CN104530543A - Halogen-free environmental-friendly flame-retardant bus-bar insulating heat-shrinkable bushing and preparation method thereof - Google Patents
Halogen-free environmental-friendly flame-retardant bus-bar insulating heat-shrinkable bushing and preparation method thereof Download PDFInfo
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- CN104530543A CN104530543A CN201410780096.8A CN201410780096A CN104530543A CN 104530543 A CN104530543 A CN 104530543A CN 201410780096 A CN201410780096 A CN 201410780096A CN 104530543 A CN104530543 A CN 104530543A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical Kinetics & Catalysis (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention discloses a halogen-free environmental-friendly flame-retardant bus-bar insulating heat-shrinkable bushing which is prepared through mixing granulation from the following materials in parts by weight: 100 parts of ethylene-methyl methacrylate copolymers, 30-40 parts of halogen-free flame retardants, 0.5-1.0 part of antioxidants, 2.0-3.0 parts of lubricants, 2-4 parts of cross-linking agents and 0-7 parts of halogen-free color powder/master batch. The prepared bus-bar heat-shrinkable bushing with various colors is suitable for 35 KV and various voltage grades below 35 KV; in addition, the bus-bar heat-shrinkable bushing prepared through extrusion, irradiation, expansion and oil coating has the advantages of excellent electrical insulation property, mechanical property, flame-retardant property, thermal ageing property and stress cracking resistant property.
Description
Technical field
The present invention relates to a kind of halogen-free environment-friendly flame-proof bus bar Insulating heat shrink and preparation method thereof, can be used for power switch cabinet median generatrix row insulation protection.
Background technology
In electric insulation product, bus bar Insulating heat shrink provides insulation protection for copper bar, prevents charged bare wire from arranging and causes the accident, the short circuit preventing animalcule from causing and electric leakage.Reduce the distance of copper bar, provide larger design freely in limited switching cabinet space, at below voltage rating 35kv, effectively prevent dust, filth, condensation flashover.At present, existing bus bar heat-shrink tube adopts EVA class polyolefine material, and this series products can produce sour gas corrosion copper bar in life-time service, for power equipment safety hides some dangers for.So people expect to have the birth of a kind of non-halogen flame-retarding high performance bus bar Insulating heat shrink, meet and day by day require strict market and customer demand.
Summary of the invention
The object of this invention is to provide a kind of halogen-free flameproof bus bar Insulating heat shrink, not only meet the test method standard of ASTM-D2671-2009 electrical equipment heat-shrinkable tube, and meet RoHS standard.Concrete technical scheme is as follows.
The application provides a kind of halogen-free environment-friendly flame-proof bus bar Insulating heat shrink, is made up of the feed composition of following weight proportion: ethylene methyl methacrylate copolymer 1 00 part; Halogen-free flame retardants 30-45 part; Oxidation inhibitor 0.5-1.0 part; Lubricant 1.0-3.0 part; Linking agent 2.0-4.0 part; Halogen toner/master batch 1-7 part.
Further, the multipolymer of ethylene methyl methacrylate described in the application-EMMA melt index MI:4-5g/min, wherein MMA:28%.
Further, halogen-free flame retardants described in the application is inorganic combustion inhibitor; Described inorganic combustion inhibitor is nanometer activation magnesium hydroxide, superfine activated aluminium hydroxide and superfine activated kaolin.
Further, oxidation inhibitor described in the application is the IRGANOX B-215 of Ciba, the synergistic mixture be made up of 33% hindered phenol antioxygen IRGANOX 1010 and 67% organophosphite IRGANOX 168; B215 composite antioxidant is the collaboration system of processing stabilizers and long-acting thermo-stabilizer.
Further, lubricant described in the application is silicone masterbatch and polyethylene wax; Polyethylene wax (PE wax), be called for short polyethylene wax as lubricant also known as macromolecule wax, its stable chemical nature, electrical property are good, and the light increasing product is translated and processing characteristics.Silicone masterbatch active constituent content high (50% polydimethylsiloxane), addition is low, good dispersity, and combustion fumes is low.Obviously can improve the surface of fire retardant material, greatly reduce high melt viscosity of filling in bittern-free flame-proof material production process, reduce moment of torsion, reduce processing temperature, and therefore eliminate the starting material decomposing phenomenon caused because processing temperature is too high, silicone masterbatch and Mg (OH) simultaneously
2, Al (OH)
3fire retardant has certain synergistic effect; Preferably, the weight proportion of described silicone masterbatch and polyethylene wax is 3-9:1.
Further, linking agent described in the application is trimethylolpropane trimethacrylate; It has high boiling point, high reaction activity, high crosslink density, low viscosity, low volatilization, low stimulation, snappiness are good.As cross-linking radiation agent: can radiation dose be reduced, shorten irradiation time, improve cross-linking density, have that viscosity is low, degree of crosslinking is high.
Further, the toner/master batch of Halogen described in the application is iron oxide red, black masterbatch, titanium dioxide or other various pigments.
Further, present invention also provides the preparation method of above-mentioned halogen-free environment-friendly flame-proof bus bar Insulating heat shrink, described method is batch mixing two-step approach: first drop into plastic grain ethylene methyl methacrylate multipolymer and auxiliary agent oxidation inhibitor, lubricant, linking agent and Halogen toner/master batch high-speed stirring in stirrer, stir and drop into halogen-free flame retardants again after 3-5 minute, high-speed stirring again afterwards, batch mixing is terminated when mixture temperature reaches 60-70 DEG C, finally by 130-140 DEG C of banburying 30-40min in evenly mixed material to milling machine, after make pyrocondensation masterbatch through singe screw tablets press, pyrocondensation masterbatch is simultaneously online to its inwall atomization oiling through extrusion moulding, electron accelerator irradiation sizing, continuously expanding and shaping 2-3 times of pyrocondensation bus bar insulation tube, finally makes halogen-free flameproof bus bar Insulating heat shrink.
Further, the halogen-free environment-friendly flame-proof bus bar Insulating heat shrink that the application provides is met and the test method required by ASTM-D2671-2009 electrical equipment heat-shrinkable tube.Its feature is to be contracted in each dot thickness uniformity in rectangular copper bar, and bending copper bar is all fitted everywhere and closely do not deposited air, at high temperature (100-115 DEG C) even if there is slight flaws (breach as longitudinal in 5mm) also can not ftracture under running.
Beneficial effect:
1) the halogen-free flameproof bus bar Insulating heat shrink made by the application is widely used in electric insulation product, for copper bar provides insulation protection, reduce the distance of copper bar, there is provided larger design freely in limited switching cabinet space, below voltage rating 35kv, effectively prevents dust, filth, condensation flashover;
2) the halogen-free flameproof bus bar Insulating heat shrink that provides of the application is compared with the existing bus bar heat-shrinkable T bush adopting EVA class polyolefine material to make, and can not produce sour gas corrosion copper bar, to power equipment without potential safety hazard in life-time service.Its feature is to be contracted in each dot thickness uniformity in rectangular copper bar, and bending copper bar is all fitted everywhere and closely do not deposited air, at high temperature (100-115 DEG C) even if there is slight flaws (breach as longitudinal in 5mm) also can not ftracture under running; And meet the test method of ASTM-D2671-2009 electrical equipment heat-shrinkable tube requirement.
Embodiment
Below by embodiment, the present invention is described in further details.
Embodiment 1
Get ethylene methyl methacrylate multipolymer (EMMA) 100kg(melt index MI:4-5g/min, MMA:28%), oxidation inhibitor (the IRGANOX B-215 of Ciba) 0.5kg, silicone masterbatch 1.5kg, polyethylene wax 0.5kg, trimethylolpropane trimethacrylate 2kg, Halogen toner/master batch 1kg, stirring at low speed in stirrer, stir after three minutes and drop into nanometer activation magnesium hydroxide 10kg again, superfine activated aluminium hydroxide 10kg, superfine activated kaolin 10kg high-speed stirring, batch mixing is terminated when mixture temperature reaches 60 DEG C, finally by 130 DEG C of banburying 30min in evenly mixed material to milling machine, after make pyrocondensation masterbatch through singe screw tablets press.Pyrocondensation masterbatch is simultaneously online to its inwall atomization oiling through extrusion moulding, electron accelerator irradiation sizing, continuously expanding and shaping 2-3 times of pyrocondensation bus bar insulation tube, finally makes halogen-free flameproof bus bar Insulating heat shrink material of the present invention;
The halogen-free flameproof bus bar Insulating heat shrink prepared as stated above, main performance index is as follows: mechanics: breaking tenacity: more than 21.3MPa; Elongation at break: more than 538.8%.Fire-retardant: heat-shrink tube is retracted on copper pipe, 70 ° of angle flames execute combustion 15s, then flame-out 15s, and 5 times so repeatedly, tubing is without flammable phenomenon.Clip cracking experiment: under 115 DEG C of conditions, cut the longitudinal breach of 5mm to tube edges, 1.5h is without cracking phenomena.Thermal ageing: 158 ± 1 DEG C, 168h, breaking tenacity 18.6MPa after thermal ageing; Elongation at break 515.50%.Thermal shocking: 250 ± 1 DEG C, 4h, does not drip and does not flow.Low temperature flexibility :-40 ± 1 DEG C, 4h, 360 degree are wound around flawless.Meet the requirement of halogen-free environmental standard and European Union RoHS environmental protection instruction.
Embodiment 2
Get ethylene methyl methacrylate multipolymer (EMMA) 100kg(melt index MI:4-5g/min, MMA:28%), oxidation inhibitor (the IRGANOX B-215 of Ciba) 1.0kg, silicone masterbatch 2.7kg, polyethylene wax 0.3kg, trimethylolpropane trimethacrylate 4kg, Halogen toner/master batch 7kg, stirring at low speed in stirrer, stir after four minutes and drop into nanometer activation magnesium hydroxide 20kg again, superfine activated aluminium hydroxide 10kg, superfine activated kaolin 15kg high-speed stirring, batch mixing is terminated when mixture temperature reaches 70 DEG C, finally by 140 DEG C of banburying 40min in evenly mixed material to milling machine, after make pyrocondensation masterbatch through singe screw tablets press.Pyrocondensation masterbatch is simultaneously online to its inwall atomization oiling through extrusion moulding, electron accelerator irradiation sizing, continuously expanding and shaping 2-3 times of pyrocondensation bus bar insulation thimble, finally makes halogen-free flameproof bus bar Insulating heat shrink material of the present invention;
The halogen-free flameproof bus bar Insulating heat shrink prepared as stated above, main performance index is as follows: mechanics: breaking tenacity: more than 22.7MPa; Elongation at break: more than 520.8%.Fire-retardant: heat-shrink tube is retracted on copper pipe, 70 ° of angle flames execute combustion 15s, then flame-out 15s, and 5 times so repeatedly, tubing is without flammable phenomenon.Clip cracking experiment: under 115 DEG C of conditions, cut the longitudinal breach of 5mm to tube edges, 1.5h is without cracking phenomena.Thermal ageing: 158 ± 1 DEG C, 168h, breaking tenacity 18.9MPa after thermal ageing; Elongation at break 509.60%.Thermal shocking: 250 ± 1 DEG C, 4h, does not drip and does not flow.Low temperature flexibility :-40 ± 1 DEG C, 4h, 360 degree are wound around flawless.Meet the requirement of halogen-free environmental standard and European Union RoHS environmental protection instruction.
Embodiment 3
Get ethylene methyl methacrylate multipolymer (EMMA) 100kg(melt index MI:4-5g/min, MMA:28%), oxidation inhibitor (the IRGANOX B-215 of Ciba) 0.8kg, silicone masterbatch 1.7kg, polyethylene wax 0.5kg, trimethylolpropane trimethacrylate 3kg, Halogen toner/master batch 4kg, stirring at low speed in stirrer, stir after five minutes and drop into nanometer activation magnesium hydroxide 15kg again, superfine activated aluminium hydroxide 15kg, superfine activated kaolin 10kg high-speed stirring, batch mixing is terminated when mixture temperature reaches 65 DEG C, finally by 135 DEG C of banburying 35min in evenly mixed material to milling machine, after make pyrocondensation masterbatch through singe screw tablets press.Pyrocondensation masterbatch is simultaneously online to its inwall atomization oiling through extrusion moulding, electron accelerator irradiation sizing, continuously expanding and shaping 2-3 times of pyrocondensation bus bar insulation thimble, finally makes halogen-free flameproof bus bar Insulating heat shrink material of the present invention;
The halogen-free flameproof bus bar Insulating heat shrink prepared as stated above, main performance index is as follows: mechanics: breaking tenacity: more than 23.1MPa; Elongation at break: more than 540.8%.Fire-retardant: heat-shrink tube is retracted on copper pipe, 70 ° of angle flames execute combustion 15s, then flame-out 15s, and 5 times so repeatedly, tubing is without flammable phenomenon.Clip cracking experiment: under 115 DEG C of conditions, cut the longitudinal breach of 5mm to tube edges, 1.5h is without cracking phenomena.Thermal ageing: 158 ± 1 DEG C, 168h, breaking tenacity 18.6MPa after thermal ageing; Elongation at break 513.60%.Thermal shocking: 250 ± 1 DEG C, 4h, does not drip and does not flow.Low temperature flexibility :-40 ± 1 DEG C, 4h, 360 degree are wound around flawless.Meet the requirement of halogen-free environmental standard and European Union RoHS environmental protection instruction.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (9)
1. a halogen-free environment-friendly flame-proof bus bar Insulating heat shrink, is characterized in that, is made up of the feed composition of following weight proportion: ethylene methyl methacrylate copolymer 1 00 part; Halogen-free flame retardants 30-45 part; Oxidation inhibitor 0.5-1.0 part; Lubricant 1.0-3.0 part; Linking agent 2.0-4.0 part; Halogen toner/master batch 1-7 part.
2. halogen-free environment-friendly flame-proof bus bar Insulating heat shrink according to claim 1, is characterized in that, described ethylene methyl methacrylate multipolymer-EMMA melt index MI:4-5g/min, wherein MMA:28%.
3. halogen-free flameproof bus bar Insulating heat shrink according to claim 1, is characterized in that, described halogen-free flame retardants is inorganic combustion inhibitor; Described inorganic combustion inhibitor is nanometer activation magnesium hydroxide, superfine activated aluminium hydroxide and superfine activated kaolin.
4. halogen-free environment-friendly flame-proof bus bar Insulating heat shrink according to claim 1, it is characterized in that, described oxidation inhibitor is the IRGANOX B-215 of Ciba, the synergistic mixture be made up of 33% hindered phenol antioxygen IRGANOX 1010 and 67% organophosphite IRGANOX 168.
5. halogen-free environment-friendly flame-proof bus bar Insulating heat shrink according to claim 1, is characterized in that, described lubricant is silicone masterbatch and polyethylene wax, and the weight proportion of described silicone masterbatch and polyethylene wax is 3-9:1.
6. halogen-free environment-friendly flame-proof bus bar Insulating heat shrink according to claim 1, it is characterized in that, described linking agent is trimethylolpropane trimethacrylate.
7. halogen-free environment-friendly flame-proof bus bar Insulating heat shrink according to claim 1, is characterized in that, described Halogen toner/master batch is iron oxide red, black masterbatch, titanium dioxide or other various pigments.
8. the preparation method of the halogen-free environment-friendly flame-proof bus bar Insulating heat shrink according to any one of claim 1-7, it is characterized in that, described method is batch mixing two-step approach: first drop into plastic grain ethylene methyl methacrylate multipolymer and auxiliary agent oxidation inhibitor, lubricant, linking agent and Halogen toner/master batch high-speed stirring in stirrer, stir and drop into halogen-free flame retardants again after 3-5 minute, high-speed stirring again afterwards, batch mixing is terminated when mixture temperature reaches 60-70 DEG C, finally by 130-140 DEG C of banburying 30-40min in evenly mixed material to milling machine, after make pyrocondensation masterbatch through singe screw tablets press, pyrocondensation masterbatch is simultaneously online to its inwall atomization oiling through extrusion moulding, electron accelerator irradiation sizing, continuously expanding and shaping 2-3 times of pyrocondensation bus bar insulation tube, finally makes halogen-free flameproof bus bar Insulating heat shrink.
9. the halogen-free environment-friendly flame-proof bus bar Insulating heat shrink according to any one of claim 1-7, it is characterized in that, described halogen-free environment-friendly flame-proof bus bar Insulating heat shrink meets and by the test method of ASTM-D2671-2009 electrical equipment heat-shrinkable tube requirement.
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| CN201410780096.8A CN104530543A (en) | 2014-12-17 | 2014-12-17 | Halogen-free environmental-friendly flame-retardant bus-bar insulating heat-shrinkable bushing and preparation method thereof |
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| CN201410780096.8A CN104530543A (en) | 2014-12-17 | 2014-12-17 | Halogen-free environmental-friendly flame-retardant bus-bar insulating heat-shrinkable bushing and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104900334A (en) * | 2015-05-08 | 2015-09-09 | 大连联合高分子材料有限公司 | 10-35kv insulating tubular bus and manufacturing method thereof |
| CN106496758A (en) * | 2016-11-08 | 2017-03-15 | 长园集团股份有限公司 | A kind of three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof |
| CN109135094A (en) * | 2018-06-06 | 2019-01-04 | 荣马电器有限公司 | A kind of fire-retardant corrosion-resistant bus duct |
| CN109593260A (en) * | 2018-11-28 | 2019-04-09 | 青岛中科汉缆高分子材料有限公司 | Halogen-free flame-retardant thermal shrinkage material in a kind of nuclear island, halogen-free flameproof heat-shrinkable tube and preparation method thereof in nuclear island |
| CN111393733A (en) * | 2020-04-03 | 2020-07-10 | 江苏鼎尚电子材料股份有限公司 | Environment-friendly flame-retardant heat-shrinkable tubing and preparation method thereof |
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| CN102432937A (en) * | 2011-08-18 | 2012-05-02 | 长园集团股份有限公司 | 1E-level K1-type halogen-free flame-retardant heat-shrinkable pipe for nuclear power plant and preparation method thereof |
| CN102924779A (en) * | 2012-11-01 | 2013-02-13 | 深圳长园电子材料有限公司 | Bus bar heat-shrinkable tube and preparation method thereof |
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2014
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104900334A (en) * | 2015-05-08 | 2015-09-09 | 大连联合高分子材料有限公司 | 10-35kv insulating tubular bus and manufacturing method thereof |
| CN106496758A (en) * | 2016-11-08 | 2017-03-15 | 长园集团股份有限公司 | A kind of three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof |
| CN106496758B (en) * | 2016-11-08 | 2019-01-29 | 长园电子（集团）有限公司 | A kind of three generations's nuclear power halogen-free non-red-phosphorus flame-retardant thermal shrinkable tube and preparation method thereof |
| CN109135094A (en) * | 2018-06-06 | 2019-01-04 | 荣马电器有限公司 | A kind of fire-retardant corrosion-resistant bus duct |
| CN109593260A (en) * | 2018-11-28 | 2019-04-09 | 青岛中科汉缆高分子材料有限公司 | Halogen-free flame-retardant thermal shrinkage material in a kind of nuclear island, halogen-free flameproof heat-shrinkable tube and preparation method thereof in nuclear island |
| CN111393733A (en) * | 2020-04-03 | 2020-07-10 | 江苏鼎尚电子材料股份有限公司 | Environment-friendly flame-retardant heat-shrinkable tubing and preparation method thereof |
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Application publication date: 20150422 |