CN102850645A - Irradiated and crosslinked flame-retardant cable sheath material and preparation method thereof - Google Patents
Irradiated and crosslinked flame-retardant cable sheath material and preparation method thereof Download PDFInfo
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- CN102850645A CN102850645A CN2012103848136A CN201210384813A CN102850645A CN 102850645 A CN102850645 A CN 102850645A CN 2012103848136 A CN2012103848136 A CN 2012103848136A CN 201210384813 A CN201210384813 A CN 201210384813A CN 102850645 A CN102850645 A CN 102850645A
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Abstract
The invention provides an irradiated and crosslinked flame-retardant cable sheath material and a preparation method thereof. According to the sheath material, an ethylene-vinyl acetate copolymer is taken as a matrix, expanded graphite is taken as a fire retardant, a poly-vinyl irradiation sensitizer is taken as a crosslinking agent, the quadri [beta-(3, 5-di-tert-butyl-4-hydroxycyclohexyl phenyl ketone) propionic acid] pentaerythritol ester-1010 is taken as an antioxygen, didecyl adipate-DDA is taken as a plasticizer, and zinc stearate-ZnSt2 is taken as a stabilizer and color master batch. The preparation method comprises the following steps of: preparing the components in a certain proportion, extruding and pelleting in a twin-screw extruder to obtain the flame-retardant cable sheath material; and after the sheath material is coextruded, irradiating a certain dosage of sheath material in an electron accelcrator, and crosslinking. The sheath is quick in preparation technology, and the irradiated and crosslinked sheath is very good in flame retardant property and has oxygen index being more than 30.
Description
Technical field
The invention belongs to cable industry, be specifically related to a kind of irradiation cross-linking flame-retardant cable sheath material and preparation method thereof.
Background technology
The flame resistant method of macromolecular material routine is to add various fire retardants to carry out fire-retardant, but along with to high-performance, efficiently, the raising that environmental friendliness flame retardance of polymer system requires, constantly improving and science more of fire-retardant evaluation method, and the countries in the world flame retardant regulation is increasingly strict, particularly two instructions of European Union " instruction of waste electronic electrical equipment "-West Electrical and Electronic Equipment Directive, WEEE and " forbidding objectionable impurities instruction in the electronic and electrical equipment "-Restriction of Hazardous Substances Directive, the promulgation of RoHS is so that traditional flame-retardant systems such as halogen have been subject to stern challenge.The direction of novel flame-retardant macromolecular material development requires flame-retardant system not only to have good flame retardant properties, also will satisfy following requirement: 1. flame retarding efficiency is high, that is: the cost performance of flame-retarded efficiency and price is high; Fire retardant and the matrix phase capacitive of 2. adding are good, are difficult for migration and ooze out, and exceed the physical and mechanical properties, electric property, tint permanence and the processing characteristics that affect material, by fire retardant material recyclable with recycle; 3. itself nontoxic or low toxicity, Poisonous Gas and to give birth to the cigarette amount few as much as possible, environmentally friendly during burning; 4. sufficient raw, manufacturing process is simple, and fire-retardant cost is low.
Magnesium hydroxide often is used to the fire-retardant of macromolecular material, but because its addition is large, usually has a strong impact on the performances such as mechanics of material.And the expansibility flame-proof agent exactly just can be satisfied these requirements.Expansion type flame retardant-IFR can be divided into Chemical expanding flame-retardant and Physical expanding flame-retardant.Classical Chemical expanding flame-retardant generally is the composite flame-retardant agent take P, N, C element as nucleus; Physical expanding flame-retardant mainly refers to expansible black lead.And expansion type flame retardant is widely used in frie retardant coating very early, IFR being used for the polymer materialss such as rubber, plastics, fiber, timber is the thing of recent two decades, because it has overcome many shortcomings of traditional flame-retarded technology, have higher flame retardant resistance, realize that fire retardant is non-halogen, become a most rising based flame retardant, and caused widely concern.But have not yet to see the relevant report for preparing in the flame-proof cable sheath material that expanded graphite is applied in.
Summary of the invention
Technical problem to be solved by this invention provides a kind of good flame retardation effect, irradiation cross-linking flame-retardant cable sheath material with low cost and preparation method thereof.
Irradiation cross-linking flame-retardant cable sheath material of the present invention comprises following component and mass fraction thereof:
Ethylene-vinyl acetate copolymer: 100 parts
Expanded graphite: 10 parts-30 parts
Polyene-based irradiation sensitizing agent: 0.5-3 part
Oxidation inhibitor: 0.5 part
Softening agent: 0.5 part
Thermo-stabilizer: 0.5 part
Masterbatch: 2-5 part
The technical parameter of described ethylene-vinyl acetate copolymer is melting index≤5 g/10min, ASTM D-1238, and 100 ℃, 1.2kg, VA content 50 wt %, mooney viscosity ML1+4 is 27 ± 4 in the time of 100 ℃, density 1.00 g/cm
3
Described expanded graphite is the graphite of inner intercalation sulfuric acid, and particle diameter is 100-300 μ m, and its expansion multiple is 200 times-500 times.
Described polyene-based irradiation sensitizing agent comprises iso-cyanuric acid triallyl ester-TAIC, trimethylolpropane trimethacrylate-TMPTMA, Viscoat 295-TMPTA, tripropylene glycol two propylene ether-ether-TPGDA etc.
Described oxidation inhibitor is preferably four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester-1010.
Described softening agent is preferably didecyl adipate, and described thermo-stabilizer is preferably Zinic stearas.
The present invention also provides the preparation method of this irradiation cross-linking flame-retardant cable sheath material, and its process is: with the above-mentioned raw materials component put into successively high-speed mixer with 500 turn/after min stirred 5min, this moment, material was no more than 60 ℃; The taking-up material is put into twin screw extruder and is extruded, wire drawing, and water-cooled, air-cooled, granulation namely obtains irradiation cross-linking flame-retardant cable sheath material masterbatch; Will be with upper jacket masterbatch and cable material after coextrusion under 110 ℃ the condition, normal temperature cross-linking radiation under high-energy electron accelerator, irradiation dose are 50kGy-80kGy, can obtain the cross-linking radiation sheath.
Described rumbatron model is GJ-2E-EB, 2 MeV, 10 mA.
The present invention compared with prior art has following advantage and effect:
1, irradiation cross-linking flame-retardant cable sheath material of the present invention has the characteristics such as Halogen, low cigarette, low toxicity, environmental protection, and cheap.
2, irradiation cross-linking flame-retardant cable sheath material preparation method technique of the present invention is quick, and material bubble can not occur in the irradiation moulding process.
3, irradiation cross-linking flame-retardant cable sheath of the present invention has superior flame retardant properties, and oxygen index can reach more than 30, low cigarette, and mechanical property, resistance to acids and bases, the superior performances such as water tolerance.
4, expanded graphite low price used in the present invention, flame retarding efficiency is high, and material bubble can not occur in the irradiation moulding process, and shaping speed is fast.
Description of drawings
Fig. 1 prepares the heat release rate curve of sheath for each embodiment,
Fig. 2 prepares the total heat release profiles of sheath for each embodiment,
Fig. 3 prepares the cigarette release rate profile of sheath for each embodiment.
Embodiment
The invention will be further described below in conjunction with specific embodiment, and following examples are mass fraction.
Get 100 parts of ethylene-vinyl acetate copolymers, 10 parts of expanded graphites, 2 parts of polyene-based irradiation sensitizing agents, 0.5 part of antioxidant 1010, after 0.5 part of softening agent didecyl adipate, 0.5 part of stablizer Zinic stearas, 2 parts of Masterbatchs are put into successively the high-speed mixer high speed and are stirred 5min, 500 turn/min, and material is no more than 60 ℃.The taking-up material is put into twin screw extruder and is extruded, wire drawing, and water-cooled, air-cooled, granulation namely obtains irradiation cross-linking flame-retardant cable sheath material masterbatch.After upper jacket masterbatch and cable material coextrusion, at high-energy electron accelerator GJ-2E-EB, 2 MeV, normal temperature cross-linking radiation under 10 mA, irradiation dose are 80kGy, can obtain the cross-linking radiation sheath.
Embodiment 2
Get 100 parts of ethylene-vinyl acetate copolymers, 20 parts of expanded graphites, 2 parts of polyene-based irradiation sensitizing agents, 0.5 part in oxidation inhibitor, 0.5 part in softening agent, 0.5 part of stablizer, after 5 parts of Masterbatchs were put into successively the high-speed mixer high speed and stirred 5min, 500 turned/min, and material is no more than 60 ℃.The taking-up material is put into twin screw extruder and is extruded, wire drawing, and water-cooled, air-cooled, granulation namely obtains irradiation cross-linking flame-retardant cable sheath material masterbatch.After upper jacket masterbatch and cable material coextrusion, at high-energy electron accelerator GJ-2E-EB, 2 MeV, normal temperature cross-linking radiation under 10 mA, irradiation dose are 80kGy, can obtain the cross-linking radiation sheath.
Embodiment 3
Get 100 parts of ethylene-vinyl acetate copolymers, 30 parts of expanded graphites, 2 parts of polyene-based irradiation sensitizing agents, 0.5 part in oxidation inhibitor, 0.5 part in softening agent, 0.5 part of stablizer, after 2 parts of Masterbatchs were put into successively the high-speed mixer high speed and stirred 5min, 500 turned/min, and material is no more than 60 ℃.The taking-up material is put into twin screw extruder and is extruded, wire drawing, and water-cooled, air-cooled, granulation namely obtains irradiation cross-linking flame-retardant cable sheath material masterbatch.After upper jacket masterbatch and cable material coextrusion, at high-energy electron accelerator GJ-2E-EB, 2 MeV, normal temperature cross-linking radiation under 10 mA, irradiation dose are 80kGy, can obtain the cross-linking radiation sheath.
The part component that adopts among the above embodiment requires:
The technical parameter of ethylene-vinyl acetate copolymer is melting index≤5 g/10min, ASTM D-1238, and 100 ℃, 1.2kg, VA content 50 wt %, mooney viscosity ML1+4 is 27 ± 4 in the time of 100 ℃, density 1.00 g/cm
3
Expanded graphite is the graphite of inner intercalation sulfuric acid, and particle diameter is 100-300 μ m, and its expansion multiple is 200 times-500 times.
Polyene-based irradiation sensitizing agent comprises iso-cyanuric acid triallyl ester, trimethylolpropane trimethacrylate, Viscoat 295 and tripropylene glycol two propylene ether-ethers.
Product performance detect:
The test of flame retardant properties will be carried out after the section of the material use cable slicing machine in above-described embodiment.Taper calorimeter data such as Fig. 1, Fig. 2, shown in Figure 3.As can be seen from the figure the flame retardant properties of sheath increases substantially.The oxygen index test shows that also the material oxygen index is increased to 23.5,28,32 successively, and mechanical property satisfies the fire-retardant and mechanical property requirements of sheath material fully all greater than 5MPa.
The concrete application approach of the present invention is a lot, and the above only is preferred implementation of the present invention, should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention, can also make some improvement, these improvement also should be considered as protection scope of the present invention.
Claims (7)
1. irradiation cross-linking flame-retardant cable sheath material is characterized in that comprising following component and mass fraction thereof:
Ethylene-vinyl acetate copolymer: 100 parts
Expanded graphite: 10 parts-30 parts
Polyene-based irradiation sensitizing agent: 0.5-3 part
Oxidation inhibitor: 0.5 part
Softening agent: 0.5 part
Thermo-stabilizer: 0.5 part
Masterbatch: 2-5 part.
2. irradiation cross-linking flame-retardant cable sheath material according to claim 1 is characterized in that, the technical parameter of ethylene-vinyl acetate copolymer is melting index≤5 g/10min, ASTM D-1238,100 ℃, 1.2kg; VA content 50 wt %, mooney viscosity ML1+4 is 27 ± 4 in the time of 100 ℃, density 1.00 g/cm
3
3. irradiation cross-linking flame-retardant cable sheath material according to claim 1 is characterized in that, described expanded graphite is the graphite of inner intercalation sulfuric acid, and particle diameter is 100-300 μ m, and its expansion multiple is 200 times-500 times.
4. irradiation cross-linking flame-retardant cable sheath material according to claim 1, it is characterized in that polyene-based irradiation sensitizing agent comprises iso-cyanuric acid triallyl ester, trimethylolpropane trimethacrylate, Viscoat 295 and tripropylene glycol two propylene ether-ethers.
5. irradiation cross-linking flame-retardant cable sheath material according to claim 1 is characterized in that, oxidation inhibitor is antioxidant 1010, and softening agent is didecyl adipate, and thermo-stabilizer is Zinic stearas.
6. the preparation method of the described irradiation cross-linking flame-retardant cable sheath material of claim 1 is characterized in that may further comprise the steps, with the above-mentioned raw materials component put into successively high-speed mixer with 500 turn/after min stirred 5min, this moment, material was no more than 60 ℃; The taking-up material is put into twin screw extruder and is extruded, wire drawing, and water-cooled, air-cooled, granulation namely obtains irradiation cross-linking flame-retardant cable sheath material masterbatch; Will be with upper jacket masterbatch and cable material after coextrusion under 110 ℃ the condition, normal temperature cross-linking radiation under high-energy electron accelerator, irradiation dose are 50kGy-80kGy, can obtain the cross-linking radiation sheath.
7. the preparation method of irradiation cross-linking flame-retardant cable sheath material according to claim 6 is characterized in that, described rumbatron model is GJ-2E-EB, 2 MeV, 10 mA.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756162A (en) * | 2013-12-31 | 2014-04-30 | 上海海事大学 | Strapping tape for deep sea buoyancy material and preparation method thereof |
| CN103756118A (en) * | 2013-12-31 | 2014-04-30 | 上海海事大学 | Annular strapping tape for deep sea buoyancy material strapping system and preparation method thereof |
| CN104151690A (en) * | 2014-07-25 | 2014-11-19 | 宁国新博能电子有限公司 | Halogen-free flame-retardant cable sheath material |
| CN105801996A (en) * | 2016-04-06 | 2016-07-27 | 东华大学 | Flame-retardant high-heat-conductivity sheath material as well as preparation and application thereof |
| CN108485050A (en) * | 2018-04-10 | 2018-09-04 | 江苏华强电力设备有限公司 | A kind of fire-retardant acid-alkali-corrosive-resisting safe power supply wiping busbar and its production technology |
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| CN1803907A (en) * | 2005-12-12 | 2006-07-19 | 广州凯恒科塑有限公司 | Radiation cross-linked low-smoke halogen-free phosphor-free nanometer flame retardant thermal shrinkage material and method for preparing the same |
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| CN1803907A (en) * | 2005-12-12 | 2006-07-19 | 广州凯恒科塑有限公司 | Radiation cross-linked low-smoke halogen-free phosphor-free nanometer flame retardant thermal shrinkage material and method for preparing the same |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756162A (en) * | 2013-12-31 | 2014-04-30 | 上海海事大学 | Strapping tape for deep sea buoyancy material and preparation method thereof |
| CN103756118A (en) * | 2013-12-31 | 2014-04-30 | 上海海事大学 | Annular strapping tape for deep sea buoyancy material strapping system and preparation method thereof |
| CN103756162B (en) * | 2013-12-31 | 2016-02-03 | 上海海事大学 | A kind of deep-sea buoyancy material strapping tape and preparation method thereof |
| CN103756118B (en) * | 2013-12-31 | 2017-01-04 | 上海海事大学 | Can be used for circumferential band of deep-sea buoyant material bounding system and preparation method thereof |
| CN104151690A (en) * | 2014-07-25 | 2014-11-19 | 宁国新博能电子有限公司 | Halogen-free flame-retardant cable sheath material |
| CN105801996A (en) * | 2016-04-06 | 2016-07-27 | 东华大学 | Flame-retardant high-heat-conductivity sheath material as well as preparation and application thereof |
| CN105801996B (en) * | 2016-04-06 | 2019-05-03 | 东华大学 | A kind of fire-retardant high thermal conductivity sheath material and its preparation and application |
| CN108485050A (en) * | 2018-04-10 | 2018-09-04 | 江苏华强电力设备有限公司 | A kind of fire-retardant acid-alkali-corrosive-resisting safe power supply wiping busbar and its production technology |
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Application publication date: 20130102 |