CN107987516B - TPU/terpolymer nylon composite halogen-free flame-retardant cable material and preparation method thereof - Google Patents
TPU/terpolymer nylon composite halogen-free flame-retardant cable material and preparation method thereof Download PDFInfo
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- CN107987516B CN107987516B CN201711261809.XA CN201711261809A CN107987516B CN 107987516 B CN107987516 B CN 107987516B CN 201711261809 A CN201711261809 A CN 201711261809A CN 107987516 B CN107987516 B CN 107987516B
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
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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
- H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
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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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- 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
- C08L2205/03—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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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a TPU/terpolymer nylon composite halogen-free flame-retardant cable material and a preparation method thereof. The cable material comprises the following raw materials in parts by weight: 30-70% of thermoplastic polyurethane elastomer, 5-25% of ternary nylon copolymer, 5-25% of compatilizer, 1-10% of hardness regulator, 10-30% of flame retardant, 1-5% of lubricant, 0-3% of antioxidant, 0-3% of titanium dioxide, 0-3% of anti-UV agent and 0-2% of hydrolysis resistant agent. The TPU/terpolymer nylon composite halogen-free flame-retardant cable material has the advantages of high mechanical property, qualified flame-retardant property, oil resistance, hydrolysis resistance, strong chemical liquid resistance, wear resistance, scratch resistance and excellent processing property, combines the characteristic of good heat resistance of a terpolymer, improves the heat resistance of the whole cable material, and can keep the hardness of the whole cable material in a more proper range of 75-85A due to the addition of a hardness regulator.
Description
Technical Field
The invention relates to the technical field of cable materials, in particular to a TPU/terpolymer nylon composite halogen-free flame-retardant cable material and a preparation method thereof.
Background
In the field of electric wire and cable materials with elastomer as base material, TPE-S, TPU and PVC are commonly used. The use of PVC materials is prohibited in the European market, but a large number of manufacturers still use the PVC materials in large scale because the PVC materials can meet the standard performance due to the lower price, but the PVC materials emit a large amount of black smoke and other toxic and harmful substances polluting the environment during combustion, so that the ecological environment is seriously affected, and the use amount of the PVC materials is reduced in the future. TPE-S is also a common elastomer material at present, and a cable material prepared by taking oil-filled SEBS and PP as base materials is widely used in a consumer data line, an earphone cable and an electric automobile charging pile cable, but the service life of the cable material is influenced by the cracking problem easily generated in the using process according to the feedback of a cable manufacturer, and the oil resistance of the cable material is not strong, so that the service life of the whole cable is reduced. The common TPU material is limited in many fields because of poor flame retardant property and heat resistance and difficult control of processing technology.
Therefore, the invention combines the information and takes TPU as a base material, thereby providing the cable material which has the advantages of excellent mechanical property, qualified flame retardant property, oil resistance, hydrolysis resistance, strong chemical liquid resistance, wear resistance, scratch resistance and excellent processing property, combines the characteristic of good heat resistance of the ternary nylon copolymer, and improves the heat resistance of the whole cable material.
Disclosure of Invention
One of the objects of the present invention is: aiming at the technical defects in the aspects of TPU electric wires and cables in China at present, the TPU/terpolymer nylon composite halogen-free flame-retardant cable material is provided, and has the advantages of excellent mechanical property, higher tearing strength, good flame retardance, excellent hydrolysis resistance and chemical liquid resistance, wear resistance, scratch resistance, lower hardness and better processing property.
The second purpose of the invention is to provide a preparation method of the TPU/ternary copolymer nylon composite halogen-free flame-retardant cable material.
In order to achieve the purpose, the invention can be realized by the following technical scheme that the TPU/ternary copolymer nylon composite halogen-free flame-retardant cable material is prepared from the following raw materials in percentage by mass:
the thermoplastic polyurethane elastomer is a polyether thermoplastic polyurethane elastomer (TPU), and has good oil resistance, wear resistance and cracking resistance. The polyether type thermoplastic polyurethane elastomer (TPU) used in the invention can be selected from Pasteur TPU resin 1185A, Hensmei TPU A85P4394 or Wanhua TPU WHT-8185 RU.
The ternary nylon copolymer is a ternary copolymer resin of nylon 6, nylon 66 and nylon 610. The ternary nylon copolymer used in the invention can be selected from M-150 copolymerized nylon provided by Shanghai Zhenwei or American DuPont 8063.
The compatilizer is a random ethylene-acrylate-maleic anhydride terpolymer. The polymer has good reactivity, crystallinity and fluidity, can have good compatibility with ternary polymerization nylon, and has excellent thermal stability in the processing process. The compatibilizer used in the present invention may be LOTADER MAH 4210 from arkema, france.
The hardness regulator is candelilla wax. The Kandelia wax mainly comprises alkyl ester, free alcohol, hydrocarbon compound, free acid and the like, can effectively adjust the hardness of the whole system, and has certain functions of improving thermal stability, moisture resistance and lubrication.
The flame retardant is an intumescent phosphorus-nitrogen flame retardant. The phosphorus-nitrogen flame retardant is one or a mixture of more than two of diethyl aluminum phosphinate, aluminum hypophosphite, resorcinol bis (diphenyl phosphate), bisphenol A-bis (diphenyl phosphate) (BDP), melamine cyanurate, melamine polyphosphate, white carbon black and nano organic montmorillonite.
The phosphorus flame retardant in the phosphorus-nitrogen flame retardant is phosphate or aluminum diethylphosphinate in an amount of 60-85 wt%, and the nitrogen flame retardant is melamine cyanurate in an amount of 15-40 wt%.
The lubricant is one or a mixture of more than two of ethylene bis-oleic acid amide, ethylene bis-stearic acid amide, silicone master batch and zinc stearate. Ethylene bis-oleamide or ethylene bis-stearamide is preferred. The lubricant of the invention is EBS EB-G of King of Japan.
The antioxidant is a compound antioxidant obtained by compounding a hindered phenol antioxidant and a thioester antioxidant or phosphite antioxidant. Preferably, the antioxidant is one or a mixture of more than two of an antioxidant 1010, an antioxidant 1098, an antioxidant 245, an antioxidant 1790, an antioxidant 445, an antioxidant DLTP and an antioxidant 168. Particularly preferably, the antioxidant is a composite antioxidant of antioxidant 445 and antioxidant 168, and the ratio is 1: 1-2.
The titanium dioxide is titanium dioxide (TiO)2) The polycrystalline compound of (1). The titanium dioxide used in the invention is R-103 or R-706 provided by DuPont.
The UV resistant agent is one of UV-531, UV-320 and UV-326. UV-531 is preferred.
The hydrolysis resistant agent is polycarbodiimide. Stabaxol P200 is preferred in Rhine, Germany.
The preparation method of the TPU/ternary copolymer nylon composite halogen-free flame-retardant cable material comprises the following steps:
(1) preparing corresponding raw materials according to the proportion of each component, and cleaning all instruments required by production;
(2) pouring all the raw materials into a high mixing pot in sequence, stirring uniformly, and adding the mixed raw materials into a double-screw extruder;
(3) putting the mixed material into a double-screw extruder for melt kneading and extrusion, wherein the extrusion temperature is 140-190 ℃, and the screw rotation speed is 10-167 rpm;
(4) and cooling the extrudate through a conveyor belt, granulating and drying to obtain the TPU/ternary copolymer nylon composite halogen-free flame-retardant cable material.
Compared with the prior art, the invention has the following advantages:
(1) the TPU/ternary copolymer nylon composite halogen-free flame-retardant cable material adopts the polyether polyurethane elastomer and is additionally provided with a plurality of auxiliary agents with oil resistance, so that the oil resistance of the whole system is further improved.
(2) The TPU/terpolymer nylon composite halogen-free flame-retardant cable material provided by the invention introduces terpolymer nylon, so that the mechanical strength and toughness of the whole system are further improved. In addition, the excellent heat resistance, self-extinguishing property and corrosion resistance of nylon are combined, so that the temperature resistance level, flame retardance and chemical liquid resistance of the whole system are further improved.
(3) The thermoplastic polyurethane elastomer and the ternary nylon copolymer used in the TPU/ternary copolymer nylon composite halogen-free flame-retardant cable material have strong water absorbability, so that the hydrolysis resistance is improved by adding the hydrolysis resistance agent. Meanwhile, the light resistance of the two is also not enough, so the addition of the UV resistant agent is improved.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to comparative examples, but the present invention is not limited to these examples.
Table one: comparative examples and weight percent (%).
The mass ratio of antioxidant 445 to antioxidant 168 in Table I was 1:2
The preparation methods of the examples in the first table all comprise the following steps:
(1) preparing corresponding raw materials according to the proportion of each component, and cleaning all instruments required by production;
(2) pouring all the raw materials into a high mixing pot in sequence, stirring uniformly, and adding the mixed raw materials into a double-screw extruder;
(3) putting the mixed material into a double-screw extruder for melt kneading and extrusion, wherein the extrusion temperature is 140-190 ℃, and the screw rotation speed is 10-167 rpm;
(4) and cooling the extrudate through a conveyor belt, granulating and drying to obtain the TPU/ternary copolymer nylon composite halogen-free flame-retardant cable material.
The comparative example was prepared in substantially the same manner as the examples. Table two: example and comparative example performance data.
As can be seen from comparison between comparative examples 1 and 2 and examples 1 to 5 in the table, although comparative examples 1 and 2 have higher tensile strength without any other resin modification, the other properties can not pass the requirements, and after the ternary nylon copolymer and the compatilizer are added in examples 1 to 5, the properties of the whole system such as hydrolysis resistance, mineral oil resistance, thermal aging resistance and the like are effectively improved, so that the specific requirements of use are met. In addition, the hardness is obviously improved after the hardness modifiers with different proportions are added.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or scope of the invention as defined in the appended claims.
Claims (9)
1. The TPU/ternary copolymer nylon composite halogen-free flame-retardant cable material is characterized by being prepared from the following raw materials in percentage by mass:
45-70% of a thermoplastic polyurethane elastomer;
5-25% of a ternary nylon copolymer;
5-25% of a compatilizer;
1-10% of a hardness regulator;
10-30% of a flame retardant;
1-5% of a lubricant;
0-3% of an antioxidant;
0-3% of titanium dioxide;
0-3% of an anti-UV agent;
0-2% of hydrolysis resistance agent;
the thermoplastic polyurethane elastomer is a polyether type thermoplastic polyurethane elastomer;
the ternary nylon copolymer is nylon 6, nylon 66 and nylon 610 ternary copolymer resin;
the compatilizer is a random ethylene-acrylate-maleic anhydride terpolymer;
the hydrolysis resistant agent is polycarbodiimide.
2. The TPU/terpolymer nylon composite halogen-free flame retardant cable material as claimed in claim 1, wherein the hardness modifier is Kandelia wax.
3. The TPU/terpolymer nylon composite halogen-free flame-retardant cable material as claimed in claim 1, wherein the flame retardant is an intumescent phosphorus nitrogen flame retardant.
4. The TPU/terpolymer nylon composite halogen-free flame retardant cable material as claimed in claim 3, wherein the intumescent phosphorus-nitrogen flame retardant is one or a mixture of any two or more of diethyl aluminum phosphinate, aluminum hypophosphite, resorcinol bis (diphenyl phosphate), bisphenol A-bis (diphenyl phosphate), melamine cyanurate and melamine polyphosphate.
5. The TPU/terpolymer nylon composite halogen-free flame-retardant cable material as claimed in claim 1, wherein the lubricant is one or a mixture of any two or more of ethylene bis-oleic acid amide, ethylene bis-stearic acid amide, silicone master batch and zinc stearate.
6. The TPU/terpolymer nylon composite halogen-free flame-retardant cable material as claimed in claim 1, wherein the antioxidant is a composite antioxidant obtained by compounding a hindered phenol antioxidant and a phosphite antioxidant or a thioester antioxidant.
7. The TPU/terpolymer nylon composite halogen-free flame-retardant cable material as claimed in claim 1, wherein the titanium dioxide is titanium dioxide (TiO)2) The polycrystalline compound of (1).
8. The TPU/terpolymer nylon composite halogen-free flame retardant cable material as claimed in claim 1, wherein the UV resistant agent is one of UV-531, UV-320 and UV-326.
9. The preparation method of the TPU/terpolymer nylon composite halogen-free flame retardant cable material as claimed in any one of claims 1 to 8, characterized by comprising the following steps:
(1) preparing corresponding raw materials according to the proportion of each component, and cleaning all instruments required by production;
(2) pouring all the raw materials into a high mixing pot in sequence, stirring uniformly, and adding the mixed raw materials into a double-screw extruder;
(3) putting the mixed material into a double-screw extruder for melt kneading and extrusion, wherein the extrusion temperature is 140-190 ℃, and the screw rotation speed is 10-167 rpm;
(4) and cooling the extrudate through a conveyor belt, granulating and drying to obtain the TPU/terpolymer nylon composite halogen-free flame-retardant cable material.
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| CN201711261809.XA CN107987516B (en) | 2017-12-04 | 2017-12-04 | TPU/terpolymer nylon composite halogen-free flame-retardant cable material and preparation method thereof |
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| CN201711261809.XA CN107987516B (en) | 2017-12-04 | 2017-12-04 | TPU/terpolymer nylon composite halogen-free flame-retardant cable material and preparation method thereof |
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| CN110591343B (en) * | 2019-09-02 | 2022-03-29 | 湖南华曙高科技股份有限公司 | High-molecular powder material, preparation method thereof and method for preparing workpiece by using material |
| CN113861379A (en) * | 2020-06-30 | 2021-12-31 | 三元科技（深圳）有限公司 | Manufacturing method of TPU (thermoplastic polyurethane) medical cable and medical cable |
| CN113881216B (en) * | 2021-11-24 | 2023-04-28 | 国网河南省电力公司镇平县供电公司 | Wear-resistant flame-retardant modified polyurethane cable material and preparation method thereof |
| CN117024959B (en) * | 2023-10-08 | 2023-12-15 | 广州海天汽车配件有限公司 | Low-compression-deformation nylon composite material for hydrogen storage tank and preparation method thereof |
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| CA2417485C (en) * | 2002-01-29 | 2010-08-17 | Kuraray Co., Ltd. | Thermoplastic polyurethane composition and process for producing the same |
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