CN102898809A - Halogen-free flame-retardant polyphenylether cable material, its preparation and application - Google Patents
Halogen-free flame-retardant polyphenylether cable material, its preparation and application Download PDFInfo
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- CN102898809A CN102898809A CN2011102125262A CN201110212526A CN102898809A CN 102898809 A CN102898809 A CN 102898809A CN 2011102125262 A CN2011102125262 A CN 2011102125262A CN 201110212526 A CN201110212526 A CN 201110212526A CN 102898809 A CN102898809 A CN 102898809A
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Abstract
Belonging to the technical field of high polymer materials, the invention relates to a halogen-free flame-retardant polyphenylether cable material and its preparation method. The halogen-free flame-retardant polyphenylether cable material comprises the following components by weight: 30-50% of polyphenylether; 10-25% of an elastomer; 10-15% of polyethylene; 8-28% of a flame retardant; 0.2-1% of an antioxidant; and 0.2-1% of a lubricant. The invention further discloses a preparation method of the halogen-free flame-retardant polyphenylether cable material. In the invention, polyethylene and the elastomer are employed to modify polyphenylether, and functionalized polyphenylether is not adopted as a compatilizer, so that the material proportioning and preparation can be simplified, and the production cost is reduced. Due to good processing performance, no halogen, flame retardance, low density, high tensile strength and other excellent properties, the halogen-free flame-retardant polyphenylether cable material can be widely used in electronic wire insulation materials.
Description
Technical field
The present invention relates to technical field of polymer materials, relate in particular to a kind of halogen-free fire-retardant polyphenyl ether CABLE MATERIALS and preparation and application.
Background technology
Polyphenylene oxide is poly-2,6-dimethyl-Isosorbide-5-Nitrae-phenylate, claims again polyphenylene oxide.Polyphenylene oxide is nontoxic, relative density is little, has that good physical strength, proof stress are lax, a creep resistance, thermotolerance, water tolerance, water-fast steam, dimensional stability.Good electrical property in very wide temperature, range of frequency is not hydrolyzed, molding shrinkage is little, and difficult combustion has self-extinguishing, inorganic acid resistance, alkali.Yet, single polyphenylene oxide resin poor fluidity, the forming process difficulty, hardness is high, is difficult to use as CABLE MATERIALS.During as CABLE MATERIALS, need to carry out modification to it.
Elastomer-modified by in polyphenylene oxide, adding, can effectively improve the processing fluidity of polyphenylene oxide, reduce its hardness, add simultaneously fire retardant, also will further improve the flame retardant resistance of polyphenylene oxide.Through the polyphenylene oxide of modification, can reach processing characteristics and the pliability similar with polyvinyl chloride cable material, but because it is the halogen-free flameproof product, so than polyvinyl chloride safety and environmental protection more.
Chinese patent specification sheets CN 101130616A discloses a kind of low-smoke zero-halogen flame-retardant polyphenyl ether wire cable material and preparation method thereof.Wherein, modified resin is elastomerics and high-impact polystyrene (HIPS), has adopted simultaneously functionalized polyphenylene ether as compatilizer, the prescription relative complex, and also cost is not low yet.
Summary of the invention
The object of the invention is to adopt elastomerics, polyethylene and fire retardant polyphenylene ether to carry out modification, a kind of novel halogen-free fire-retardant polyphenyl ether CABLE MATERIALS and preparation method thereof is provided, to overcome deficiency of the prior art.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme to realize:
A kind of halogen-free fire-retardant polyphenyl ether CABLE MATERIALS, its raw material comprises the component of following weight percentage:
Polyphenylene oxide 30-50%;
Elastomerics 10-25%;
Polyethylene 10-15%
Fire retardant 8-28%;
Oxidation inhibitor 0.2-1%;
Lubricant 0.2-1%.
Better, the viscosity of described polyphenylene oxide is between 0.38dl/1-0.52dl/l.
Better, described elastomerics is the styrenic elastomerics, such as butadiene-styrene copolymer SBS, hydrogenated butadiene-styrene copolymer SEBS etc.As, butadiene-styrene copolymer SBS can be selected from the trades mark such as SBS-3206 of Tai Xiang Co., Ltd; Hydrogenated butadiene-styrene copolymer SEBS can be selected from the trades mark such as SEBS1651 that high-performance polymer company is risen by U.S. section.
Better, described poly melting index is 0.2-7g/10min.
Better, described fire retardant is halogen-free flame retardants, described halogen-free flame retardants is melamine cyanurate (MCA), from Suzhou triumphant horse chemistry science and technology limited Company.
Better, described oxidation inhibitor is antioxidant 1076, namely (β-positive octadecanol ester of (4-hydroxy phenyl-3,5-di-t-butyl) propionic acid) can directly buy from the market.
Better, described lubricant is ethylene bis stearamide (EBS).
The preparation method of halogen-free fire-retardant polyphenyl ether CABLE MATERIALS of the present invention may further comprise the steps:
(1) polyphenylene oxide, elastomerics, polyethylene, fire retardant, oxidation inhibitor and lubricant are put into high-speed mixer according to proportioning, under the rotating speed of 1500-3000rpm high-speed mixing 1-3 minute;
(2) after the high-speed mixing, in the mixing machine of step (1), low speed mixing and discharging under the rotating speed of 500-1000rpm;
(3) raw material that mixes is put into the twin screw extruder extruding pelletization, obtain described halogen-free fire-retardant polyphenyl ether CABLE MATERIALS.
Better, in the step (3), the rotating speed of described double-screw extruding pelletizing machine is 180-600 rev/min, temperature is 200-280 ℃.
Described high-speed mixer is the GH-200DY type high-speed mixer that Beijing plastics machinery factory produces; Described twin screw extruder is the TSE-75 type twin screw extruder that Nanjing Rhea superpolymer equipment company limited produces.
Halogen-free fire-retardant polyphenyl ether CABLE MATERIALS of the present invention has following advantage:
1, the present invention has utilized the high strength of polyphenylene oxide self and the characteristics of flame retardant resistance, has improved the original poor fluidity of polyphenylene oxide, shortcoming that hardness is high by adding polyethylene and styrenic elastomerics, has prepared high-intensity halogen-free fire-retardant polyphenyl ether CABLE MATERIALS.
2, the present invention adopts polyethylene and elastomerics polyphenylene ether to carry out modification, and does not use functionalized polyphenylene ether as compatilizer, has simplified proportioning and the preparation of material, has reduced production cost.
3, halogen-free fire-retardant polyphenyl ether CABLE MATERIALS material of the present invention because have good processability, halogen-free flameproof, the premium properties such as density is low, tensile strength is high, the electric wire Insulation Material can be widely used in, and traditional flame-proof polyvinyl chloride (PVC) CABLE MATERIALS can be replaced.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that these embodiment only are used for explanation the present invention and are not used in restriction protection scope of the present invention.
Embodiment 1
The preparation method of the halogen-free fire-retardant polyphenyl ether CABLE MATERIALS of the present embodiment may further comprise the steps:
(1) takes by weighing raw material according to 1 listed each component of embodiment in the table 1 and weight percentage thereof;
(2) above-mentioned raw materials is put into high-speed mixer, high speed 3000rpm mixed approximately 1-3 minute;
(3) with again low speed 800rpm mixing and discharging of the raw material after the high-speed mixing;
(4) raw material that mixes is put into the twin screw extruder extruding pelletization, obtain the halogen-free fire-retardant polyphenyl ether CABLE MATERIALS of the present embodiment, wherein, the rotating speed of twin screw extruder is controlled at 200-300 rev/min, and temperature is controlled in 250-280 ℃ the scope.
The halogen-free fire-retardant polyphenyl ether CABLE MATERIALS that embodiment 1 makes is carried out performance test, and its test result is as shown in table 2.
Embodiment 2
The preparation method of the halogen-free fire-retardant polyphenyl ether CABLE MATERIALS of the present embodiment may further comprise the steps:
(1) takes by weighing raw material according to 2 listed each component of embodiment in the table 1 and weight percentage thereof;
(2) above-mentioned raw materials is put into high-speed mixer, high speed 2000rpm mixed approximately 1-3 minute;
(3) with again low speed 1000rpm mixing and discharging of the raw material after the high-speed mixing;
(4) raw material that mixes is put into the twin screw extruder extruding pelletization, obtain the halogen-free fire-retardant polyphenyl ether CABLE MATERIALS of the present embodiment, wherein, the rotating speed of twin screw extruder is controlled at 180-200 rev/min, and temperature is controlled in 250-280 ℃ the scope.
The halogen-free fire-retardant polyphenyl ether CABLE MATERIALS that embodiment 2 makes is carried out performance test, and its test result is as shown in table 2.
Embodiment 3
The preparation method of the halogen-free fire-retardant polyphenyl ether CABLE MATERIALS of the present embodiment may further comprise the steps:
(1) takes by weighing raw material according to 3 listed each component of embodiment in the table 1 and weight percentage thereof;
(2) above-mentioned raw materials is put into high-speed mixer, high speed 2500rpm mixed approximately 1-3 minute;
(3) with again low speed 500rpm mixing and discharging of the raw material after the high-speed mixing;
(4) raw material that mixes is put into the twin screw extruder extruding pelletization, obtain the halogen-free fire-retardant polyphenyl ether CABLE MATERIALS of the present embodiment, wherein, the rotating speed of twin screw extruder is controlled at 400-500 rev/min, and temperature is controlled in 200-220 ℃ the scope.
The halogen-free fire-retardant polyphenyl ether CABLE MATERIALS that embodiment 3 makes is carried out performance test, and its test result is as shown in table 2.
Embodiment 4
The preparation method of the halogen-free fire-retardant polyphenyl ether CABLE MATERIALS of the present embodiment may further comprise the steps:
(1) takes by weighing raw material according to 4 listed each component of embodiment in the table 1 and weight percentage thereof;
(2) above-mentioned raw materials is put into high-speed mixer, high speed 1500rpm mixed approximately 1-3 minute;
(3) with again low speed 1000rpm mixing and discharging of the raw material after the high-speed mixing;
(4) raw material that mixes is put into the twin screw extruder extruding pelletization, obtain the halogen-free fire-retardant polyphenyl ether CABLE MATERIALS of the present embodiment, wherein, the rotating speed of twin screw extruder is controlled at 500-600 rev/min, and temperature is controlled in 220-250 ℃ the scope.
The halogen-free fire-retardant polyphenyl ether CABLE MATERIALS that embodiment 4 makes is carried out performance test, and its test result is as shown in table 2.
The raw material of table 1 embodiment 1-4 forms and proportioning (unit: kilogram)
In the table 1: the viscosity of polyphenylene oxide 1 is 0.38dl/l, blue star chemical industry, LXRO40;
The viscosity of polyphenylene oxide 2 is 0.45dl/l, blue star chemical industry, LXRO45;
The viscosity of polyphenylene oxide 3 is 0.52dl/l, blue star chemical industry, LXRO50;
Polyethylene 1, melting index are 0.2g/10min, BASF-YPC petrochemical industry, 1810D
Polyethylene 2, melting index are 7g/10min; Yanshan Petrochemical, 1C7A.
Fire retardant, Suzhou triumphant horse chemistry science and technology limited Company, melamine cyanurate (MCA)
Comparative Examples 1
Comparative Examples 1 is referring to Chinese patent specification sheets CN 101130616A low-smoke zero-halogen flame-retardant polyphenyl ether wire cable material and preparation method thereof.Its composition (mass parts) is as follows:
Polyphenylene oxide PPO 40～80;
High-impact polystyrene HIPS 20～60;
Elastomerics 10～70;
Functionalized polyphenylene ether 10～20;
Fire retardant 10～60;
Smoke suppressor 5～20;
Oxidation inhibitor 1～3;
Environmental protection Masterbatch 3～5.
The material property of table 2 embodiment 1-4
In the table 2, the testing method of each project is as follows:
The mensuration of melt flow rate (MFR) is carried out according to the regulation of the mensuration of GB3682-2000 thermoplastics melt mass flow rate and melt volume-flow rate.
The mensuration of density is according to the mensuration part 1 of the non-foam plastic density of GB1033.1-2008 plastics: the pickling process regulation in pickling process, liquid specific gravity bottle method and the volumetry is carried out.
The mensuration of tensile strength is carried out according to GB/T 1040-1992 plastic tensile method for testing performance regulation, during test with the speed stretching sample of 25mm/min.
The mensuration of elongation at break is carried out according to GB/T 1040-1992 plastic tensile method for testing performance regulation, during test with the speed stretching sample of 25mm/min.
The mensuration of 20 ℃ of lower volume resistivity is carried out according to GB/T 1410-1989 solid insulating material volume specific resistance and surface resistivity test method regulation.
The mensuration of specific inductivity is carried out in the test method regulation of power frequency, audio frequency, the lower relative permittivity of high frequency (comprising metric wave length) and dielectric dissipation factor according to GB 1409-88 solid insulating material.
The mensuration of dielectric dissipation factor is carried out in the test method regulation of power frequency, audio frequency, the lower relative permittivity of high frequency (comprising metric wave length) and dielectric dissipation factor according to GB 1409-88 solid insulating material.
The mensuration of shore hardness is carried out according to GB 2411-1980 plastics shore hardness test method regulation.
Flame retardant properties is according to the testing method test of 1080 VW-1 among the UL1581.
Comparative Examples and embodiment contrast as can be known from table 2, the halogen-free fire-retardant polyphenyl ether CABLE MATERIALS of the present invention preparation has preferably processing characteristics simultaneously, and (melt flow rate (MFR) is larger, mobile better), higher tensile strength, preferably flame retardant resistance, preferably electrical property, lower hardness and lower density.Polyphenylene oxide (PPO) material of material of the present invention and Comparative Examples 1 of the prior art is compared, and principal feature is: formula constituent difference of the present invention and quantity still less especially do not use functionalized polyphenylene ether as compatilizer; The density of product of the present invention is lower, the product density 〉=1.14g/cm of Comparative Examples 1
3, and density of material≤1.06g/cm of the present invention
3, and halogen-free fire-retardant polyphenyl ether CABLE MATERIALS of the present invention has above-mentioned performance index simultaneously, is a kind of novel halogen-free fire-retardant polyphenyl ether CABLE MATERIALS, therefore is more suitable for using as electric wire class CABLE MATERIALS.
Claims (10)
1. halogen-free fire-retardant polyphenyl ether CABLE MATERIALS, its raw material comprises the component of following weight percentage:
Polyphenylene oxide 30-50%;
Elastomerics 10-25%;
Polyethylene 10-15%
Fire retardant 8-28%;
Oxidation inhibitor 0.2-1%;
Lubricant 0.2-1%.
2. halogen-free fire-retardant polyphenyl ether CABLE MATERIALS as claimed in claim 1 is characterized in that, the viscosity of described polyphenylene oxide is between 0.38dl/1-0.52dl/l; Described poly melting index is 0.2-7g/10min.
3. halogen-free fire-retardant polyphenyl ether CABLE MATERIALS as claimed in claim 1 is characterized in that, described elastomerics is the styrenic elastomerics.
4. halogen-free fire-retardant polyphenyl ether CABLE MATERIALS as claimed in claim 3 is characterized in that, described styrenic elastomerics is butadiene-styrene copolymer SBS or hydrogenated butadiene-styrene copolymer SEBS.
5. halogen-free fire-retardant polyphenyl ether CABLE MATERIALS as claimed in claim 1 is characterized in that, described fire retardant is halogen-free flame retardants; Described halogen-free flame retardants is melamine cyanurate.
6. halogen-free fire-retardant polyphenyl ether CABLE MATERIALS as claimed in claim 1 is characterized in that, described oxidation inhibitor is β-positive octadecanol ester of (4-hydroxy phenyl-3,5-di-t-butyl) propionic acid.
7. halogen-free fire-retardant polyphenyl ether CABLE MATERIALS as claimed in claim 1 is characterized in that, described lubricant is ethylene bis stearamide.
8. such as the preparation method of the arbitrary described halogen-free fire-retardant polyphenyl ether CABLE MATERIALS of claim 1-7, comprise the steps:
(1) polyphenylene oxide, elastomerics, polyethylene, fire retardant, oxidation inhibitor and lubricant are put into high-speed mixer according to proportioning, under the rotating speed of 1500-3000rpm high-speed mixing 1-3 minute;
(2) after the high-speed mixing, in the mixing machine of step (1), low speed mixing and discharging under the rotating speed of 500-1000rpm;
(3) raw material that mixes is put into the twin screw extruder extruding pelletization, obtain described halogen-free fire-retardant polyphenyl ether CABLE MATERIALS.
9. the preparation method of halogen-free fire-retardant polyphenyl ether CABLE MATERIALS as claimed in claim 8 is characterized in that, in the step (3), the rotating speed of described double-screw extruding pelletizing machine is 180-600 rev/min, and temperature is 200-280 ℃.
10. such as the application of the arbitrary described halogen-free fire-retardant polyphenyl ether CABLE MATERIALS of claim 1-7 on electric wire.
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| CN2011102125262A CN102898809A (en) | 2011-07-27 | 2011-07-27 | Halogen-free flame-retardant polyphenylether cable material, its preparation and application |
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| CN103289282A (en) * | 2013-05-06 | 2013-09-11 | 安徽格林生态高分子材料技术有限公司 | Cable sheath material containing modified poly-phenyl ether resin and preparation method thereof |
| CN103554891A (en) * | 2013-10-25 | 2014-02-05 | 安徽文峰电子科技集团有限公司 | Oil-resistant and ultraviolet-resistant modified epoxy chloropropane rubber cable material |
| CN104575771A (en) * | 2014-12-31 | 2015-04-29 | 东莞市高能磁电技术有限公司 | Halogen-free flame retardant insulated power cable adopting polyphenyl ether composite material |
| CN105315604A (en) * | 2015-10-30 | 2016-02-10 | 安徽天星光纤通信设备有限公司 | Anti-fatigue flame-retardant cable material and preparation method thereof |
| CN107248428A (en) * | 2017-06-22 | 2017-10-13 | 安徽电缆股份有限公司 | Environment-friendly type power cable |
| CN112898762A (en) * | 2020-12-24 | 2021-06-04 | 中辰电缆股份有限公司 | High-performance flame-retardant cable material and preparation method thereof |
| CN113603960A (en) * | 2021-09-14 | 2021-11-05 | 广东聚石化学股份有限公司 | Halogen-free flame-retardant material and preparation method and application thereof |
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Application publication date: 20130130 |