3 minutes at high speed.
And (3) mixing the uniformly mixed raw materials by a double-screw extruder set, extruding, cooling, granulating, drying and packaging to obtain the composite material.
Example 2
The weather-resistant low-density polyethylene insulating material comprises the following components in parts by weight:
the specific kinds of the respective components are the same as those in example 1.
The preparation method of this example is also the same as that of example 1.
Example 3
The specific kinds of the respective components are the same as those in example 1.
The preparation method of this example is also the same as that of example 1.
Example 4
This example differs from example 1 in that the high pressure low density polyethylene has a density of 0.9g/cm3The rest is the same as in example 1.
Example 5
This example differs from example 1 in that the high pressure low density polyethylene has a density of 0.936g/cm3The rest is the same as in example 1.
Example 6
This example is different from example 1 in that the high density polyethylene has a crystallinity of 60%,
example 7
This example differs from example 1 in that the high strength polyethylene has a weight average molecular weight of 100000, and is otherwise the same as example 1.
Example 8
This example is different from example 1 in that the ethylene-octene copolymer has a melt index of 10g/10min, and is otherwise the same as example 1.
Example 9
This example differs from example 1 in that the ethylene-octene copolymer HAs a shore a of 50HA, all other things being equal to example 1.
Example 10
This example is different from example 1 in that the VA content of the ethylene-vinyl acetate copolymer is 10%, and the other examples are the same as example 1.
Comparative example 1
The comparative example is different from example 1 in that it does not contain an ethylene-octene copolymer and an ethylene-vinyl acetate copolymer, and specifically comprises the following components:
the specific kinds of the respective components are the same as those in example 1.
The comparative example was also prepared in the same manner as in example 1.
Comparative example 2
The comparative example is different from example 1 in that it contains only high-pressure low-density polyethylene, and does not contain high-density polyethylene, ethylene-octene copolymer and ethylene-vinyl acetate copolymer, and has the following specific composition:
the specific kinds of the respective components are the same as those in example 1.
The comparative example was also prepared in the same manner as in example 1.
Comparative example 3
This comparative example differs from example 1 in that it does not contain an ethylene-octene copolymer and has the following specific composition:
the specific kinds of the respective components are the same as those in example 1.
The comparative example was also prepared in the same manner as in example 1.
Comparative example 4
The comparative example is different from example 1 in that it does not contain an ethylene-vinyl acetate copolymer and has the following specific composition:
the specific kinds of the respective components are the same as those in example 1.
The comparative example was also prepared in the same manner as in example 1.
The polyethylene insulations obtained in examples 1 to 10 and comparative examples 1 to 4 were subjected to a performance test, and the test results are shown in table 1.
Wherein the test criteria are as follows:
the test standard of the density is carried out according to GB/T1033, the test standard of the melt flow rate is carried out according to GB/T3682, the test standard of the tensile strength is carried out according to GB/T1040, the test standard of the elongation at break is carried out according to GB/T1040, the test standard of the environmental stress crack resistance is carried out according to GB/T2951, the test standard of the oxidation induction period is carried out according to GB/T2951, the test standard of the volume resistivity is carried out according to GB/T1410, the test standard of the dielectric strength is carried out according to GB/T1409, and the test standard of the artificial weathering is carried out according to GB/T12527.
TABLE 1
As can be seen from Table 1, the density of the high pressure low density polyethylene of example 4 is too low, and although the strength is satisfactory (13 MPa or more), the melt flow rate is large, and the melt flow rate of the material is required to be less than or equal to 0.4g/10min by national standard.
Example 5 the high pressure low density polyethylene had too high a density, which, although the strength was satisfactory (. gtoreq.13 MPa), resulted in a high melt flow rate, which is required by the national standards to be < 0.4g/10 min.
Example 6 the crystallinity of the high strength polyethylene is too low, which causes the melt flow rate to be larger, the national standard requires that the melt flow rate of the material is less than or equal to 0.4g/10min, the environmental stress cracking resistance is not passed for 500h, and the volume resistivity is also lower.
Example 7 the weight average molecular weight of the high strength polyethylene is 100000, which can make the melt flow rate larger, the national standard requires that the melt flow rate of the material is less than or equal to 0.4g/10min, and the volume resistivity is also lower.
Example 8 the ethylene-octene copolymer has a melt index of 10g/10min, although the strength is satisfactory (13 MPa or more), but the melt flow rate is high, the national standard requires that the melt flow rate of the material is less than or equal to 0.4g/10min, and the density is high (standard requires that the density is less than or equal to 0.940 g/cm)3)。
The Shore A of the ethylene-octene copolymer in example 9 is 50HA, although the strength meets the requirement (more than or equal to 13MPa), the melt flow rate is larger, the national standard requires that the melt flow speed of the material is less than or equal to 0.4g/10min, and the density is larger (the standard requires that the density is less than or equal to 0.940 g/cm)3)。
Example 10 ethylene-vinyl acetate copolymer having a VA content of 10% results in a higher density (less than or equal to 0.940g/cm as required by the standards)3). Comparative example 1, which did not contain ethylene-octene copolymer and ethylene-vinyl acetate copolymer, resulted in a higher density (standard requirement ≦ 0.940 g/cm)3)。
Comparative example 2, which contained only high pressure low density polyethylene, did not contain high density polyethylene, ethylene-octene copolymer and ethylene-vinyl acetate copolymer, would result in poor machine-shaping, rough surface, and higher cost, although each test property was superior.
Comparative example 3, which did not contain ethylene-octene copolymer, would result in a higher density (standard requirement ≦ 0.940 g/cm)3)。
Comparative example 4 does not contain an ethylene-vinyl acetate copolymer, and although the individual mechanical properties are excellent, the impact resistance is poor.
The present invention is illustrated by the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, i.e. it is not meant to imply that the present invention must rely on the above-mentioned detailed process equipment and process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The weather-resistant low-density polyethylene insulating material is characterized by comprising the following components in parts by weight:
2. the weatherable low density polyethylene insulation according to claim 1, wherein said high pressure low density polyethylene has a density of 0.910-0.935g/cm3。
3. The weather resistant low density polyethylene insulation according to claim 1 or 2, wherein the high strength polyethylene has a crystallinity of 80% or more and a weight average molecular weight of more than 150000.
4. The weatherable low density polyethylene insulation according to one of claims 1 to 3, wherein the ethylene-octene copolymer HAs a melt index of 2g/10min or less and a Shore A hardness of greater than 70 HA.
5. The weatherable low density polyethylene insulation according to one of claims 1-4, wherein the ethylene vinyl acetate has a VA content of greater than 25%.
6. The weatherable low density polyethylene insulation according to any one of claims 1 to 5, wherein the ultraviolet absorber is any one of or a mixture of at least two of CHISORB234, CHISORB 326 and UV 531.
7. The weatherable low density polyethylene insulation according to any one of claims 1 to 6, wherein the antioxidant is a primary antioxidant and a secondary antioxidant;
preferably, the primary antioxidant is a hindered phenol 1010 and/or a hindered phenol 1222;
preferably, the auxiliary antioxidant is any one or a mixture of at least two of thioester type DSTP, TPL and phosphite ester 168.
8. The weatherable low density polyethylene insulation according to one of claims 1 to 7, wherein the brightener is PPA-FX5924 and/or PPA-8122.
9. The weatherable low density polyethylene insulation according to one of claims 1 to 8, characterized in that said lubricant is polyethylene wax having a weight average molecular weight of more than 500000.
10. A method for preparing the weather-resistant low density polyethylene insulation according to any one of claims 1 to 8, wherein the method comprises the steps of:
uniformly mixing high-pressure low-density polyethylene, high-density polyethylene, ethylene-octene copolymer and ethylene-vinyl acetate copolymer according to a ratio, adding a lubricant, an antioxidant, a brightener and an ultraviolet absorbent, uniformly mixing, and carrying out mixing, extrusion, cooling, grain cutting and drying to obtain the weather-resistant low-density polyethylene insulating material.
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| CN113045812A (en) * | 2021-03-24 | 2021-06-29 | 上海上力特种电缆有限公司 | Communication cable sheath material and anti-crack communication cable |
| CN114702741A (en) * | 2022-03-31 | 2022-07-05 | 金发科技股份有限公司 | Low-density polyethylene material and preparation method and application thereof |
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| CN114702741A (en) * | 2022-03-31 | 2022-07-05 | 金发科技股份有限公司 | Low-density polyethylene material and preparation method and application thereof |
| CN114702741B (en) * | 2022-03-31 | 2023-11-03 | 金发科技股份有限公司 | Low-density polyethylene material and preparation method and application thereof |
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