CN109851976B - Halogen-free modified TPE flame-retardant cable material and preparation method thereof - Google Patents
Halogen-free modified TPE flame-retardant cable material and preparation method thereof Download PDFInfo
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- CN109851976B CN109851976B CN201910071644.2A CN201910071644A CN109851976B CN 109851976 B CN109851976 B CN 109851976B CN 201910071644 A CN201910071644 A CN 201910071644A CN 109851976 B CN109851976 B CN 109851976B
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Abstract
The invention provides a halogen-free modified TPE flame-retardant cable material and a preparation method thereof, wherein the halogen-free modified TPE flame-retardant cable material consists of hydrogenated styrene-butadiene-styrene, ethylene-propylene copolymer, polypropylene, a flame-retardant synergist, a flame retardant, an antioxidant and a plasticizer, and further comprises a lubricant and the like, the raw materials are mixed and granulated in a proper weight ratio, and the preparation process flow is as follows: firstly, part of raw materials are stirred in a stirrer in a high-mixing mode for 20-30 minutes, and then the raw materials are extruded by a double screw, pulled into strips, cooled by water, air-dried, cut into particles and packaged; the halogen-free modified TPE flame-retardant cable material prepared by the formula and the process has the characteristics of high flame retardance, high ultraviolet light resistance, low odor, low cost, clean and efficient production mode and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a halogen-free modified TPE flame-retardant cable material and a preparation method thereof.
Background
Along with the requirement of people on products is higher and higher, the traditional PVC cable material is gradually replaced by a more green and environment-friendly TPE cable material due to factors such as dense smoke generated by combustion, HCl containing corrosive gas, insufficient elasticity and the like.
In the chinese patent "CN 101831134B", the flame retardant is a polyphenylene ether resin and a phosphorus-nitrogen composite flame retardant, wherein the polyphenylene ether resin can improve char formation, thereby improving flame retardant performance, but the addition of the polyphenylene ether resin can cause the ultraviolet light resistance of the product to be poor and the rubber compound to contain a large amount of volatile odor, and because the polyphenylene ether resin itself is slightly light, the addition of a large amount of polyphenylene ether is not easily applicable to white and other light-colored rubber compounds, and can cause the material cost to be too high, which is not beneficial to the application and popularization of the TPE material.
In consideration of the defects of halogen-free modified TPE flame-retardant cable materials in the market, the novel flame-retardant synergist and the flame retardant are used for modification, so that the ultraviolet light resistance and the low odor of the TPE material are improved, the good flame-retardant property and the low cost characteristic of the material are ensured, and the material can be widely blended into various colors.
Disclosure of Invention
The invention mainly aims at the defects of the prior art and provides a halogen-free modified TPE flame-retardant cable material and a preparation method thereof.
In order to solve the technical problems, the invention aims to realize the following technical scheme:
the halogen-free modified TPE flame-retardant cable material comprises the following raw materials in parts by weight: 15-30 parts by weight of hydrogenated styrene-butadiene-styrene; 10-25 parts of plasticizer; 10-20 parts of polypropylene; 10-20 parts by weight of an ethylene-propylene copolymer; 12-20 parts of flame-retardant synergist; 20-30 parts of a flame retardant; 0.2 to 0.4 weight portion of antioxidant; 0.5 to 1.5 weight portions of lubricant.
Wherein: the hydrogenated styrene-butadiene-styrene is pure resin powder with the weight average molecular weight of 100000-150000.
Wherein: the plasticizer is white oil with the kinematic viscosity (25 ℃) of between 150 and 500 mm/s.
Wherein: the polypropylene is copolymerization type polypropylene with the melt index of 3-15g/10 min.
Wherein: the ethylene-propylene copolymer has tensile strength of more than 30.0 MPa and elongation at break of more than 550%.
Wherein: the flame retardant is a compound of melamine cyanurate and aluminum diethylphosphinate in a ratio of 1:1-1: 3.
Wherein: the flame-retardant synergist is boron-series low-melting-point glass powder, the melting point temperature is 390-450 ℃, and the average particle size is 5-8 microns.
Wherein: the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
Wherein: the lubricant is silicone master batch, wherein the silicone content is 65-75%.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a halogen-free modified TPE flame-retardant cable material comprises the following steps:
a: weighing the raw materials according to the weight ratio;
b: adding hydrogenated styrene-butadiene-styrene, white oil, polypropylene, ethylene-propylene copolymer, lubricant, flame retardant synergist, flame retardant and antioxidant into a 300L stirring pot, and stirring and mixing for 20-30 minutes in the stirring pot;
c: b, discharging the mixed raw materials in the step b to a double-screw machine with the diameter of 65mm, and extruding and plasticizing at the extrusion temperature of 180-220 ℃;
d: and (3) carrying out bracing water cooling, air cooling, grain cutting and packaging on the extruded and plasticized rubber material through a double-screw eye die.
The halogen-free modified TPE flame-retardant cable material with high weather resistance, low odor, excellent flame retardance and lower cost can be prepared, the adopted raw materials are environment-friendly and non-toxic raw materials, the 100% recycling can be realized, the production mode is clean and efficient, and no pollution is caused to the environment.
Detailed Description
The preparation method of the halogen-free modified TPE flame-retardant cable material comprises the following steps:
a: weighing the raw materials according to the weight ratio of one of the comparative examples 1-2 and the examples 3-5;
b: adding hydrogenated styrene-butadiene-styrene, white oil, polypropylene, ethylene-propylene copolymer, lubricant, charring agent, flame retardant and stabilizer into a 300L stirring pot, and mixing at low speed for 15-25 min;
c. b, discharging the mixed raw materials in the step b to a double-screw machine with the diameter of 65mm, and extruding and plasticizing at the extrusion temperature of 180-220 ℃;
d: and (3) carrying out bracing water cooling, air cooling, grain cutting and packaging on the extruded and plasticized rubber material through a double-screw eye die. For a further understanding of the invention, reference will now be made in detail to specific embodiments of the invention:
in comparative examples 1-2 and examples 3-5, hydrogenated styrene-butadiene-styrene was pure resin powder with a weight average molecular weight of 100000-150000, plasticizer was white oil with a kinematic viscosity (at 25 ℃) of 150-500 mm/s, polypropylene was copolymer polypropylene with a melt index of 3-15g/10min, ethylene-propylene copolymer was a copolymer of tensile strength greater than 30.0 MPa and elongation at break greater than 550%, flame retardant was a mixture of melamine cyanurate and aluminum diethylphosphinate in a ratio of 1:1-1:3, flame retardant synergist was boron-based low-melting glass powder, melting temperature was 390-450 ℃, average particle size was 5-8 μm white powder, antioxidant was tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, the lubricant is silicone master batch, wherein the silicone content is 65-75%. In the process of melting the boron-based low-melting-point glass powder by heating, a part of the boron-based low-melting-point glass powder forms a glass-state heat insulation protective layer, and a part of the boron-based low-melting-point glass powder reacts with free radicals in resin to form refractory substances for heat insulation and oxygen insulation, so that the flame retardant effect is achieved.
Comparative example 1:
26 parts by weight of hydrogenated styrene-butadiene-styrene, 20 parts by weight of plasticizer, 9 parts by weight of polypropylene, 15 parts by weight of ethylene-propylene copolymer, 30 parts by weight of flame retardant, 15 parts by weight of polyphenylene ether resin, 0.2 part by weight of stabilizer and 1.5 parts by weight of lubricant are weighed. Mixing the materials in a stirrer at a low speed for 25 minutes, discharging the materials to a double-screw extruder with the diameter of 65mm, and extruding and plasticizing at the extrusion processing temperature of 180-220 ℃.
Comparative example 2:
26 parts by weight of hydrogenated styrene-butadiene-styrene, 20 parts by weight of plasticizer, 9 parts by weight of polypropylene, 15 parts by weight of ethylene-propylene copolymer, 40 parts by weight of flame retardant, 0.2 part by weight of stabilizer and 1.5 parts by weight of lubricant are weighed. Mixing the materials in a stirrer at a low speed for 25 minutes, discharging the materials to a double-screw extruder with the diameter of 65mm, and extruding and plasticizing at the extrusion processing temperature of 180-220 ℃.
Example 3:
26 parts of hydrogenated styrene-butadiene-styrene, 20 parts of plasticizer, 9 parts of polypropylene, 15 parts of ethylene-propylene copolymer, 30 parts of flame retardant, 12 parts of flame retardant synergist, 0.2 part of stabilizer and 1.5 parts of lubricant are weighed. Mixing the materials in a stirrer at a low speed for 25 minutes, discharging the materials to a double-screw extruder with the diameter of 65mm, and extruding and plasticizing at the extrusion processing temperature of 180-220 ℃.
Example 4:
weighing 26 parts by weight of hydrogenated styrene-butadiene-styrene, 20 parts by weight of plasticizer, 9 parts by weight of polypropylene, 15 parts by weight of ethylene-propylene copolymer, 25 parts by weight of flame retardant, 16 parts by weight of flame retardant synergist, 0.2 part by weight of stabilizer and 1.5 parts by weight of lubricant. Mixing the materials in a stirrer at a low speed for 25 minutes, discharging the materials to a double-screw extruder with the diameter of 65mm, and extruding and plasticizing at the extrusion processing temperature of 180-220 ℃.
Example 5:
26 parts of hydrogenated styrene-butadiene-styrene, 20 parts of plasticizer, 9 parts of polypropylene, 15 parts of ethylene-propylene copolymer, 20 parts of flame retardant synergist, 0.2 part of stabilizer and 1.5 parts of lubricant are weighed. Mixing the materials in a stirrer at a low speed for 25 minutes, discharging the materials to a double-screw extruder with the diameter of 65mm, and extruding and plasticizing at the extrusion processing temperature of 180-220 ℃.
And (3) performance testing:
elongation tensile was tested according to UL1581 standard;
the flame retardance is tested according to UL 94V-0 standard, and the thickness of a test strip is 3.2 mm;
odor test was tested according to VDA276 standard;
UV light resistance test according to GB/T16422.3-1997, test conditions: the exposure was performed by irradiation at black standard temperature 60 ℃. + -. 3 ℃ for 4h, followed by exposure by non-irradiation condensation at black standard temperature 50 ℃. + -. 3 ℃ for 4h, which was 1 cycle, for a total of 12 cycles.
The formulations (parts by weight) and raw material property test items of comparative examples 1 to 2 and examples 3 to 5 are as follows (1):
as can be seen from comparison of the examples in the table (1), the flame-retardant synergistic agent low-melting-point glass powder is compounded with melamine cyanurate and aluminum diethylphosphinate to serve as a flame retardant, so that the flame-retardant synergistic agent has obvious advantages in low odor and UV resistance.
The halogen-free modified TPE flame-retardant cable material and the preparation method thereof provided by the invention are described in detail, the principle and the implementation mode of the invention are explained by applying specific examples, and the description of the examples is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art of the present invention, there may be variations in the specific embodiments and the application scope according to the idea of the present invention, and as described above, the content of the present specification should not be construed as a limitation to the present invention.
Claims (8)
1. The halogen-free modified TPE flame-retardant cable material comprises the following raw materials in parts by weight: 15-30 parts by weight of hydrogenated styrene-butadiene-styrene; 10-25 parts of plasticizer; 10-20 parts of polypropylene; 10-20 parts by weight of an ethylene-propylene copolymer; 12-20 parts of flame-retardant synergist; 20-30 parts of a flame retardant; 0.2 to 0.4 weight portion of antioxidant; 0.5-1.5 parts by weight of a lubricant;
the flame retardant is a compound of melamine cyanurate and aluminum diethylphosphinate in a ratio of 1:1-1: 3;
the flame-retardant synergist is boron-series low-melting-point glass powder, the melting point temperature is 390-450 ℃, and the particle size is 5-8 microns white powder.
2. The halogen-free modified TPE flame retardant cable material as claimed in claim 1, wherein: the hydrogenated styrene-butadiene-styrene is pure resin powder with the weight average molecular weight of 100000-150000.
3. The halogen-free modified TPE flame retardant cable material as claimed in claim 1, wherein: the plasticizer is white oil with kinematic viscosity between 150 and 500 mm/s.
4. The halogen-free modified TPE flame retardant cable material as claimed in claim 1, wherein: the polypropylene is copolymerization type polypropylene with the melt index of 3-15g/10 min.
5. The halogen-free modified TPE flame retardant cable material as claimed in claim 1, wherein: the ethylene-propylene copolymer has tensile strength of more than 30.0 MPa and elongation at break of more than 550%.
6. The halogen-free modified TPE flame retardant cable material as claimed in claim 1, wherein: the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
7. The halogen-free modified TPE flame retardant cable material as claimed in claim 1, wherein: the lubricant is silicone master batch, wherein the silicone content is 65-75%.
8. A preparation method of a halogen-free modified TPE flame-retardant cable material comprises the following steps:
a: weighing the raw materials as defined in any one of claims 1 to 7 in a weight ratio;
b: adding hydrogenated styrene-butadiene-styrene, white oil, polypropylene, ethylene-propylene copolymer, lubricant, flame retardant synergist, flame retardant and antioxidant into a 300L stirring pot, and mixing at low speed for 20-30 minutes in the stirring pot;
c: b, discharging the mixed raw materials in the step b to a double-screw machine with the diameter of 65mm, and extruding and plasticizing at the extrusion temperature of 180-220 ℃;
d: and (3) carrying out bracing water cooling, air cooling, grain cutting and packaging on the extruded and plasticized rubber material through a double-screw eye die.
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| CN112391024A (en) * | 2020-10-16 | 2021-02-23 | 深圳市沃尔核材股份有限公司 | Anti-cracking TPE sheath material for charging cable and preparation and application thereof |
| CN112341745A (en) * | 2020-10-16 | 2021-02-09 | 深圳市沃尔核材股份有限公司 | TPE sheath material for charging cable and preparation and application thereof |
| CN112812491B (en) * | 2020-12-30 | 2022-09-23 | 江西博硕电子有限公司 | External coating material and preparation method and application thereof |
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| CN106398083A (en) * | 2016-08-31 | 2017-02-15 | 苏州亨利通信材料有限公司 | Oil-resistant halogen-free flame retardant TPE (Thermo Plastics Elastomer) cable material and preparation method thereof |
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Patent Citations (5)
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| CN103635534A (en) * | 2011-06-29 | 2014-03-12 | 东丽株式会社 | Thermoplastic resin composition and molded article comprising same |
| CN104086940A (en) * | 2014-07-04 | 2014-10-08 | 博硕科技(江西)有限公司 | Halogen-free flame retardant TPE (thermoplastic polyurethane elastomer) injection molding material and preparation method thereof |
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