CN101696294B - Semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube and preparation method thereof - Google Patents

Semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube and preparation method thereof Download PDF

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Publication number
CN101696294B
CN101696294B CN2009101850360A CN200910185036A CN101696294B CN 101696294 B CN101696294 B CN 101696294B CN 2009101850360 A CN2009101850360 A CN 2009101850360A CN 200910185036 A CN200910185036 A CN 200910185036A CN 101696294 B CN101696294 B CN 101696294B
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parts
shrinkable tube
fire retardant
heat
semi
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CN101696294A (en
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张志强
庄向阳
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Jiangsu Dasheng Thermal Shrinkage Protection Products Co ltd
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JIANGSU DASHENG THERMAL THRINKAGE MATERIAL CO Ltd
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Abstract

The invention relates to a heat-shrinkable tube, in particular to a semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube and a preparation method thereof. The semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube is made of wall materials, wherein an external wall material contains the following raw materials in parts by mass: 90 parts of polyolefin mixed resin, 10 parts of conductive black, 10 parts of assistants and 30 parts of fire retardant. The preparation method of the heat-shrinkable tube comprises the following steps of preparation of internal and external wall materials, extrusion, irradiation and expansion-moulding. Compared with a traditional heat-shrinkable tube, the invention has the technical characteristics that the wall materials are fire retardant, and the heat-shrinkable tube is applied to a 35 kV high voltage, has all the service performances of the traditional heat-shrinkable tube and also has watertightness, leakproofness, corrosion-resistance and dampproof performance; in addition, the heat-shrinkable tube completely meets the environmental protection requirement of ROHS of countries of European Union and has the advantages of low-temperature shrinkage, three-time to four-time stable expansion, low longitudinal shrinking rate and the like.

Description

Semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube and preparation method thereof
One, technical field:
The present invention relates to a kind of heat-shrinkable tube, be specifically related to a kind of semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube and preparation method thereof.
Two, background technology
The pyrocondensation product is from being born till now; tempo be we can say and advanced by leaps and bounds; Application Areas is constantly widened, and is mainly used in insulation protection at the beginning of the pyrocondensation products production, is widely used in Aeronautics and Astronautics, boats and ships, automobile, household electrical appliances, communication and field of petrochemical industry till now.The pyrocondensation product plays effects such as anticorrosion, the against shock dislocation of sealed damp-proof, waterproof and circuit to cable junction and bifurcation, therefore both required heat-shrinkable tube that good physicals and electrical property are arranged, as performances such as wearability, shock resistance, insulation strength height; Requiring again simultaneously has good chemical property, as erosion resistance and weathering resistance etc.But common heat-shrink tube can't satisfy these requirements simultaneously, this has just proposed a new problem to us, that be exactly must exploitation be a kind of can waterproof sealing, a kind of novel pyrocondensation product of certain mechanical strength, good electrical properties and chemical property is arranged again.
But it is less to use 35kV hot high pressure compression material, the invention provides a kind of material contracting with heat that can work under the 35kV high pressure conditions.
Three, summary of the invention:
Technical purpose
The purpose of this invention is to provide a kind of semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube; this heat-shrink tube can be under the 35kV high pressure; keep excellent mechanical intensity, fire-retardant, electrical property and chemical property characteristics, and have good economic benefit and environmental protection benefit, be fit to apply on a large scale.
Technical scheme
The present invention has following technical scheme to finish: a kind of semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube is made up of the wall material, and according to mass fraction, its mesospore material is made up of for 30 parts 90 parts of polyolefine hybrid resins, 10 parts of graphitized carbon blacks, 10 parts of auxiliary agents and fire retardant; Described fire retardant is a decabromodiphenyl oxide.
By mass percentage: described polyolefine hybrid resin is the polyolefine hybrid resin that 1~30%EVA630,1~20%EVA421,20~50%EVA283 and four kinds of polyolefine material melt blendings of 10~30%EVA220 make;
Described auxiliary agent is made up of paraffin, antioxidant, anti copper agent, processing stabilizers and sensitization crosslinking coagent; Antioxidant four (β-(3 wherein, the 5-di-tert-butyl-hydroxy phenyl) tetramethylolmethane 1-3 part propionic acid), anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part, processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part, sensitization crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part, surplus is a paraffin;
A kind of preparation method of semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube:
A, the preparation of described semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube external wall material:
The polyolefine hybrid resin is 50 parts of the polyolefine hybrid resins that will make according to mass percent: 1~30%EVA630,1~20%EVA421,20~50%EVA283 and four kinds of polyolefine material melt blendings of 10~30%EVA220; 10 parts of described auxiliary agents, antioxidant four (β-(3 wherein, the 5-di-tert-butyl-hydroxy phenyl) pentaerythritol ester 1-3 part propionic acid), anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part, processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part is changed crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part, and surplus is a paraffin; Described fire retardant is 30 parts of decabromodiphenyl oxides.
Above-mentioned raw material adding Banbury mixer or height are stirred machine; stirring the back adds in the twin-screw mixer machine; under 140~160 ℃ temperature condition; through fully stirring and banburying; screw speed 125rpm, 110~135 ℃ of melting temperatures fully merge each component; be prepared into the external wall material of described semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube then through the tablets press granulation, standby.
B, extrude:
The wall material of steps A preparation is added in the forcing machine, through the fuselage heating and melting, back extrusion moulding from extruder head, through the tank cooling, wind-force dries up then, behind the surperficial lettering, receives on all rotating disks through tractor;
C, irradiation:
All rotating disks are put on the pay off rack,, introduce in the radiation chamber through the adjustable tension bracket of overtension, the present invention adopts irradiation device for electronic accelerator, irradiation dose is 12Mrad, to the twin wall emitter lateral work in-process of making circulate irradiation and cooling, is 30~60 circles at the number of times of exposure cell's internal recycle irradiation.Passing through the wire coiler rolling on all rotating disks;
D, expansion:
The single wall heat-shrink tube pipe that irradiation is good is placed on the pay off rack, adjust tension force, introduce in the dilator, add through overbalance, after the twin wall emitter lateral work in-process reach 100 ℃ of technological temperatures, introduce Standard Module and expand and cool off, introduce tank then and fully cool off, product temperature is reduced to room temperature, and rolling is packaged into described semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube finished product then.
The main production equipments inventory
Machinery or device name Model specification The country origin place of production Rated output
Rumbatron DD Chinese Shanghai 2.0Mev
Multi-functional irradiation transmission system / Chinese Shanghai 80KW
The granulation Banbury mixer 75L Chinese Shanghai 150KW
Forcing machine SJ-120 The China Zhangjiagang 123KW
Twin screw extruder TE-70 Nanjing of China 75KW
Principle: because cross-linking radiation changes polyolefinic molecular structure, this variation makes polyolefine have memory effect under certain condition.Heat-shrinkable tube utilizes the principle of this memory effect just, behind the heat-shrinkable tube work in-process cross-linking radiation, with behind its expansion cooling and shaping, is exactly finished product after the heating.In use, the heating back is because memory effect retracts to the preceding state of expansion again.
Beneficial effect:
1, wall material: because the wall material adopts hybrid resin, this hybrid resin can be in 35kV high pressure works better.
2, remedied the shortcoming that the ordinary hot collapsible tube can not waterproof sealing.This product possesses whole use propertieies of ordinary hot collapsible tube fully, has also possessed performances such as waterproof sealing moisture-proof anticorrosive simultaneously.
3, this product satisfies the environmental requirement of state ROHS such as European Union instruction fully, has that low temperature shrinks, three times to four times stable expansions, has advantages such as vertical shrinking percentage is low.
Four, embodiment
Embodiment 1
A kind of semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube is made up of the wall material, and according to mass fraction, its mesospore material is made up of for 30 parts 90 parts of polyolefine hybrid resins, 10 parts of graphitized carbon blacks, 10 parts of auxiliary agents and fire retardant; Described fire retardant is a decabromodiphenyl oxide.
By mass percentage: described polyolefine hybrid resin is the polyolefine hybrid resin that 1~30%EVA630,1~20%EVA421,20~50%EVA283 and four kinds of polyolefine material melt blendings of 10~30%EVA220 make;
Press mass fraction, described auxiliary agent is made up of paraffin, antioxidant, anti copper agent, processing stabilizers and sensitization crosslinking coagent, wherein antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) tetramethylolmethane 1-3 part; Anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part, processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part is changed crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part, and surplus is a paraffin;
A kind of preparation method of semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube:
A, the preparation of described semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube external wall material:
The polyolefine hybrid resin is 50 parts of the polyolefine hybrid resins that will make according to mass percent: 1~30%EVA630,1~20%EVA421,20~50%EVA283 and four kinds of polyolefine material melt blendings of 10~30%EVA220.10 parts of described first auxiliary agents, wherein antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 1-3 part; Anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part; Processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part; Change crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part; Surplus is a paraffin; Described fire retardant is 30 parts of decabromodiphenyl oxides.
Above-mentioned raw materials is added Banbury mixer or height stirs machine; stirring the back adds in the twin-screw mixer machine; under 140~160 ℃ temperature condition; through fully stirring and banburying; screw speed 125rpm, 110~135 ℃ of melting temperatures fully merge each component; be prepared into the external wall material of described semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube then through the tablets press granulation, standby.
B, extrude:
The wall material of steps A preparation is added in the forcing machine, and through extrusion moulding from extruder head behind the fuselage heating and melting, through the tank cooling, wind-force dries up then, behind the surperficial lettering, receives on all rotating disks through tractor;
C, irradiation:
All rotating disks are put on the pay off rack,, introduce in the radiation chamber through the adjustable tension bracket of overtension, the present invention adopts irradiation device for electronic accelerator, irradiation dose is 12Mrad, to the twin wall emitter lateral work in-process of making circulate irradiation and cooling, is 30~60 circles at the number of times of exposure cell's internal recycle irradiation.Passing through the wire coiler rolling on all rotating disks;
D, expansion:
The single wall heat-shrink tube pipe that irradiation is good is placed on the pay off rack, adjust tension force, introduce in the dilator, add through overbalance, after the twin wall emitter lateral work in-process reach 100 ℃ of technological temperatures, introduce Standard Module and expand and cool off, introduce tank then and fully cool off, product temperature is reduced to room temperature, and rolling is packaged into described semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube finished product then.
Embodiment 2
A kind of semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube is made up of the wall material, and according to mass fraction, its mesospore material is made up of for 30 parts 90 parts of polyolefine hybrid resins, 10 parts of graphitized carbon blacks, 10 parts of auxiliary agents and fire retardant; Described fire retardant is a decabromodiphenyl oxide.
By mass percentage: described polyolefine hybrid resin is the polyolefine hybrid resin that 15%EVA630,20%EVA421,45%EVA283 and four kinds of polyolefine material melt blendings of 20%EVA220 make;
Press mass fraction, described auxiliary agent is made up of paraffin, antioxidant, anti copper agent, processing stabilizers and sensitization crosslinking coagent, wherein antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) tetramethylolmethane 1-3 part; Anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part, processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part is changed crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part, and surplus is a paraffin;
A kind of preparation method of semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube:
A, the preparation of described semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube external wall material:
The polyolefine hybrid resin is 50 parts of the polyolefine hybrid resins that will make according to mass percent: 15%EVA630,20%EVA421,45%EVA283 and four kinds of polyolefine material melt blendings of 20%EVA220.10 parts of described auxiliary agents, wherein antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 1-3 part; Anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part; Processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part; Change crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part; Surplus is a paraffin; Described fire retardant is 30 parts of decabromodiphenyl oxides.
Above-mentioned raw materials is added Banbury mixer or height stirs machine; stirring the back adds in the twin-screw mixer machine; under 140~160 ℃ temperature condition; through fully stirring and banburying; screw speed 125rpm, 110~135 ℃ of melting temperatures fully merge each component; be prepared into the external wall material of described semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube then through the tablets press granulation, standby.
B, extrude:
The wall material wall material of steps A preparation is added in the forcing machine, and through extrusion moulding from extruder head behind the fuselage heating and melting, through the tank cooling, wind-force dries up then, behind the surperficial lettering, receives on all rotating disks through tractor;
C, irradiation:
All rotating disks are put on the pay off rack,, introduce in the radiation chamber through the adjustable tension bracket of overtension, the present invention adopts irradiation device for electronic accelerator, irradiation dose is 12Mrad, to the twin wall emitter lateral work in-process of making circulate irradiation and cooling, is 30~60 circles at the number of times of exposure cell's internal recycle irradiation.Passing through the wire coiler rolling on all rotating disks;
D, expansion:
The single wall heat-shrink tube pipe that irradiation is good is placed on the pay off rack, adjust tension force, introduce in the dilator, add through overbalance, after the twin wall emitter lateral work in-process reach 100 ℃ of technological temperatures, introduce Standard Module and expand and cool off, introduce tank then and fully cool off, product temperature is reduced to room temperature, and rolling is packaged into described semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube finished product then.
Embodiment 3
A kind of semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube is made up of the wall material, and according to mass fraction, its mesospore material is made up of for 30 parts 90 parts of polyolefine hybrid resins, 10 parts of graphitized carbon blacks, 10 parts of auxiliary agents and fire retardant; Described fire retardant is a decabromodiphenyl oxide.
By mass percentage: described polyolefine hybrid resin is the polyolefine hybrid resin that 30%EVA630,20%EVA421,40%EVA283 and four kinds of polyolefine material melt blendings of 10%EVA220 make;
Press mass fraction, described auxiliary agent is made up of paraffin, antioxidant, anti copper agent, processing stabilizers and sensitization crosslinking coagent, wherein antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) tetramethylolmethane 1-3 part; Anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part, processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part is changed crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part, and surplus is a paraffin;
A kind of preparation method of semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube:
A, the preparation of described semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube external wall material:
The polyolefine hybrid resin is 50 parts of the polyolefine hybrid resins that will make according to mass percent: 30%EVA630,20%EVA421,40%EVA283 and four kinds of polyolefine material melt blendings of 10%EVA220.10 parts of described auxiliary agents, wherein antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 1-3 part; Anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part; Processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part; Change crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part; Surplus is a paraffin; Described fire retardant is 30 parts of decabromodiphenyl oxides.
Above-mentioned raw materials is added Banbury mixer or height stirs machine; stirring the back adds in the twin-screw mixer machine; under 140~160 ℃ temperature condition; through fully stirring and banburying; screw speed 125rpm, 110~135 ℃ of melting temperatures fully merge each component; be prepared into the external wall material of described semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube then through the tablets press granulation, standby.
B, extrude:
The inner wall material of the external wall material of steps A preparation and step B preparation is added into respectively in the two extruders that an angle of 90 degrees puts, through extrusion moulding from shared extruder head behind the fuselage heating and melting, form bilayer structure, then through the tank cooling, wind-force dries up, behind the lettering of surface, receive on all rotating disks through tractor; The quality amount ratio of external wall material and Nell wall material: 1: 1~3: 1;
C, irradiation:
All rotating disks are put on the pay off rack,, introduce in the radiation chamber through the adjustable tension bracket of overtension, the present invention adopts irradiation device for electronic accelerator, irradiation dose is 12Mrad, to the twin wall emitter lateral work in-process of making circulate irradiation and cooling, is 30~60 circles at the number of times of exposure cell's internal recycle irradiation.Passing through the wire coiler rolling on all rotating disks;
D, expansion:
The single wall heat-shrink tube that irradiation is good is placed on the pay off rack, adjust tension force, introduce in the dilator, add through overbalance, after the twin wall emitter lateral work in-process reach 100 ℃ of technological temperatures, introduce Standard Module and expand and cool off, introduce tank then and fully cool off, product temperature is reduced to room temperature, and rolling is packaged into described semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube finished product then.

Claims (2)

1. semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube, it is characterized in that: be made up of the wall material, according to mass parts, described wall material is made up of for 30 parts 90 parts of polyolefine hybrid resins, 10 parts of graphitized carbon blacks, 10 parts of auxiliary agents and fire retardant; Described polyolefine hybrid resin is the polyolefine hybrid resin that 1~30%EYA630,1~20%EVA421,20~50%EVA283 and four kinds of polyolefine material melt blendings of 10~30%EVA220 make by mass percentage; Described auxiliary agent is: antioxidant 1-3 part, and anti copper agent 0.5-1 part, processing stabilizers 0.02-2 part, smoke suppressor 2-4 part, sensitization crosslinking coagent 1-2 part, surplus is a paraffin; Described fire retardant is a decabromodiphenyl oxide;
Described antioxidant is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester; Anti copper agent is a hydroxy-terminated polybutadienes vinyl cyanide fluid rubber; Processing stabilizers is rare-earth stabilizer REC-LS-D or REC-LS-F; Smoke suppressor is a zinc borate; The sensitization crosslinking coagent is a TriMethylolPropane(TMP).
2. semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube according to claim 1 is characterized in that: the polyolefine hybrid resin that described polyolefine hybrid resin makes for 15%EVA630,20%EVA421,45%EVA283 and four kinds of polyolefine material melt blendings of 20%EVA220 by mass percentage; Described auxiliary agent is 1 part of an antioxidant, 1 part of anti copper agent, and 2 parts of processing stabilizers, 3 parts of smoke suppressors, 1 part of sensitization crosslinking coagent, surplus is a paraffin.
CN2009101850360A 2009-10-28 2009-10-28 Semi-conducting high-voltage fire retardant single-wall heat-shrinkable tube and preparation method thereof Expired - Fee Related CN101696294B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4163117A (en) * 1978-04-19 1979-07-31 Raychem Corporation Heat-recoverable articles and their use
CN1410496A (en) * 2001-10-10 2003-04-16 华新丽华股份有限公司 Environmental protection cable wire coating composition
CN101255246A (en) * 2007-06-06 2008-09-03 深圳长园电子材料有限公司 Antistatic thermo-shrinkage material and manufacturing method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4163117A (en) * 1978-04-19 1979-07-31 Raychem Corporation Heat-recoverable articles and their use
CN1410496A (en) * 2001-10-10 2003-04-16 华新丽华股份有限公司 Environmental protection cable wire coating composition
CN101255246A (en) * 2007-06-06 2008-09-03 深圳长园电子材料有限公司 Antistatic thermo-shrinkage material and manufacturing method thereof

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Granted publication date: 20110914