CN105199329A - Irradiation cross-linked thermoplastic polyester elastomer cable material and cable production method - Google Patents
Irradiation cross-linked thermoplastic polyester elastomer cable material and cable production method Download PDFInfo
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- CN105199329A CN105199329A CN201510715893.2A CN201510715893A CN105199329A CN 105199329 A CN105199329 A CN 105199329A CN 201510715893 A CN201510715893 A CN 201510715893A CN 105199329 A CN105199329 A CN 105199329A
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Abstract
The invention discloses an irradiation cross-linked thermoplastic polyester elastomer cable material. The irradiation cross-linked thermoplastic polyester elastomer cable material comprises, by weight, 100 parts of thermoplastic polyester elastomer (TPEE), 15-40 parts of ethylene-vinyl acetate copolymer (EVA), 50-80 parts of a fire retardant, 0.3-2 parts of a lubricant, 0.3-3 parts of an antioxidant and 0.1-1 part of an ultraviolet light stabilizer. The invention also discloses a method for producing cables through using the cable material. Cable products produced by using the cable material have excellent room temperature and high temperature mechanical performances; irradiation crosslinking realizes good flame retardation performance on the premise of meeting environmental protection, and also realizes cost reduction; and the cable material can reach 125DEG C temperature resistance level, has excellent scratch and wear resistance, and can be widely used in the fields of automobile wires and high and low temperature resistant cables.
Description
Technical field
The present invention relates to a kind of elastomer cable material and cable production method, be specifically related to a kind of irradiate crosslinked thermoplastic polyester elastomer cable material and cable production method.
Background technology
Along with the progress of science and technology and the lifting of standard of living, day by day universal motor vehicle makes the attention rate of the public to traffic safety day by day increase, and the automobile electric wire at engine and car light position requires to realize steady operation under narrow and small wiring space and hot environment, this proposes very high requirement to the performance of automobile electric wire.
Thermoplastic polyester elastomer (TPEE) is the line-type block polymer that a class contains the hard section of polybutylene terephthalate crystallization and aliphatic polyester or polyester soft segment, there is good mechanical property, oil-proofness, solvent resistance and outstanding high-temperature mechanical property and low-temperature performance, possess the workability of the snappiness of rubber and the intensity of engineering plastics and thermoplastics simultaneously.The performance excellent because of it and easily processing mode, TPEE to be widely used in requiring elasticity, high-low temperature resistant, warping strength, oil resistant require the field of sufficient intensity, as electric wire, trolley part, sealing member etc. in recent years.
But the singularity of TPEE material makes it there is following shortcoming in processing with in using: 1.TPEE flame retardant rating is lower, and melting drippage situation is serious; 2. the fusing point of the hard section of polyester is higher, and when temperature is too high, melt viscosity sharply declines, and affects production stability and quality product.
Summary of the invention
The present invention is directed to existing issue, a kind of cross-linking radiation elastomer cable material based on thermoplastic polyester elastomer (TPEE) and cable production method are provided.Under the guarantee environment friendly of CABLE MATERIALS and the prerequisite of flame retardant properties, significantly reduce cost, possess excellent room temperature and high-temperature mechanical property simultaneously, the user demand of high-low temperature resistant cable can be met.
For achieving the above object, the invention provides a kind of irradiate crosslinked thermoplastic polyester elastomer cable material, comprising the feed composition of following weight part:
Thermoplastic polyester elastomer (TPEE) 100 parts;
Ethylene-vinyl acetate copolymer (EVA) 15 ~ 40 parts;
Fire retardant 50 ~ 80 parts;
Lubricant 0.2 ~ 2 part;
0.3 ~ 3 part, oxidation inhibitor;
UV light stabilizing agent 0.1 ~ 1 part.
Preferably, the vinyl acetate co-monomer content range of ethylene-vinyl acetate copolymer used (EVA) is 14% ~ 28%.
Preferably, fire retardant used is the combination of melamine cyanurate (MCA) in nitrogen, phosphorus flame retardant, organic secondary phosphine acid salt, and is the main body of compounding flame retardant with MCA.
Preferably, be with lubricator silicone master batch.
Preferably; oxidation inhibitor used is four [methyl-β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester (antioxidant 1010), N; N '-bis-[3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl] combination of one or more of the two lauryl alcohol ester (oxidation inhibitor 412s) of quadrol (oxidation inhibitor 1098), three [2,4-di-tert-butyl-phenyl] phosphorous acid ester (irgasfos 168) or thio-2 acid.
Preferably, UV light stabilizing agent used is two (2,2,6,6-tetramethyl--4-piperidines) sebates (anti ultraviolet agent 770).
The preparation method of described irradiate crosslinked thermoplastic polyester elastomer cable material, comprises the following steps:
1) batch weighing: weigh good various raw material by formula.
2) powder mixing is played: load weighted TPEE, EVA, fire retardant, lubricant, oxidation inhibitor, UV light stabilizing agent added after stirring in high-speed mixer, discharging, obtains mixture.
3) compound melt extruded at 190 ~ 230 DEG C by the twin screw extruder that length-to-diameter ratio is larger, tie rod, cooling, granulation, obtain irradiate crosslinked thermoplastic polyester elastomer cable material finished product masterbatch.
4) described finished wire CABLE MATERIALS extrudes wire rod through twin screw extruder and conductor (metallic conductor such as copper or aluminium), is cross-linked by gained wire rod, cross-linked dosage 10 ~ 17Mrad, can obtains finished product cable by electron accelerator irradiation.
Beneficial effect of the present invention:
The present invention adopts TPEE to be main base material, ensure room temperature and the high-temperature mechanical property of CABLE MATERIALS, add EVA elastomerics, effectively solve TPEE CABLE MATERIALS and vary with temperature in the course of processing and the sharply viscosity reduction that occurs, the one-tenth charcoal that EVA is good simultaneously can promote the flame retardant properties of system simultaneously; Cross-linking radiation is compared chemicure method and is had more clean feature, and make the anti-dripping of matrix material and become charcoal effectively to be promoted, this makes the addition of organic phosphorus flame retardant be reduced, significantly reduce cost, there is obvious lifting to the room temperature of material and high-temperature mechanical property simultaneously, greatly reduce the generation of non-reversible deformation; Melamine cyanurate is main body and the nitrogen composite with organic secondary phosphine acid salt, phosphorus flame-retardant system show and excellent become charcoal and flame retardant properties, system is not halogen-containing, in use can not to be heated or the sun is exposed to the sun and produces poisonous halogen-containing materials because of energising, environmental protection, meets European Union RoHs(" about being limited in electronic and electrical equipment the instruction using some objectionable constituent " simultaneously) standard and European Union REACH(" registration of chemical, assessment, mandate and restriction ") environmental requirement of decree; Cross-linking radiation also makes the temperature resistant grade of cable sheath get a promotion to meet the user demand of high-low temperature resistant electric wire.
Embodiment
By describing technology contents of the present invention, formula rate in detail, being realized object and effect, be explained in detail below in conjunction with embodiment.
Below describe several specific embodiments that present embodiment produces irradiate crosslinked thermoplastic polyester elastic body jacket cable, unless otherwise indicated, all numbers all by weight:
embodiment 1
Fill a prescription composed as follows:
Thermoplastic polyester elastomer (TPEE) 100 parts;
Ethylene-vinyl acetate copolymer (EVA) 30 parts;
Melamine cyanurate (MCA) 40 parts;
Organic secondary phosphine acid salt 25 parts;
Silicone 2 parts;
Antioxidant 1010 2 parts;
Anti ultraviolet agent 7701 parts.
Preparation process is as follows:
After weighing and add by above-mentioned component formula and stir in high-speed mixer, discharging, obtains mixture.Compound is melt extruded at 190 ~ 230 DEG C by the twin screw extruder that length-to-diameter ratio is larger, tie rod, cooling, granulation, obtain irradiate crosslinked thermoplastic polyester elastomer cable material finished product masterbatch.Described finished wire CABLE MATERIALS extrudes wire rod through twin screw extruder and conductor (metallic conductor such as copper or aluminium), is cross-linked by gained wire rod, cross-linked dosage 16Mrad, can obtains finished product cable by electron accelerator irradiation.
embodiment 2
Fill a prescription composed as follows:
Thermoplastic polyester elastomer (TPEE) 100 parts;
Ethylene-vinyl acetate copolymer (EVA) 35 parts;
Melamine cyanurate (MCA) 35 parts;
Organic secondary phosphine acid salt 30 parts;
Silicone 2 parts;
Antioxidant 1010 2 parts;
Anti ultraviolet agent 7700.5 parts.
Preparation process is as follows:
After weighing and add by above-mentioned component formula and stir in high-speed mixer, discharging, obtains mixture.Compound is melt extruded at 190 ~ 230 DEG C by the twin screw extruder that length-to-diameter ratio is larger, tie rod, cooling, granulation, obtain irradiate crosslinked thermoplastic polyester elastomer cable material finished product masterbatch.Described finished wire CABLE MATERIALS extrudes wire rod through twin screw extruder and conductor (metallic conductor such as copper or aluminium), is cross-linked by gained wire rod, cross-linked dosage 16Mrad, can obtains finished product cable by electron accelerator irradiation.
embodiment 3
Fill a prescription composed as follows:
Thermoplastic polyester elastomer (TPEE) 100 parts;
Ethylene-vinyl acetate copolymer (EVA) 20 parts;
Melamine cyanurate (MCA) 30 parts;
Organic secondary phosphine acid salt 25 parts;
Silicone 1.5 parts;
Antioxidant 1010 1 part
Oxidation inhibitor 412s0.5 part;
Anti ultraviolet agent 7700.5 parts.
Preparation process is as follows:
After weighing and add by above-mentioned component formula and stir in high-speed mixer, discharging, obtains mixture.Compound is melt extruded at 190 ~ 230 DEG C by the twin screw extruder that length-to-diameter ratio is larger, tie rod, cooling, granulation, obtain irradiate crosslinked thermoplastic polyester elastomer cable material finished product masterbatch.Described finished wire CABLE MATERIALS extrudes wire rod through twin screw extruder and conductor (metallic conductor such as copper or aluminium), is cross-linked by gained wire rod, cross-linked dosage 14Mrad, can obtains finished product cable by electron accelerator irradiation.
embodiment 4
Fill a prescription composed as follows:
Thermoplastic polyester elastomer (TPEE) 100 parts;
Ethylene-vinyl acetate copolymer (EVA) 40 parts;
Melamine cyanurate (MCA) 40 parts;
Organic secondary phosphine acid salt 35 parts;
Silicone 2 parts;
Oxidation inhibitor 412s2 part;
Anti ultraviolet agent 7700.5 parts.
Preparation process is as follows:
After weighing and add by above-mentioned component formula and stir in high-speed mixer, discharging, obtains mixture.Compound is melt extruded at 190 ~ 230 DEG C by the twin screw extruder that length-to-diameter ratio is larger, tie rod, cooling, granulation, obtain irradiate crosslinked thermoplastic polyester elastomer cable material finished product masterbatch.Described finished wire CABLE MATERIALS extrudes wire rod through twin screw extruder and conductor (metallic conductor such as copper or aluminium), is cross-linked by gained wire rod, cross-linked dosage 14Mrad, can obtains finished product cable by electron accelerator irradiation.
embodiment 5
Fill a prescription composed as follows:
Thermoplastic polyester elastomer (TPEE) 100 parts;
Ethylene-vinyl acetate copolymer (EVA) 15 parts;
Melamine cyanurate (MCA) 35 parts;
Organic secondary phosphine acid salt 20 parts;
Silicone 1.5 parts;
Antioxidant 1010 1.5 parts;
Anti ultraviolet agent 7700.3 parts.
Preparation process is as follows:
After weighing and add by above-mentioned component formula and stir in high-speed mixer, discharging, obtains mixture.Compound is melt extruded at 190 ~ 230 DEG C by the twin screw extruder that length-to-diameter ratio is larger, tie rod, cooling, granulation, obtain irradiate crosslinked thermoplastic polyester elastomer cable material finished product masterbatch.Described finished wire CABLE MATERIALS extrudes wire rod through twin screw extruder and conductor (metallic conductor such as copper or aluminium), is cross-linked by gained wire rod, cross-linked dosage 14Mrad, can obtains finished product cable by electron accelerator irradiation.
embodiment 6
Fill a prescription composed as follows:
Thermoplastic polyester elastomer (TPEE) 100 parts;
Ethylene-vinyl acetate copolymer (EVA) 20 parts;
Melamine cyanurate (MCA) 40 parts;
Organic secondary phosphine acid salt 20 parts;
Silicone 1 part;
Irgasfos 168 1.5 parts;
Anti ultraviolet agent 7700.3 parts.
Preparation process is as follows:
After weighing and add by above-mentioned component formula and stir in high-speed mixer, discharging, obtains mixture.Compound is melt extruded at 190 ~ 230 DEG C by the twin screw extruder that length-to-diameter ratio is larger, tie rod, cooling, granulation, obtain irradiate crosslinked thermoplastic polyester elastomer cable material finished product masterbatch.Described finished wire CABLE MATERIALS extrudes wire rod through twin screw extruder and conductor (metallic conductor such as copper or aluminium), is cross-linked by gained wire rod, cross-linked dosage 14Mrad, can obtains finished product cable by electron accelerator irradiation.
The performance perameter table that the finished product cable that table 1 is produced for embodiment 1 ~ 6 is mainly tested.
The performance perameter table that table 1 is tested
The present invention adopts TPEE to be main base material, makes CABLE MATERIALS have excellent room temperature and high-temperature mechanical property; Add EVA elastomerics, efficiently solve CABLE MATERIALS temperature in the course of processing and raise and the sharply viscosity reduction of appearance, the one-tenth charcoal that EVA is good also makes the flame retardant properties of system get a promotion; Cross-linking radiation is compared chemicure method and is had more clean feature, after irradiation the anti-drippage of matrix material with become charcoal and have obvious lifting, organic phosphorus flame retardant addition is reduced, effectively controls cost, obtain the obvious lifting of room temperature and high-temperature mechanical property simultaneously; Melamine cyanurate is main body and the nitrogen composite with organic secondary phosphine acid salt, phosphorus flame-retardant system realize halogen-free environmental on the basis of excellent fire-retardancy, in use can not being heated or the sun is exposed to the sun and produces poisonous halogen-containing materials because of energising, meeting European Union RoHs(" about being limited in electronic and electrical equipment the instruction using some objectionable constituent " simultaneously) standard and European Union REACH(" registration of chemical, assessment, mandate and restriction ") environmental requirement of decree; System of the present invention and cross-linking radiation processing means also make finished product cable show excellent oil-proofness and scrape abrasion resistance energy.
The present invention is not limited to above-mentioned embodiment, and those skilled in the art also can make multiple change accordingly, but to be anyly equal to the present invention or similar change all should be encompassed in the scope of the claims in the present invention.
Claims (8)
1. an irradiate crosslinked thermoplastic polyester elastomer cable material, is characterized in that, comprises following composition by weight:
Thermoplastic polyester elastomer (TPEE) 100 parts;
Ethylene-vinyl acetate copolymer (EVA) 15 ~ 40 parts;
Fire retardant 50 ~ 80 parts;
Lubricant 0.3 ~ 2 part;
0.3 ~ 3 part, oxidation inhibitor;
UV light stabilizing agent 0.1 ~ 1 part.
2. irradiate crosslinked thermoplastic polyester elastomer cable material as claimed in claim 1, is characterized in that: the segmented copolymer that described thermoplastic polyester elastomer (TPEE) is the hard section of polybutylene terephthalate and aliphatic polyester or polyester soft segment.
3. irradiate crosslinked thermoplastic polyester elastomer cable material as claimed in claim 1, is characterized in that: the vinyl acetate co-monomer content range of described ethylene-vinyl acetate copolymer (EVA) is 14% ~ 28%.
4. irradiate crosslinked thermoplastic polyester elastomer cable material as claimed in claim 1, it is characterized in that: the melamine cyanurate (MCA) in described fire retardant employing nitrogen, phosphorus flame retardant, the combination of organic secondary phosphine acid salt, and be the main body of compounding flame retardant with MCA.
5. irradiate crosslinked thermoplastic polyester elastomer cable material as claimed in claim 1, is characterized in that: described lubricant adopts silicone master batch.
6. irradiate crosslinked thermoplastic polyester elastomer cable material as claimed in claim 1; it is characterized in that: described oxidation inhibitor is four [methyl-β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester (antioxidant 1010), N; N '-bis-[3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl] combination of one or more of the two lauryl alcohol ester (oxidation inhibitor 412s) of quadrol (oxidation inhibitor 1098), three [2,4-di-tert-butyl-phenyl] phosphorous acid ester (irgasfos 168) or thio-2 acid.
7. irradiate crosslinked thermoplastic polyester elastomer cable material as claimed in claim 1, is characterized in that: described UV light stabilizing agent is two (2,2,6,6-tetramethyl--4-piperidines) sebate (anti ultraviolet agent 770).
8. a production method for irradiate crosslinked thermoplastic polyester elastomer cable, comprises the following steps:
1) batch weighing: weighed various raw material by irradiate crosslinked thermoplastic polyester elastomer cable material formula described in claim 1 ~ 7;
2) powder mixing is played: added by load weighted irradiate crosslinked thermoplastic polyester elastomer cable material after stirring in high-speed mixer, discharging, obtains mixture;
3) compound melt extruded at 190 ~ 230 DEG C by the twin screw extruder that length-to-diameter ratio is larger, tie rod, cooling, granulation, obtain irradiate crosslinked thermoplastic polyester elastomer cable material finished product masterbatch;
4) described finished cable material extrudes wire rod through twin screw extruder and conductor, is cross-linked by gained wire rod by electron accelerator irradiation, and cross-linked dosage 10-17Mrad can obtain finished cable.
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| CN201510715893.2A CN105199329A (en) | 2015-10-29 | 2015-10-29 | Irradiation cross-linked thermoplastic polyester elastomer cable material and cable production method |
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| CN201510715893.2A CN105199329A (en) | 2015-10-29 | 2015-10-29 | Irradiation cross-linked thermoplastic polyester elastomer cable material and cable production method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106947223A (en) * | 2017-04-20 | 2017-07-14 | 江汉大学 | Thermoplastic polyester elastomer fire-retardant combination and preparation method thereof |
| CN107474491A (en) * | 2017-08-02 | 2017-12-15 | 江苏道勤新材料科技有限公司 | A kind of sheath material of solar photovoltaic cable |
| CN107955337A (en) * | 2017-11-08 | 2018-04-24 | 江阴凯博通信科技有限公司 | A kind of radio frequency line PE sheaths |
| CN108997718A (en) * | 2018-07-05 | 2018-12-14 | 南通大学 | High-termal conductivity halogen-free flameproof TPEE elastic composition |
| CN110746682A (en) * | 2019-11-14 | 2020-02-04 | 苏州铂玛新材料有限公司 | Oil-resistant irradiation crosslinked wire and cable material for rail transit vehicles and preparation method thereof |
| CN114854116A (en) * | 2022-05-12 | 2022-08-05 | 乐庭电线工业（惠州）有限公司 | Halogen-free flame-retardant cross-linked polyolefin rubber material for rail transit and preparation method thereof |
| CN116606532A (en) * | 2023-05-08 | 2023-08-18 | 江苏上上电缆集团新材料有限公司 | Shock-resistant buffer material for polypropylene insulated cable and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947223A (en) * | 2017-04-20 | 2017-07-14 | 江汉大学 | Thermoplastic polyester elastomer fire-retardant combination and preparation method thereof |
| CN107474491A (en) * | 2017-08-02 | 2017-12-15 | 江苏道勤新材料科技有限公司 | A kind of sheath material of solar photovoltaic cable |
| CN107955337A (en) * | 2017-11-08 | 2018-04-24 | 江阴凯博通信科技有限公司 | A kind of radio frequency line PE sheaths |
| CN107955337B (en) * | 2017-11-08 | 2021-05-14 | 江阴凯博通信科技有限公司 | Radio frequency line PE sheath |
| CN108997718A (en) * | 2018-07-05 | 2018-12-14 | 南通大学 | High-termal conductivity halogen-free flameproof TPEE elastic composition |
| CN110746682A (en) * | 2019-11-14 | 2020-02-04 | 苏州铂玛新材料有限公司 | Oil-resistant irradiation crosslinked wire and cable material for rail transit vehicles and preparation method thereof |
| CN114854116A (en) * | 2022-05-12 | 2022-08-05 | 乐庭电线工业（惠州）有限公司 | Halogen-free flame-retardant cross-linked polyolefin rubber material for rail transit and preparation method thereof |
| CN114854116B (en) * | 2022-05-12 | 2024-02-09 | 乐庭电线工业（惠州）有限公司 | Halogen-free flame-retardant crosslinked polyolefin sizing material for rail transit and preparation method thereof |
| CN116606532A (en) * | 2023-05-08 | 2023-08-18 | 江苏上上电缆集团新材料有限公司 | Shock-resistant buffer material for polypropylene insulated cable and preparation method and application thereof |
| CN116606532B (en) * | 2023-05-08 | 2024-07-26 | 江苏上上电缆集团新材料有限公司 | Shock-resistant buffer material for polypropylene insulated cable and preparation method and application thereof |
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Application publication date: 20151230 |