CN102219948A - Thermoplastic low-smoke zero-halogen inflaming-retarding polyolefin cable material - Google Patents
Thermoplastic low-smoke zero-halogen inflaming-retarding polyolefin cable material Download PDFInfo
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- CN102219948A CN102219948A CN 201110153649 CN201110153649A CN102219948A CN 102219948 A CN102219948 A CN 102219948A CN 201110153649 CN201110153649 CN 201110153649 CN 201110153649 A CN201110153649 A CN 201110153649A CN 102219948 A CN102219948 A CN 102219948A
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Abstract
The invention discloses a thermoplastic low-smoke zero-halogen inflaming-retarding polyolefin cable material which is prepared by carrying out high-speed mixing, smelting, kneading, extruding and granulating on the following raw materials in parts by weight: 40-55 of aluminum hydroxide, 25-40 of metallocene polyolefin elastomer, 5-10 of low density polyethylene, 5-10 of compatilizer and auxiliaries such as color masterbatch and the like. Compared with the traditional rubber and plastic cable materials, the cable material disclosed by the invention has a good inflaming-retarding property, a good mechanical property and is free of halogen; when in burning, the cable material produces low smoke, dose not release harmful gases and can be popularized; a large amount of petrifaction resources can be saved, and electric fire hazard risk can be reduced, thus the cable material is environmentally-friendly and safe; and simultaneously, raw materials are available, and cost is low, thus the cable material has good economic and social benefits.
Description
The ㈠ technical field: the present invention relates to a kind of thermoplastic low-smoke halide-free fireproof composite polyolefine CABLE MATERIALS, this CABLE MATERIALS is on traditional rubber-plastics material basis, is matrix with the rare hydrocarbon copolymer of metallocene
Resin adds environment-friendly type non-bittern combustion inhibitor and the excellent especially required sheath material of photoelectricity cable of a kind of flame retardant effect of making simultaneously.
The ㈡ prior art: low smoke halogen-free fire retardant polyolefin cable material is widely used in the upgraded product of PVC CABLE MATERIALS.Compare with PVC, it has low cigarette, and is nontoxic, the advantage of Halogen.The low-smoke halogen-free cable matrix material generally is that a large amount of inorganic combustion inhibitor (metal hydroxides) is added in the polyolefin resin, such as polyethylene, and ethylene-acrylic acid second resin copolymer, olefines rubber (terpolymer EP rubber) etc.And to reach good flame-retardant effect, must in the low smoke and zero halogen system, add a large amount of inorganic combustion inhibitors, but because the consistency between matrix resin and the inorganic combustion inhibitor is very poor, thereby just cause the deterioration of mechanical property and the difficulty in the processing, particularly can't satisfy the sheath of photoelectricity cable factory and use.And if the fire retardant add-on is very little, then can cause flame retardant effect not enough again, can not satisfy the requirement of current social to high flame-retardant cable.Therefore how when allowing CABLE MATERIALS both possess good processing properties and mechanical property, possesses the research focus that excellent flame-retardant has just become current low-smoke non-halogen flame-retardant material again.
The ㈢ summary of the invention: purpose of the present invention just provides a kind of thermoplastic low-smoke halogen-free flame-resistant polyene
The hydrocarbon CABLE MATERIALS is because the existence of octene composition in the metallocene-polyolefin in the CABLE MATERIALS for common polyethylene, just can add the same of very heavy dose of inorganic combustion inhibitor
The time, still keep favorable mechanical performance and processing characteristics.
Thermoplastic low-smoke halide-free fireproof composite polyolefine CABLE MATERIALS of the present invention is the raw material by following weight part
Aluminium hydroxide 40-55
Metallocene polyolefin elastomers 25-40
New LDPE (film grade) 5-10
Compatilizer 5-10
Silane coupling agent 2.0-2.5
Lubricant 1.5-2.0
Oxidation inhibitor 0.1-0.2
Look mother 0.1-0.2
Through high-speed mixing, banburying, mediate, extrude, granulation makes.
A. matrix resin
In CABLE MATERIALS, the most widely used high molecular polymer that two big classes are arranged: polyolefine and synthetic rubber.Polyolefine mainly comprises vinyl resins, ethene and alpha olefin copolymer, ethylene and vinyl acetate copolymer, ethylene acrylic acid co polymer.And synthetic rubber mainly comprises isoprene-isobutylene rubber, styrene-butadiene rubber(SBR), terpolymer EP rubber or the like.
In the above-mentioned prescription, we select for use polyolefine as matrix resin.Say that further metallocene polyolefin elastomers and new LDPE (film grade) that we adopt metallocene catalysis to make are composite as matrix resin.
Metallocene polyolefin elastomers of the presently claimed invention need satisfy following condition:
(1) molecular weight distribution, Mw/Mm is greater than 1.5;
(2) density is more preferably between 0.870-0.885g/cm3 between 0.860-0.890g/cm3;
(3) melting index (190 ℃, 2.16Kg) greater than 0.3g/10Min,, be more preferably greater than 0.5g/10Min.
New LDPE (film grade) of the presently claimed invention need meet the following conditions:
(1) density is between 0.910-0.925;
(2) melting index (190 ℃, 2.16Kg) greater than 1g/10Min.
B. compatilizer
Compatilizer of the presently claimed invention is a kind of in the polymkeric substance that is made with maleic anhydride graft reaction or copolymerization respectively of polyethylene or α polyolefine or ethylene vinyl acetate copolymer.Desired compatilizer percentage of grafting needs greater than 0.5, is greater than 1 better.
C. fire retardant
Fire retardant involved in the present invention is the metal inorganic compound fire retardant: aluminium hydroxide.Desired aluminium hydroxide need satisfy following condition:
(1) aluminium hydroxide content is more preferably greater than 99.5% greater than 99%;
(2) than whiteness greater than 95%, be more preferably greater than 97%;
(3) the aluminium hydroxide particle diameter is more preferably less than 2 μ m less than 5 μ m;
(4) moisture content is more preferably less than 0.3% less than 0.5%.
D. auxiliary agent
The auxiliary agent that the present invention comprised has coupling agent, lubricant, look mother and oxidation inhibitor etc.Coupling agent is a silane coupling agent, and lubricant is a dimethyl silicone oil, and the look mother is common PE or EVA look mother, and oxidation inhibitor is common suffocated amine antioxidant.
The present invention's processing method routinely is prepared from.
Described ordinary method is: above-mentioned raw materials through mixing in the accurate metering input high speed mixer, is joined then and carries out banburying in the Banbury mixer, and the temperature of control Banbury mixer is lower than 150 ℃.Banburying 30 minutes is then with the material process double-screw extruding pelletizing that mixes.Make the fireproofing cable material without halide finished product after the cooling.
The present invention compares traditional rubber plastic cable material, because the existence of octene composition in the metallocene-polyolefin in the CABLE MATERIALS, for common polyethylene, just can when adding very heavy dose of inorganic combustion inhibitor, still keep excellent mechanical property and processing characteristics; Not halogen-containing, low cigarette does not discharge obnoxious flavour during burning, and its penetration and promotion can be saved a large amount of petrochemical industry resources, reduces electric disaster hidden-trouble, Environmental Safety; Raw material is easy to get simultaneously, and cost is lower, and good economic benefit and social benefit are arranged.
(4) embodiment
Embodiment 1
Accurately take by weighing following raw material:
Aluminium hydroxide 40kg
Metallocene polyolefin elastomers 40kg
New LDPE (film grade) 10kg
Compatilizer 5kg
Silane coupling agent 2.0kg
Dimethyl silicone oil 1.5kg
Suffocated amine antioxidant 0.1kg
PE look female 0.2kg
With mixing in the raw material input high speed mixer that weighs up, join then and carry out banburying in the Banbury mixer, the temperature of control Banbury mixer is lower than 150 ℃; Banburying 30 minutes is then with the kneading of material process twin screw, the extruding pelletization that mix.Promptly make the fireproofing cable material without halide finished product after the cooling.
Used aluminium hydroxide content is 99.5% in the above-mentioned prescription, and than whiteness 97%, particle diameter is 3.5 μ m, moisture content 0.5%;
Used metallocene polyolefin elastomers molecular weight distribution, Mw/Mm is 1.7; Density is 0.870g/cm3; Melting index (190 ℃, 2.16Kg) be 0.5g/10Min;
Used new LDPE (film grade) density is 0.920; Melting index (190 ℃ 2.16Kg) are 3g/10Min;
Used compatilizer is the polymkeric substance that α polyolefine and maleic anhydride copolymerization are made, and percentage of grafting is 1.
Embodiment 2
Accurately take by weighing following raw material:
Aluminium hydroxide 55kg
Metallocene polyolefin elastomers 26kg
New LDPE (film grade) 5kg
Compatilizer 10kg
Silane coupling agent 2.5kg
Dimethyl silicone oil 2.0kg
Black masterbatch 0.15kg
Suffocated amine antioxidant 0.2kg
With mixing in the raw material input high speed mixer that weighs up, join then and carry out banburying in the Banbury mixer, the temperature of control Banbury mixer is lower than 150 ℃; Banburying 30 minutes is then with the kneading of material process twin screw, the extruding pelletization that mix.Promptly make the fireproofing cable material without halide finished product after the cooling.
Used aluminium hydroxide content is 99.9% in the above-mentioned prescription, and than whiteness 97%, particle diameter is 1 μ m, moisture content 0.1%;
Used metallocene polyolefin elastomers molecular weight distribution, Mw/Mm is 6; Density is 0.890g/cm3; Melting index (190 ℃, 2.16Kg) be 0.3g/10Min;
Used new LDPE (film grade) density is 0.910; Melting index (190 ℃ 2.16Kg) are 5g/10Min;
Used compatilizer is the polymkeric substance that polyethylene and maleic anhydride graft reaction are made, and percentage of grafting is 2.0.
Embodiment 3
Accurately take by weighing following raw material:
Aluminium hydroxide 48kg
Metallocene polyolefin elastomers 35kg
New LDPE (film grade) 7kg
Compatilizer 7kg
Silane coupling agent 2.2kg
Dimethyl silicone oil 1.8kg
Suffocated amine antioxidant 0.15kg
EVA look mother (white) 0.10kg
With mixing in the raw material input high speed mixer that weighs up, join then and carry out banburying in the Banbury mixer, the temperature of control Banbury mixer is lower than 150 ℃; Banburying 30 minutes is then with the kneading of material process twin screw, the extruding pelletization that mix.Promptly make the fireproofing cable material without halide finished product after the cooling.
Used aluminium hydroxide content is 99.6% in the above-mentioned prescription, and than whiteness 95%, particle diameter is 2 μ m, moisture content 0.4%;
Used metallocene polyolefin elastomers molecular weight distribution, Mw/Mm is 1.5; Density is 0.860g/cm3; Melting index (190 ℃, 2.16Kg) be 0.4g/10Min;
Used new LDPE (film grade) density is 0.925; Melting index (190 ℃ 2.16Kg) are 1.5g/10Min;
Used compatilizer is the polymkeric substance that ethylene vinyl acetate copolymer and maleic anhydride graft reaction are made, and percentage of grafting is 1.5.
The product quality indicator that embodiment 1-3 is produced all meets the JB/T10707-200 standard, and is on probation through the user, can substitute import fully.Its main performance index is as shown in the table:
The oxygen index of traditional CABLE MATERIALS generally all is lower than 26, and toxicity index is greater than 3, the present invention
The oxygen index of product and toxicity index performance are far superior to the traditional cable material, mechanical physics and chemistry
Can be identical with the traditional cable material with processing characteristics.
Claims (6)
1. the thermoplastic low-smoke halide-free fireproof composite polyolefine CABLE MATERIALS is characterized in that the raw material by following weight part
Aluminium hydroxide 40-55
Metallocene polyolefin elastomers 25-40
New LDPE (film grade) 5---10
Compatilizer 5---10
Silane coupling agent 2.0-2.5
Lubricant 1.5-2.0
Oxidation inhibitor 0.1-0.2
Look mother 0.1-0.2
Through high-speed mixing, banburying, mediate, extrude, granulation makes.
2. thermoplastic low-smoke halide-free fireproof composite polyolefine CABLE MATERIALS according to claim 1 is characterized in that described aluminium hydroxide need satisfy following condition:
A, aluminium hydroxide content are more preferably greater than 99.5% greater than 99%;
B, than whiteness greater than 95%, be more preferably greater than 97%;
C, aluminium hydroxide particle diameter are more preferably less than 2 μ m less than 5 μ m;
D, moisture content are more preferably less than 0.3% less than 0.5%.
3. thermoplastic low-smoke halide-free fireproof composite polyolefine CABLE MATERIALS according to claim 1 is characterized in that described metallocene polyolefin elastomers need satisfy following condition:
A, molecular weight distribution, Mw/Mm is greater than 1.5;
B, density are more preferably between 0.870-0.885g/cm3 between 0.860-0.890g/cm;
C, at 190 ℃, the melting index under the 2.16Kg greater than 0.3g/10min, is more preferably greater than 0.5g/10min.
4. thermoplastic low-smoke halide-free fireproof composite polyolefine CABLE MATERIALS according to claim 1 is characterized in that described new LDPE (film grade) need satisfy following condition:
A, density are between 0.910-0.925;
B, at 190 ℃, the melting index under the 2.16Kg is greater than 1g/10Min.
5. thermoplastic low-smoke halide-free fireproof composite polyolefine CABLE MATERIALS according to claim 1, it is characterized in that described compatilizer is a kind of in the polymkeric substance that is made with maleic anhydride graft reaction or copolymerization respectively of polyethylene or α polyolefine or ethylene vinyl acetate copolymer, the compatilizer percentage of grafting that requires needs greater than 0.5, is greater than 1 better.
6. thermoplastic low-smoke halide-free fireproof composite polyolefine CABLE MATERIALS according to claim 1 is characterized in that described oxidation inhibitor is common suffocated amine antioxidant, and lubricant is a dimethyl silicone oil, and the look mother is common PE or EVA look mother.
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| CN 201110153649 CN102219948A (en) | 2011-06-09 | 2011-06-09 | Thermoplastic low-smoke zero-halogen inflaming-retarding polyolefin cable material |
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| CN 201110153649 CN102219948A (en) | 2011-06-09 | 2011-06-09 | Thermoplastic low-smoke zero-halogen inflaming-retarding polyolefin cable material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585346A (en) * | 2012-02-29 | 2012-07-18 | 江苏技术师范学院 | Halogen-free flame-retardant POE (Polyolefin Elastomer) compound material and preparation method thereof |
| CN102746546A (en) * | 2012-06-15 | 2012-10-24 | 安徽华通电缆集团有限公司 | Halogen-free environmentally-friendly power cable material for wind power generation, and its preparation method |
| CN103030917A (en) * | 2012-12-28 | 2013-04-10 | 浙江万马高分子材料有限公司 | Cracking-resistant thermoplastic low-smoke halogen-free flame-retardant polyolefin cable material |
| CN106589750A (en) * | 2016-12-07 | 2017-04-26 | 中广核三角洲（中山）高聚物有限公司 | Halogen-free flame retardant sheathing material with low heat release rate |
| IT201900004127A1 (en) | 2019-03-21 | 2020-09-21 | Prysmian Spa | Flame retardant electrical cable |
| CN114276610A (en) * | 2021-12-30 | 2022-04-05 | 河北尚华塑料科技有限公司 | Low-hardness low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
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| CN101323687A (en) * | 2008-07-28 | 2008-12-17 | 广东电缆厂有限公司 | Highly effective flame-retardant environment-protective cross-linking plastic and making process thereof |
| CN102020804A (en) * | 2009-09-15 | 2011-04-20 | 山东安澜高分子材料有限公司 | Thermoplastic crack resistant type low smoke zero halogen flame-retardant polyolefin cable sheath material and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101323687A (en) * | 2008-07-28 | 2008-12-17 | 广东电缆厂有限公司 | Highly effective flame-retardant environment-protective cross-linking plastic and making process thereof |
| CN102020804A (en) * | 2009-09-15 | 2011-04-20 | 山东安澜高分子材料有限公司 | Thermoplastic crack resistant type low smoke zero halogen flame-retardant polyolefin cable sheath material and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585346A (en) * | 2012-02-29 | 2012-07-18 | 江苏技术师范学院 | Halogen-free flame-retardant POE (Polyolefin Elastomer) compound material and preparation method thereof |
| CN102746546A (en) * | 2012-06-15 | 2012-10-24 | 安徽华通电缆集团有限公司 | Halogen-free environmentally-friendly power cable material for wind power generation, and its preparation method |
| CN102746546B (en) * | 2012-06-15 | 2016-08-03 | 安徽华通电缆集团有限公司 | A kind of halogen-free environment-friendly type power cable for wind power generation material and preparation method thereof |
| CN103030917A (en) * | 2012-12-28 | 2013-04-10 | 浙江万马高分子材料有限公司 | Cracking-resistant thermoplastic low-smoke halogen-free flame-retardant polyolefin cable material |
| CN103030917B (en) * | 2012-12-28 | 2015-04-22 | 浙江万马高分子材料有限公司 | Cracking-resistant thermoplastic low-smoke halogen-free flame-retardant polyolefin cable material |
| CN106589750A (en) * | 2016-12-07 | 2017-04-26 | 中广核三角洲（中山）高聚物有限公司 | Halogen-free flame retardant sheathing material with low heat release rate |
| CN109294148A (en) * | 2016-12-07 | 2019-02-01 | 中广核高新核材科技（苏州）有限公司 | The irradiation crosslinked polyolefin insulating material of low heat release high-temperature resistant |
| CN106589750B (en) * | 2016-12-07 | 2019-06-18 | 中广核三角洲（中山）高聚物有限公司 | A kind of Halogen-free flame retardant sheath material of low-heat rate of release |
| IT201900004127A1 (en) | 2019-03-21 | 2020-09-21 | Prysmian Spa | Flame retardant electrical cable |
| EP3712907A1 (en) | 2019-03-21 | 2020-09-23 | Prysmian S.p.A. | Flame retardant electrical cable |
| US10923246B2 (en) | 2019-03-21 | 2021-02-16 | Prysmian S.P.A. | Flame retardant electrical cable |
| CN114276610A (en) * | 2021-12-30 | 2022-04-05 | 河北尚华塑料科技有限公司 | Low-hardness low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
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Application publication date: 20111019 |