CN102226031A - Polyphenylether/thermoplastic elastomer composition used for cables and preparation method thereof - Google Patents
Polyphenylether/thermoplastic elastomer composition used for cables and preparation method thereof Download PDFInfo
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- CN102226031A CN102226031A CN 201110159179 CN201110159179A CN102226031A CN 102226031 A CN102226031 A CN 102226031A CN 201110159179 CN201110159179 CN 201110159179 CN 201110159179 A CN201110159179 A CN 201110159179A CN 102226031 A CN102226031 A CN 102226031A
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Abstract
The invention relates to a polyphenylether/thermoplastic elastomer composition used for cables and a preparation method thereof, relating to halogen-free, flame-retardant, high-temperature and low-temperature resistant and environmentally-friendly materials. The polyphenylether/thermoplastic elastomer composition comprises the following components in parts by weight: 10-15 parts of polyphenylether, 30-45 parts of SEBS (styrene-ethylene-butadiene-styrene block copolymer), 30-45 parts of POE (polyoxyethylene), 25-45 parts of flame retardant, 5-10 parts of smoke suppressant, 0.5-6 parts of flame-retardant synergist, 0.1-9 parts of compatibilizer, 0.1-2 parts of antioxidant and 0.01-2 parts of processing aid. According to the invention, the addition of a functionalized thermoplastic elastomer effectively improves the compatibility between the non-polar elastomer and polyphenylether, and the complex synergistic effect of red phosphorus and magnesium hydroxide improves the flexibility, flame retardancy, high-temperature and low-temperature resistance, water resistance and electrical insulation properties of wire and cable coating materials prepared by using a Swiss BUSS four-screw reciprocating mixing machine.
Description
Technical field
The present invention relates to halogen-free flameproof, high-low temperature resistant ep-type material, especially a kind of cable polyphenylene oxide/composition for thermoplastic elastomer and preparation method thereof.
Background technology
In today of economic develop rapidly, electric wire is called as " artery " and " nerve " of national economy as the hinge of information transmission and energy transformation.Traditional polyvinyl chloride (PVC) as the electric wire coating material is still being dominated market, because at high temperature decomposing, it produces a large amount of pungencys and corrosive gases, not only serious harm people's healthy, contaminate environment, and etching apparatus are brought the tremendous economic loss.Along with the raising that in the world fireproof environmental is required, exploitation high-performance, high-low temperature resistant non-halogen flame-retardant cable have become trend.Polyphenylene oxide mechanical property excellence, high temperature resistant, do not absorb water, insulating property are good; The thermoplastic elastomer processing characteristics is good, snappiness good, and the application on electric cable material with low smoke and halogen free has obtained promoting.So the two preferred interworking is prepared halogen-free flameproof, the high-low temperature resistant polyphenylene oxide/composition for thermoplastic elastomer coating material as electric wire, has a extensive future.
Example test result display material pliability is relatively poor among China publication CN101130616A and the CN101928453A, as is used for making mobile phone, computer data line etc. and can not gives comfort.Reduce hardness by adding a large amount of softening softening agent among the publication CN101358028A, make that the intensity of gained blend is lower, resistance toheat is not good.Publication CN101698742A improves polyphenylene oxide and elastomeric consistency with the method for dynamic crosslinking, and elastomer content is higher in the example, and processing temperature reaches 280 ℃, and high temperature has disadvantageous effect to material property.
Summary of the invention
In order to overcome above-mentioned defective, the technical problem to be solved in the present invention is: at existing problem, provide a kind of cable polyphenylene oxide/composition for thermoplastic elastomer.
In order to overcome the defective that exists in the background technology, the technical solution adopted for the present invention to solve the technical problems is: a kind of cable polyphenylene oxide/composition for thermoplastic elastomer, and its composition and ratio are as follows by umber:
10～25 parts of polyphenylene oxide (PPO),
Styrene/ethylene-butylene/styrene multipolymer
(SEBS) 50～90 parts,
Ethylene/octene
(POE) 50～90 parts,
0.1～9 part of compatilizer,
25～55 parts of fire retardants,
0.5～6 part of fire retarding synergist,
5～10 parts of smoke suppressors,
0.1～2 part in oxidation inhibitor,
0.01～2 part of processing aid;
Polyphenylene oxide described in the present invention (PPO) is to gather 2,6-dimethyl 1,4 phenylate, and number-average molecular weight is 2.8 * 10
4～3.6 * 10
4, limiting viscosity is to record in the 38mL/g(25 ℃ of chloroform).
SEBS elastomerics described in the present invention is styrene-ethylene/butadiene-styrene block copolymer that hydrogenation hydrogenation forms, and molecular weight is 2.7 * 10
5～3.3 * 10
5, and belong to simple linear polymer.
POE described in the present invention is an ethylene-octene copolymer, and tensile strength 5～15MPa, elongation at break are greater than 600%, and molecular weight is 1.5 * 10
5～2.5 * 10
5, MFR is 1.0～20g/min(230 ℃, 2.16Kg).
For polymer scale is lumped together, a kind of in the maleic anhydride that adopts the melt extrusion technology preparation, acrylic or methacrylic acid glycidyl ester graft phenylethene/ethene-butylene/styrene multipolymer (SEBS-g-MAH, SEBS-g-AA, SEBS-g-GMA), the ethylene/octene (POE-g-MAH, POE-g-AA, POE-g-GMA) of compatilizer described in the present invention, can improve the consistency of matrix material and the dispersiveness of filler greatly, enhance product performance.
Fire retardant described in the present invention is the composite flame-retardant agent of magnesium hydroxide and the red phosphorus composition that coating is handled through shell, and its mass ratio is 1:7-10.It is the micro encapsulation red phosphorus of cyst wall preparation with siloxanes, melamine-formaldehyde, Resins, epoxy or urethane that the described red phosphorus that coating is handled through shell adopts situ aggregation method, phosphorus content wherein〉80%, good with the matrix resin affinity, described magnesium hydroxide granularity is 1000～5000.
Fire retarding synergist described in the present invention is a kind of in methylsiloxane, ethylene methacrylic radical siloxane, the methylphenyl siloxane.
Smoke suppressor described in the present invention is melamine cyanurate (MCA), zinc borate (2ZnO3B
2O
33.5H
2O), a kind of in molybdenum oxide or the ammonium octamolybdate.
Oxidation inhibitor described in the present invention is Hinered phenols antioxidant 1010, and its structural formula is:
Phosphite ester kind antioxidant 168, its structural formula is:
Thio-2 acid di-esters oxidation inhibitor DSTDP, its structural formula is
In a kind of, make up arbitrarily composite forming.
Processing aid described in the present invention comprises a kind of in stearic acid and derivative (calcium stearate etc.) or the polyethylene wax.
Cable described in the present invention preparation method of polyphenylene oxide/composition for thermoplastic elastomer, carry out according to following steps:
1) sets each component of accurate weighing according to prescription;
2) with above-mentioned 1) component be divided into three parts by the classification of resin, fire retardant and small powder, small powder comprises smoke suppressor, compatilizer, fire retarding synergist, oxidation inhibitor, processing aid, and adds weightless electronic scale separately;
3) through weightless electronic weighing system, enter this (BUSS) machine spiral shell cylinder of Switzerland's cloth from charging opening equably according to preestablishing ratio; By the reciprocating type calendering process of distinctive four sea whelks of BUSS machine, underwater cutpellet is finished granulation process, obtains finished product.
Beneficial effect of the present invention:
1) the invention provides a kind of soft durometer suitable (Shore A 84～88), not halogen-containing, and have polyphenylene oxide/composition for thermoplastic elastomer formula technique and production method thereof that the electric wire and cable jacket/insulation layer of high-low temperature resistant, high flame resistance is used.
2) this polyphenylene oxide/composition for thermoplastic elastomer meets environmental regulation requirements such as " two green instructions ", can recycling use, meet the trend of the green recycling economy development of current China.
Embodiment
Embodiment one to six
The embodiment operating procedure: the cable preparation method of composition for thermoplastic elastomer has following steps:
1) sets each component of accurate weighing according to table 1 prescription;
2) with above-mentioned 1) component be divided into three parts by the classification of resin, fire retardant and small powder, small powder comprises smoke suppressor, compatilizer, fire retarding synergist, oxidation inhibitor, processing aid, and adds weightless electronic scale separately;
3) through weightless electronic weighing system, enter this (BUSS) machine spiral shell cylinder of Switzerland's cloth from charging opening equably according to preestablishing ratio; By the reciprocating type calendering process of distinctive four sea whelks of BUSS machine, underwater cutpellet is finished granulation process, obtains finished product.
Following table is the proportioning raw materials of embodiment one to six and the correlated performance parameter (unit is g) of corresponding finished:
Table 1
Following table is every the key technical indexes of the finished product of embodiment one to six preparation
Table 2 the key technical indexes
Claims (10)
1. a cable is with polyphenylene oxide/composition for thermoplastic elastomer, it is characterized in that its form and ratio as follows by umber:
10～25 parts of polyphenylene oxide,
50～90 parts of styrene/ethylene-butylene/styrene multipolymer,
50～90 parts of ethylene/octene,
0.1～9 part of compatilizer,
25～55 parts of fire retardants,
0.5～6 part of fire retarding synergist,
5～10 parts of smoke suppressors,
0.1～2 part in oxidation inhibitor,
0.01～2 part of processing aid.
2. a kind of cable according to claim 1 is characterized in that with polyphenylene oxide/composition for thermoplastic elastomer wherein said polyphenylene oxide is to gather 2,6-dimethyl 1,4 phenylate, and number-average molecular weight is 2.8 * 10
4～3.6 * 10
4Wherein said styrene/ethylene-butylene/styrene multipolymer is styrene-ethylene/butadiene-styrene block copolymer that hydrogenation hydrogenation forms, and molecular weight is 2.7 * 10
5～3.3 * 10
5Wherein said ethylene/octene molecular weight is 1.5 * 10
5～2.5 * 10
5
3. a kind of cable according to claim 1 is with polyphenylene oxide/composition for thermoplastic elastomer, it is characterized in that a kind of in the maleic anhydride that adopts the melt extrusion technology preparation, acrylic or methacrylic acid glycidyl ester graft phenylethene/ethene-butylene/styrene multipolymer, the ethylene/octene of wherein said compatilizer.
4. a kind of cable according to claim 1 is characterized in that with polyphenylene oxide/composition for thermoplastic elastomer wherein said fire retardant is the composite flame-retardant agent of magnesium hydroxide and the red phosphorus composition that coating is handled through shell, and its mass ratio is 1:7-10.
5. a kind of cable according to claim 1 is with polyphenylene oxide/composition for thermoplastic elastomer, it is characterized in that wherein said fire retarding synergist is a kind of in methylsiloxane, ethylene methacrylic radical siloxane, the methylphenyl siloxane.
6. a kind of cable according to claim 1 is with polyphenylene oxide/composition for thermoplastic elastomer, it is characterized in that wherein said smoke suppressor is a kind of in melamine cyanurate, zinc borate, molybdenum oxide or the ammonium octamolybdate.
7. a kind of cable according to claim 1 is characterized in that with polyphenylene oxide/composition for thermoplastic elastomer wherein said oxidation inhibitor is Hinered phenols antioxidant 1010, and its structural formula is:
Phosphite ester kind antioxidant 168, its structural formula is:
Thio-2 acid di-esters oxidation inhibitor DSTDP, its structural formula is
In a kind of, carry out that arbitrary combination is composite to form.
8. a kind of cable according to claim 1 is with polyphenylene oxide/composition for thermoplastic elastomer, it is characterized in that wherein said processing aid is a kind of in stearic acid and derivative or the polyethylene wax.
9. a kind of cable polyphenylene oxide/composition for thermoplastic elastomer according to claim 4, it is characterized in that it is the micro encapsulation red phosphorus of cyst wall preparation with siloxanes, melamine-formaldehyde, Resins, epoxy or urethane that the wherein said red phosphorus that coating is handled through shell adopts situ aggregation method, phosphorus content wherein〉80%, described magnesium hydroxide granularity is 1000～5000.
10. the described a kind of cable of claim 1 carries out according to following steps with the preparation method of polyphenylene oxide/composition for thermoplastic elastomer:
1) sets each component of accurate weighing according to prescription;
2) with above-mentioned 1) component be divided into three parts by the classification of resin, fire retardant and small powder, small powder comprises smoke suppressor, compatilizer, fire retarding synergist, oxidation inhibitor, processing aid, and adds weightless electronic scale separately;
3) through weightless electronic weighing system, enter this machine spiral shell cylinder of cloth from charging opening equably according to preestablishing ratio; By the reciprocating type calendering process of distinctive four sea whelks of this machine of cloth, underwater cutpellet is finished granulation process, obtains finished product.
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|---|---|---|---|
| CN 201110159179 CN102226031B (en) | 2011-06-15 | 2011-06-15 | Polyphenylether/thermoplastic elastomer composition used for cables and preparation method thereof |
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|---|---|---|---|
| CN 201110159179 CN102226031B (en) | 2011-06-15 | 2011-06-15 | Polyphenylether/thermoplastic elastomer composition used for cables and preparation method thereof |
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| CN102226031B CN102226031B (en) | 2013-07-17 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181169A (en) * | 2011-04-21 | 2011-09-14 | 深圳市塑源实业有限公司 | Preparation method of thermoplastic elastomer (TPE) alloy material for polyethylene terephthalate (PBT) bonding encapsulation |
| CN102585428A (en) * | 2012-03-15 | 2012-07-18 | 浙江北化阻燃材料有限公司 | Flexible halogen-free flame-retardant polyphenyl ether electric wire cable shield material and preparation method thereof |
| CN102675853A (en) * | 2012-05-21 | 2012-09-19 | 金发科技股份有限公司 | High-glowing-filament-temperature resistant polyphenyl ether/styrene resin composite |
| CN102731898A (en) * | 2012-07-23 | 2012-10-17 | 天津有容蒂康高分子材料有限公司 | Material for electric wire and cable |
| CN102775766A (en) * | 2012-08-17 | 2012-11-14 | 武汉工程大学 | Flame-retardant rigid polyurethane foaming plastic composite material and preparation method thereof |
| CN103450621A (en) * | 2013-08-15 | 2013-12-18 | 江苏三角洲塑化有限公司 | High-temperature-resistant low-smoke halogen-free flame-retardant thermoplastic elastomer cable material and preparation method thereof |
| CN103897324A (en) * | 2012-12-27 | 2014-07-02 | 中纺投资发展股份有限公司 | Halogen-free flame-retardant polyphenyl ether composition and preparation method thereof |
| CN105111672A (en) * | 2015-08-27 | 2015-12-02 | 无为县茂林电缆材料有限公司 | High-temperature-resistant crack-resistant flame-retardant cable material and preparation method thereof |
| CN107033523A (en) * | 2017-05-16 | 2017-08-11 | 浙江大学 | Electric wire halogen-free flame-retardant thermoplastic elastomer composition of anti-UV discolorations and preparation method thereof |
| CN110483957A (en) * | 2019-07-29 | 2019-11-22 | 江阴爱科森博顿聚合体有限公司 | A kind of preparation method of the dedicated PBT material of high rigidity optical cable |
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| CN101955626A (en) * | 2010-10-12 | 2011-01-26 | 江苏安格特新材料科技有限公司 | Cable thermoplastic elastomer composition and preparation method thereof |
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2011
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| CN101358028A (en) * | 2008-09-02 | 2009-02-04 | 宁波一舟塑胶有限公司 | Halogen-free flame-retardant thermoplastic elastomer electrical cable material using polyphenylene ether as base material and preparation method thereof |
| CN101831134A (en) * | 2010-05-10 | 2010-09-15 | 宁波市青湖弹性体科技有限公司 | Thermoplastic halogen-free flame retarding elastomer composition for electric wire and cable covering materials |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181169A (en) * | 2011-04-21 | 2011-09-14 | 深圳市塑源实业有限公司 | Preparation method of thermoplastic elastomer (TPE) alloy material for polyethylene terephthalate (PBT) bonding encapsulation |
| CN102585428A (en) * | 2012-03-15 | 2012-07-18 | 浙江北化阻燃材料有限公司 | Flexible halogen-free flame-retardant polyphenyl ether electric wire cable shield material and preparation method thereof |
| CN102675853A (en) * | 2012-05-21 | 2012-09-19 | 金发科技股份有限公司 | High-glowing-filament-temperature resistant polyphenyl ether/styrene resin composite |
| CN102675853B (en) * | 2012-05-21 | 2014-07-23 | 金发科技股份有限公司 | High-glowing-filament-temperature resistant polyphenyl ether/styrene resin composite |
| CN102731898A (en) * | 2012-07-23 | 2012-10-17 | 天津有容蒂康高分子材料有限公司 | Material for electric wire and cable |
| CN102775766B (en) * | 2012-08-17 | 2014-02-26 | 武汉工程大学 | Flame-retardant rigid polyurethane foaming plastic composite material and preparation method thereof |
| CN102775766A (en) * | 2012-08-17 | 2012-11-14 | 武汉工程大学 | Flame-retardant rigid polyurethane foaming plastic composite material and preparation method thereof |
| CN103897324A (en) * | 2012-12-27 | 2014-07-02 | 中纺投资发展股份有限公司 | Halogen-free flame-retardant polyphenyl ether composition and preparation method thereof |
| CN103450621A (en) * | 2013-08-15 | 2013-12-18 | 江苏三角洲塑化有限公司 | High-temperature-resistant low-smoke halogen-free flame-retardant thermoplastic elastomer cable material and preparation method thereof |
| CN105111672A (en) * | 2015-08-27 | 2015-12-02 | 无为县茂林电缆材料有限公司 | High-temperature-resistant crack-resistant flame-retardant cable material and preparation method thereof |
| CN107033523A (en) * | 2017-05-16 | 2017-08-11 | 浙江大学 | Electric wire halogen-free flame-retardant thermoplastic elastomer composition of anti-UV discolorations and preparation method thereof |
| CN107033523B (en) * | 2017-05-16 | 2019-01-11 | 浙江大学 | The halogen-free flame-retardant thermoplastic elastomer composition and preparation method thereof of the anti-UV discoloration of wire and cable |
| CN110483957A (en) * | 2019-07-29 | 2019-11-22 | 江阴爱科森博顿聚合体有限公司 | A kind of preparation method of the dedicated PBT material of high rigidity optical cable |
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Effective date of registration: 20150925 Address after: Daitou town of Liyang City Ferry Street 213311 Jiangsu city of Changzhou province 8-2 No. 7 Patentee after: Liyang Chang Technology Transfer Center Co., Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: Changzhou University |