CN111925655B - Wear-resistant flexible PEI cable material, preparation method thereof and cable - Google Patents
Wear-resistant flexible PEI cable material, preparation method thereof and cable Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
- H01B3/306—Polyimides or polyesterimides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01B3/46—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 silicones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/3045—Sulfates
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2203/00—Applications
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- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention discloses a wear-resistant flexible PEI cable material which comprises the following components in parts by weight: 20-35 parts of PEI resin, 35-55 parts of siloxane copolymerized PEI resin, 5-15 parts of wear-resistant modified resin, 8-15 parts of filler, 3-5 parts of compatilizer, 0.2-0.5 part of antioxidant, 0.1-0.3 part of light stabilizer and 0.2-0.6 part of lubricant; the melt index of the PEI resin is 8-20 g/10min @337 ℃/6.6Kg, the silicon content of the siloxane copolymerized PEI resin is more than 20%, and the melt index of the siloxane copolymerized PEI resin is 6-15 g/10min @295 ℃/6.6 Kg. The invention also discloses a preparation method of the PEI cable material and a cable prepared from the PEI cable material. The wear-resistant flexible PEI cable material is suitable for special cables which cannot meet the requirements of conventional cable materials and have high temperature resistance, cold resistance, high flame retardance, no toxicity and high tensile property.
Description
Technical Field
The invention relates to the technical field of engineering plastics and special cable materials, in particular to a wear-resistant flexible PEI cable material, a preparation method thereof and a cable.
Background
In recent years, with the rapid development of advanced manufacturing industry, the demand of 'replacing steel with plastic' in the field of materials is more and more urgent. In particular, the demands for high temperature resistance, high strength, high modulus, stable size, light weight, electrical insulation, wear resistance, self-lubrication and sealing materials in the fields of aerospace, war industry, nuclear power, automobiles, electronics, communication, machinery and the like are sharply increased. The polymer material, especially special engineering plastic, can fully bear the mission of meeting the use requirement. Among a plurality of special engineering plastics, Polyetherimide (PEI) material has extremely high heat-resistant grade, the initial thermal decomposition temperature is above 500 ℃, the long-term use temperature can reach 200 ℃, the short-term use temperature is above 250 ℃, and meanwhile, the PEI material becomes the only available material in the high-temperature field due to excellent mechanical property, radiation resistance, corrosion resistance, dielectric property, insulating property, flame retardant property and the like. However, the material is hard and brittle and is not easy to apply to a cable coating layer, so the material must be modified to have certain flexibility, a large amount of inorganic filler is often added to reduce the cost, and the abrasion resistance of the material is greatly reduced due to the addition of the filler. Therefore, the PEI cable material which is flexible, cheap and wear-resistant has great application value.
Disclosure of Invention
The invention aims to solve the technical problem of providing a wear-resistant flexible PEI cable material which simultaneously has high tensile strength, high elongation at break, high cantilever beam notch impact strength at the normal temperature of 23 ℃ and low temperature of-30 ℃ and high heat deformation temperature, and is suitable for special cables which cannot meet the requirements of conventional cable materials and have high temperature resistance, cold resistance, high flame retardance, no toxicity and high tensile property.
In order to solve the technical problems, the invention provides a wear-resistant flexible PEI cable material which comprises the following components in parts by weight:
the melt index of the PEI resin is 8-20 g/10min @337 ℃/6.6 Kg; the silicon content of the siloxane copolymerized PEI resin is more than 20%, and the melt index of the siloxane copolymerized PEI resin is 6-15 g/10min @295 ℃/6.6 Kg.
Further, the wear-resistant modified resin is selected from one or more of Polytetrafluoroethylene (PTFE) micropowder, PA4T, PA46 and PA 6T.
Further, the filler is selected from one or more of calcium carbonate, barium sulfate and talcum powder.
Further, the compatilizer is one or more of EMA-g-MAH, POE-g-MAH, EVA-g-MAH, EBA-g-MAH and SEBS-g-MAH.
Further, the antioxidant is selected from one or more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and N, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine.
Further, the light stabilizer is selected from one or more of salicylate, benzoate, benzophenone, benzotriazole, substituted acrylonitrile, oxamide, organic nickel complex and hindered amine light stabilizer.
Further, the lubricant is selected from one or more of high temperature polyethylene wax, pentaerythritol tetrastearate (PETs), silicone, and EBS.
The invention provides a preparation method of the wear-resistant flexible PEI cable material, which comprises the following steps:
uniformly mixing the dried components in proportion, and then extruding and granulating the obtained mixture in a double-screw extruder, wherein the extrusion temperature of each area of the double-screw extruder is 250-320 ℃, the feeding speed is 30-100Kg/h, and the screw rotating speed is 110-250 rpm; and cooling and pelletizing to obtain the wear-resistant flexible PEI cable material.
Further, the preparation method of the wear-resistant flexible PEI cable material comprises the following steps:
the method comprises the following steps: respectively dehumidifying and drying PEI resin and siloxane copolymerized PEI resin at 150 ℃ and 105 ℃ for 4-6 h, and then weighing the granules and the powder separately according to the proportion; the granules are PEI, siloxane copolymerized PEI resin and a compatilizer, and the powder is wear-resistant modified resin, a filler, an antioxidant, a light stabilizer and a lubricant;
step two: respectively adding the weighed granular materials and the weighed powder materials into respective high-speed mixers, mixing at the speed of 250-1000 r/min for 3-5 min, and discharging to obtain a granular material weight loss scale and a powder material weight loss scale;
step three: feeding the granular material weight loss scale and the powder weight loss scale into a double-screw extruder according to a set feeding proportion, controlling the extrusion temperature of the double-screw extruder to be 250-320 ℃, and controlling the rotating speed of a screw to be 160-250 rpm;
step four: and cooling the molten extrudate extruded by the die head of the double-screw extruder, and preparing the molten extrudate into granules by a granulator to obtain the wear-resistant flexible PEI cable material.
In a third aspect of the invention there is provided a cable made from a material comprising the wear resistant flexible PEI cable material according to the first aspect.
The invention has the beneficial effects that:
1. the PEI-modified PEI-modified material takes PEI resin as a base material, and completely compatible siloxane copolymerized PEI resin is added, and due to the fact that molecular chains of the siloxane copolymerized PEI resin have flexibility, the flexibility of PEI materials can be effectively improved, the materials have good notched impact strength at normal temperature and low temperature, the notched impact strength of a cantilever beam at 23 ℃ is more than or equal to 200J/m, the notched impact strength of a cantilever beam at 30 ℃ is more than or equal to 150J/m, the retention rate of the tensile strength of the materials after a long-term aging test at 200 ℃ for 3000h is more than or equal to 75%, and the retention rate of elongation at break is more than or equal to 75%;
2. the invention ensures that the prepared PEI alloy not only has better wear resistance (0.35 mm) by matching with the wear-resistant resin, the barium sulfate filler and the compatilizer2The number of times of the wire scraping and grinding test can reach more than 1000) and flexibility (the flexural modulus is less than or equal to 400MPa), and simultaneously has better tensile strength and elongation at break (the tensile strength is more than or equal to 30MPa, and the elongation at break is more than or equal to 350%);
3. the wear-resistant flexible PEI cable material has high flame-retardant and environment-friendly performance, meets the environmental protection regulations related to European Union RoSH standards, REACH regulations and the like (meets the limit requirements of the European Union REACH regulation No. 1907/2006, European Union RoHS instruction 2011/65/EU annex II correction instruction (EU)2015/863 and meets the European Union standard EN 50620), has the flame-retardant index reaching the level of UL940.75mm V-0 and the oxygen index LOI reaching 45 percent.
Detailed Description
The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention and to practice it, but the examples are not intended to limit the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1
The novel wear-resistant flexible PEI cable material comprises the following components in parts by weight:
wherein the melt index of the PEI resin is 18g/10min, the silicon content of the siloxane copolymerized PEI resin is 40%, and the melt index is 12g/10 min; the wear-resistant modified resin is FTFE micro powder, the filler is barium sulfate, the compatilizer is SEBS-g-MAH, the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010), the light stabilizer is a benzoate light stabilizer, and the lubricant is high-temperature polyethylene wax.
The preparation method of the wear-resistant flexible PEI cable material comprises the following steps:
the method comprises the following steps: respectively dehumidifying and drying PEI resin and siloxane copolymerized PEI resin at 150 ℃ and 105 ℃ for 4-6 h, and then weighing the granules (PEI, Si-PEI and compatilizer) and the powder (wear-resistant modified resin, filler, antioxidant, light stabilizer and lubricant) according to the proportion;
step two: respectively adding the weighed granular materials and the weighed powder materials into a high-speed mixer, mixing for 3-5 min at the speed of 250-1000 r/min, and then respectively discharging to a granular material weight loss scale and a powder material weight loss scale;
step three: setting the blanking proportion of a weight loss scale according to the weight parts of the granules and the powder, feeding the granule weight loss scale and the powder weight loss scale into a double-screw extruder according to the set blanking proportion, controlling the extrusion temperature of the double-screw extruder to be 250-320 ℃, and controlling the rotating speed of a screw to be 160-250 rpm;
step four: and cooling the molten extrudate extruded by the die head of the double-screw extruder, and preparing the molten extrudate into granules by a granulator to obtain the wear-resistant flexible PEI cable material.
Examples 2 to 6
The abrasion resistant flexible PEI cable materials of examples 2-6 were prepared using substantially the same raw materials and methods as in example 1, except that the specific components and ratios were slightly different, as shown in table 1.
TABLE 1 compositions and amounts of PEI cable material in examples 1-6
Comparative examples 1 to 4
Comparative examples 1-4 are essentially the same as example 1 in terms of raw materials and components, except that the specific components and ratios are slightly different, as shown in table 2. A PEI cable material was prepared by the same preparation method as example 1.
TABLE 2 composition and amount of PEI cable material in comparative examples 1-4
Performance testing
The alloy materials prepared in the above examples 1 to 6 and comparative examples 1 to 4 were subjected to performance tests, and the specific test methods and test results are shown in table 3.
Table 3 results of performance testing
As can be seen from the results in the table above, compared with the comparative example, the wear-resistant flexible PEI cable material of the example has high tensile strength, breaking strain, heat resistance, oil resistance, flexibility (low flexural modulus), and high izod notched impact strength, high flame retardancy, and wear resistance at 23 ℃ at room temperature and-30 ℃ at low temperature, and has higher reliability compared with the conventional cable material.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. The wear-resistant flexible PEI cable material is characterized by comprising the following components in parts by weight:
the melt index of the PEI resin is 8-20 g/10min @337 ℃/6.6 Kg; the silicon content of the siloxane copolymerized PEI resin is more than 20%, and the melt index of the siloxane copolymerized PEI resin is 6-15 g/10min @295 ℃/6.6 Kg.
2. The abrasion-resistant flexible PEI cable material of claim 1 wherein the abrasion-resistant modified resin is selected from one or more of polytetrafluoroethylene micropowder, PA4T, PA46, PA 6T.
3. A wear resistant flexible PEI cable material according to claim 1, wherein said filler is selected from one or more of calcium carbonate, barium sulfate, talc.
4. The abrasion resistant flexible PEI cable material of claim 1 wherein the compatibilizer is one or more of EMA-g-MAH, POE-g-MAH, EVA-g-MAH, EBA-g-MAH, and SEBS-g-MAH.
5. A wear resistant flexible PEI cable material according to claim 1, wherein said antioxidant is selected from the group consisting of pentaerythritol tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-t-butylphenyl) phosphite, N-octadecyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate and N, N' -bis- (3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl) hexanediamine.
6. The abrasion resistant flexible PEI cable material of claim 1 wherein said light stabilizer is selected from the group consisting of one or more of salicylates, benzoates, benzophenones, benzotriazole, substituted acrylonitriles, oxamides, organo nickel complexes and hindered amine light stabilizers.
7. The abrasion resistant flexible PEI cable material of claim 1, wherein said lubricant is selected from the group consisting of one or more of high temperature polyethylene wax, pentaerythritol tetrastearate, silicone, and EBS.
8. A method for preparing a wear resistant flexible PEI cable material according to any of the claims 1-7, characterized in that it comprises the following steps:
uniformly mixing the dried components in proportion, and then extruding and granulating the obtained mixture in a double-screw extruder, wherein the extrusion temperature of each area of the double-screw extruder is 250-320 ℃, the feeding speed is 30-100Kg/h, and the screw rotating speed is 110-250 rpm; and cooling and pelletizing to obtain the wear-resistant flexible PEI cable material.
9. The method of preparing a wear resistant flexible PEI cable material according to claim 8, wherein the method of preparing comprises the steps of:
the method comprises the following steps: respectively dehumidifying and drying PEI resin and siloxane copolymerized PEI resin at 150 ℃ and 105 ℃ for 4-6 h, and then weighing the granules and the powder separately according to the proportion; the granules are PEI resin, siloxane copolymerized PEI resin and compatilizer, and the powder is wear-resistant modified resin, filler, antioxidant, light stabilizer and lubricant;
step two: respectively adding the weighed granular materials and the weighed powder materials into a high-speed mixer, mixing for 3-5 min at the speed of 250-1000 r/min, and then feeding until a granular material weight loss scale and a powder material weight loss scale are obtained;
step three: feeding the granular material weight loss scale and the powder weight loss scale into a double-screw extruder according to a set feeding proportion, controlling the extrusion temperature of the double-screw extruder to be 250-320 ℃, and controlling the rotating speed of a screw to be 160-250 rpm;
step four: and cooling the molten extrudate extruded by the die head of the double-screw extruder, and preparing the molten extrudate into granules by a granulator to obtain the wear-resistant flexible PEI cable material.
10. A cable prepared from a material comprising the wear resistant flexible PEI cable material according to any one of claims 1-7.
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| CN1791641A (en) * | 2003-05-20 | 2006-06-21 | 通用电气公司 | Flame resistant thermoplastic composition, articles thereof and method of making articles |
| CN101309973A (en) * | 2005-09-16 | 2008-11-19 | 通用电气公司 | Flame retardant polymer blends |
| CN107250280A (en) * | 2015-02-23 | 2017-10-13 | 沙特基础工业全球技术有限公司 | Anti creepage trace composition, the product formed by it and its manufacture method |
| WO2019150060A1 (en) * | 2018-02-05 | 2019-08-08 | Arkema France | Blends of polyaryletherketones having improved impact-resistance, elongation at break and flexibility |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1791641A (en) * | 2003-05-20 | 2006-06-21 | 通用电气公司 | Flame resistant thermoplastic composition, articles thereof and method of making articles |
| CN101309973A (en) * | 2005-09-16 | 2008-11-19 | 通用电气公司 | Flame retardant polymer blends |
| CN107250280A (en) * | 2015-02-23 | 2017-10-13 | 沙特基础工业全球技术有限公司 | Anti creepage trace composition, the product formed by it and its manufacture method |
| WO2019150060A1 (en) * | 2018-02-05 | 2019-08-08 | Arkema France | Blends of polyaryletherketones having improved impact-resistance, elongation at break and flexibility |
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