CN102585329A - Halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof - Google Patents
Halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof Download PDFInfo
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- CN102585329A CN102585329A CN2012100124344A CN201210012434A CN102585329A CN 102585329 A CN102585329 A CN 102585329A CN 2012100124344 A CN2012100124344 A CN 2012100124344A CN 201210012434 A CN201210012434 A CN 201210012434A CN 102585329 A CN102585329 A CN 102585329A
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Abstract
The invention relates to a halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube which consists of the following components by weight: 100 parts of base resin, 60 to 80 parts of melamine phosphate ester, 10 to 20 parts of melamine cyanuric acid, 10 to 20 parts of pentaerythritol, 1 to 3 parts of complex antioxidant and 2 to 5 parts of lubricant. The base resin is a mixture of one or a plurality of the following substances: low-density polyethylene, ethylene methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-octene copolymer and ethylene-propylene-diene monomer; and the complex antioxidant is formed by compounding pentaerythrite tetra [beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate] with disteaxyl thiodipropionate according to a ratio of 1:1. The halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube disclosed by the invention does not contain red phosphorus. The flame-retardant performance of the halogen-free non-red-phosphorus flame-retardant shrinkable tube can pass through the VM-1 test.
Description
Technical field
the present invention relates to a kind of thermal shrinkage pipe material and preparation method thereof.
Background technology
; On July 1st, 2006; The RoHS of European Union instruction comes into force; In November, 2006, China's electron trade standard SJ/T 11363-2006 " requirements of limiting the quantity of of hazardous and noxious substances in the electronics and IT products " came into force; Forbid in electronics and IT products, using lead, mercury, cadmium, sexavalent chrome, PBBs (PBB) and polybromodiphenyl ether six kinds of objectionable impuritiess such as (PBDE); Be the reply RoHS of European Union instruction, each manufacturer substitutes PBBs (PBB) and polybromodiphenyl ether (PBDE) with red phosphorus, makes fire retardant thermal shrinkage tube.
but the red phosphorus burning time can discharge deleterious irritating smog; Corrosion people's skin and mucous membrane; Harm people's health, red phosphorus overlaps between the positive and negative electrode of wiring board, also can give birth to electrochemical reaction with metallic copper, silver hair on the wiring board; The positive and negative electrode of wiring board is connected, caused the wiring board fault.So in June, 2007, Apple issued " apple Halogen specifications ", took the lead in proposing to limit the use of red phosphorus in the whole world.Owing to there is not suitable fire retardant to substitute red phosphorus, therefore present practical situation are: or continue to use red phosphorus as fire retardant, or do not use red phosphorus, but flame retardant effect is poor especially.
therefore, it is pumping up of industry in fact that a kind of thermal shrinkage pipe material that does not have red phosphorus and good flame retardation effect is provided.
Summary of the invention
The technical problem that
the present invention will solve is: overcome the defective that existing heat-shrink tube uses the easy initiating failure of red phosphorus, a kind of thermal shrinkage pipe material that does not have red phosphorus and good flame retardation effect and preparation method thereof is provided.
In order to solve the problems of the technologies described above, the present invention proposes following technical scheme: a kind of Halogen does not have the red phosphorus flame-retardant heat-shrink tube, and it is made up of the following component according to the weight meter:
100 parts of basic resin;
60-80 parts of trimeric cyanamide SULPHOSUCCINIC ACID ESTERs;
10-20 parts of melamine cyanurates;
Tetramethylolmethane 10-20 part;
Composite antioxidant 1-3 part;
Lubricant 2-5 part;
Said basic resin is one or more the mixture in the following substances: new LDPE (film grade); Ethylene-methyl acrylate copolymer; Ethylene-ethyl acrylate copolymer; Ethylene-butyl acrylate copolymer; Ethene-acetic acid is alkene copolymer; Ethylene-octene copolymer; Terpolymer EP rubber;
said composite antioxidant is that four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and thio-2 acid two (18) ester form according to 1:1 is composite.
The further qualification of
technique scheme is: said lubricant is one or more the mixture in the following substances: polyethylene wax, Zinic stearas.
In order to solve the problems of the technologies described above, the present invention proposes following technical scheme: a kind ofly prepare the preparation method that Halogen does not have the red phosphorus flame-retardant heat-shrink tube, comprise the steps:
Step 1: get 100 parts of basic resin by weight, trimeric cyanamide SULPHOSUCCINIC ACID ESTER 60-80 part, melamine cyanurate 10-20 part, tetramethylolmethane 10-20 part, composite antioxidant 1-3 part, lubricant 2-5 part;
Step 2:, be extruded into tubing with single screw extrusion machine then through banburying mixing granulator or parallel double-screw extruder mixing granulator;
step 3: said tubing is through cobalt 60 or rumbatron 50-180KGy radiation crosslinking, and the tubing behind the radiation crosslinking is expanded 2-4 doubly under 90-150 ℃ of temperature.
The present invention has following beneficial effect and is: Halogen of the present invention does not have the red phosphorus flame-retardant heat-shrink tube and does not contain red phosphorus and lead, mercury, cadmium, sexavalent chrome, PBBs (PBB) and polybromodiphenyl ether hazardous and noxious substances such as (PBDE); Flame retardant properties can be passed through VW-1 test; Tensile strength is greater than 11MPa; Elongation at break is greater than 260%, and product surface is smooth, and processing characteristics is excellent
Embodiment
The present invention proposes a kind of Halogen does not have the red phosphorus flame-retardant heat-shrink tube, and it is made up of the following component according to the weight meter:
100 parts of basic resin;
60-80 parts of trimeric cyanamide SULPHOSUCCINIC ACID ESTERs;
10-20 parts of melamine cyanurates;
Tetramethylolmethane 10-20 part;
Composite antioxidant 1-3 part;
lubricant 2-5 part.
said basic resin is one or more the mixture in the following substances: new LDPE (film grade); Ethylene-methyl acrylate copolymer; Ethylene-ethyl acrylate copolymer; Ethylene-butyl acrylate copolymer; Ethene-acetic acid is alkene copolymer; Ethylene-octene copolymer; Terpolymer EP rubber.
said composite antioxidant is that four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and thio-2 acid two (18) ester form according to 1:1 is composite.
said lubricant is one or more the mixture in the following substances: polyethylene wax; Zinic stearas.
The present invention proposes to prepare the preparation method that described Halogen does not have the red phosphorus flame-retardant heat-shrink tube, comprises the steps:
Step 1: get 100 parts of basic resin by weight, trimeric cyanamide SULPHOSUCCINIC ACID ESTER 60-80 part, melamine cyanurate 10-20 part, tetramethylolmethane 10-20 part, composite antioxidant 1-3 part, lubricant 2-5 part;
Step 2:, be extruded into tubing with single screw extrusion machine then through banburying mixing granulator or parallel double-screw extruder mixing granulator;
step 3: said tubing is through cobalt 60 or rumbatron 50-180KGy radiation crosslinking, and the tubing behind the radiation crosslinking is expanded 2-4 doubly under 90-150 ℃ of temperature.
Preparation embodiment 1
get ethene-acetic acid 80 parts of alkene copolymers, 10 parts of ethylene-octene copolymers, 10 parts of terpolymer EP rubbers, 60 parts of trimeric cyanamide SULPHOSUCCINIC ACID ESTERs, 20 parts of melamine cyanurates, 20 parts of tetramethylolmethanes, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and thio-2 acid two (18) ester according to 3 parts of the composite composite antioxidants that forms of 1:1,3 parts of polyethylene waxs, 2 parts of Zinic stearass.
above material is through the banburying mixing granulator, and single screw extrusion machine is extruded into tubing, and said tubing is through cobalt 60 or rumbatron 100KGy radiation crosslinking.
Tubing behind the radiation crosslinking is expanded 2 times under 120 ℃ of temperature, obtaining Halogen, not have the performance of red phosphorus flame-retardant heat-shrink tube following:
flame retardant resistance: through VW-1, tensile strength: 13.1Mpa, elongation at break: 360%, product surface is smooth.
Preparation embodiment 2
10 parts of new LDPE (film grade)s, 90 parts of ethylene-methyl acrylate copolymers, 80 parts of trimeric cyanamide SULPHOSUCCINIC ACID ESTERs, 10 parts of melamine cyanurates, 10 parts of tetramethylolmethanes, four [β-(3 are got in
; The 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and thio-2 acid two (18) ester be according to 1 part of the composite composite antioxidant that forms of 1:1,2 parts of Zinic stearass.
above material is through the banburying mixing granulator, and single screw extrusion machine is extruded into tubing, and said tubing is through cobalt 60 or rumbatron 100KGy radiation crosslinking.
Tubing behind the radiation crosslinking is expanded 2 times under 120 ℃ of temperature, obtaining Halogen, not have the performance of red phosphorus flame-retardant heat-shrink tube following:
flame retardant resistance: through VW-1, tensile strength: 12Mpa, elongation at break: 300%, product surface is smooth.
Preparation embodiment 3
90 parts of ethylene-ethyl acrylate copolymers, 10 parts of terpolymer EP rubbers, 70 parts of trimeric cyanamide SULPHOSUCCINIC ACID ESTERs, 15 parts of melamine cyanurates, 15 parts of tetramethylolmethanes, four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and thio-2 acid two (18) ester are got according to 2 parts of the composite composite antioxidants that forms of 1:1,3.5 parts of polyethylene waxs in
.
above material is through the banburying mixing granulator, and single screw extrusion machine is extruded into tubing, and said tubing is through cobalt 60 or rumbatron 100KGy radiation crosslinking.
Tubing behind the radiation crosslinking is expanded 2 times under 120 ℃ of temperature, obtaining Halogen, not have the performance of red phosphorus flame-retardant heat-shrink tube following:
Flame retardant resistance: through VW-1, tensile strength: 11.6Mpa, elongation at break: 380%, product surface is smooth
Claims (3)
1. a Halogen does not have the red phosphorus flame-retardant heat-shrink tube, and it is made up of the following component according to the weight meter:
100 parts of basic resin;
Trimeric cyanamide SULPHOSUCCINIC ACID ESTER 60-80 part;
Trimeric cyanamideCyanuric acid 10-20 part;
Tetramethylolmethane 10-20 part;
Composite antioxidant 1-3 part;
Lubricant 2-5 part;
Said basic resin is one or more the mixture in the following substances: new LDPE (film grade); Ethylene-methyl acrylate copolymer; Ethylene-ethyl acrylate copolymer; Ethylene-butyl acrylate copolymer; Ethene-acetic acid is alkene copolymer; Ethylene-octene copolymer; Terpolymer EP rubber;
Said composite antioxidant is that four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters and thio-2 acid two (18) ester form according to 1:1 is composite.
2. Halogen according to claim 1 does not have the red phosphorus flame-retardant heat-shrink tube, it is characterized in that: said lubricant is one or more the mixture in the following substances: polyethylene wax, Zinic stearas.
3. one kind prepares the preparation method that Halogen as claimed in claim 1 does not have the red phosphorus flame-retardant heat-shrink tube, comprises the steps:
Step 1: get 100 parts of basic resin by weight, trimeric cyanamide SULPHOSUCCINIC ACID ESTER 60-80 part,
Trimeric cyanamideCyanuric acid 10-20 part, tetramethylolmethane 10-20 part, composite antioxidant 1-3 part, lubricant 2-5 part;
Step 2:, be extruded into tubing with single screw extrusion machine then through banburying mixing granulator or parallel double-screw extruder mixing granulator;
Step 3: said tubing is through cobalt 60 or rumbatron 50-180KGy radiation crosslinking, and the tubing behind the radiation crosslinking is expanded 2-4 doubly under 90-150 ℃ of temperature.
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| CN2012100124344A CN102585329A (en) | 2012-01-16 | 2012-01-16 | Halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof |
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| CN2012100124344A CN102585329A (en) | 2012-01-16 | 2012-01-16 | Halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131115A (en) * | 2013-03-25 | 2013-06-05 | 上海交通大学 | Flame-retardant polyolefin thermoplastic elastomer composition and preparation method thereof |
| CN103465386A (en) * | 2013-09-18 | 2013-12-25 | 长园集团股份有限公司 | Preparation method of halogen-free and red-phosphorus-free flame-retardant heat shrinkable material |
| CN104761805A (en) * | 2015-04-13 | 2015-07-08 | 扬州春天线缆有限公司 | Low-smoke zero-halogen digital communication cable |
| CN105001491A (en) * | 2015-07-15 | 2015-10-28 | 安徽鸿海电缆有限公司 | High-strength electrical-ageing-proof cable |
| CN106188784A (en) * | 2016-08-18 | 2016-12-07 | 苏州泰斯拓伟机电设备有限公司 | A kind of high-temperature resistant irradiation cross polyolefin heat-shrink tube |
| CN106221207A (en) * | 2016-08-18 | 2016-12-14 | 苏州泰斯拓伟机电设备有限公司 | A kind of polyethylene/nylon heat-shrink tube and preparation method thereof |
| CN106217917A (en) * | 2016-08-25 | 2016-12-14 | 苏州泰斯拓伟机电设备有限公司 | A kind of Making method of environment-friendlyflame flame retardant polyolefin hot pyrocondensation pipe |
| CN106243476A (en) * | 2016-08-18 | 2016-12-21 | 苏州泰斯拓伟机电设备有限公司 | A kind of heat-shrink tube of tolerable temperature cataclysm |
| CN106317651A (en) * | 2016-08-18 | 2017-01-11 | 苏州泰斯拓伟机电设备有限公司 | Ethylene-propylene-diene monomer rubber heat-shrinkable tube and preparation method thereof |
| CN106317559A (en) * | 2016-08-18 | 2017-01-11 | 苏州泰斯拓伟机电设备有限公司 | Wear-proof environment-friendly heat shrinkable tube and preparing method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103131115A (en) * | 2013-03-25 | 2013-06-05 | 上海交通大学 | Flame-retardant polyolefin thermoplastic elastomer composition and preparation method thereof |
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| CN103465386A (en) * | 2013-09-18 | 2013-12-25 | 长园集团股份有限公司 | Preparation method of halogen-free and red-phosphorus-free flame-retardant heat shrinkable material |
| CN104761805A (en) * | 2015-04-13 | 2015-07-08 | 扬州春天线缆有限公司 | Low-smoke zero-halogen digital communication cable |
| CN105001491A (en) * | 2015-07-15 | 2015-10-28 | 安徽鸿海电缆有限公司 | High-strength electrical-ageing-proof cable |
| CN106188784A (en) * | 2016-08-18 | 2016-12-07 | 苏州泰斯拓伟机电设备有限公司 | A kind of high-temperature resistant irradiation cross polyolefin heat-shrink tube |
| CN106221207A (en) * | 2016-08-18 | 2016-12-14 | 苏州泰斯拓伟机电设备有限公司 | A kind of polyethylene/nylon heat-shrink tube and preparation method thereof |
| CN106243476A (en) * | 2016-08-18 | 2016-12-21 | 苏州泰斯拓伟机电设备有限公司 | A kind of heat-shrink tube of tolerable temperature cataclysm |
| CN106317651A (en) * | 2016-08-18 | 2017-01-11 | 苏州泰斯拓伟机电设备有限公司 | Ethylene-propylene-diene monomer rubber heat-shrinkable tube and preparation method thereof |
| CN106317559A (en) * | 2016-08-18 | 2017-01-11 | 苏州泰斯拓伟机电设备有限公司 | Wear-proof environment-friendly heat shrinkable tube and preparing method thereof |
| CN106217917A (en) * | 2016-08-25 | 2016-12-14 | 苏州泰斯拓伟机电设备有限公司 | A kind of Making method of environment-friendlyflame flame retardant polyolefin hot pyrocondensation pipe |
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Application publication date: 20120718 |