CN101698718B - Semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube and preparation method thereof - Google Patents
Semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 100
- 229920000098 polyolefin Polymers 0.000 claims abstract description 89
- 239000003063 flame retardant Substances 0.000 claims abstract description 83
- 239000011347 resin Substances 0.000 claims abstract description 65
- 229920005989 resin Polymers 0.000 claims abstract description 65
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 230000005855 radiation Effects 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 130
- 239000000203 mixture Substances 0.000 claims description 120
- 239000007822 coupling agent Substances 0.000 claims description 88
- 238000000034 method Methods 0.000 claims description 61
- 238000003756 stirring Methods 0.000 claims description 61
- 239000012752 auxiliary agent Substances 0.000 claims description 42
- 230000008878 coupling Effects 0.000 claims description 40
- 238000010168 coupling process Methods 0.000 claims description 40
- 238000005859 coupling reaction Methods 0.000 claims description 40
- 239000007921 spray Substances 0.000 claims description 40
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 33
- 239000000347 magnesium hydroxide Substances 0.000 claims description 33
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 32
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 30
- -1 polydimethylsiloxane Polymers 0.000 claims description 30
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 28
- 239000003963 antioxidant agent Substances 0.000 claims description 27
- 230000003078 antioxidant effect Effects 0.000 claims description 26
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 23
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 23
- 239000005995 Aluminium silicate Substances 0.000 claims description 20
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 20
- 235000012211 aluminium silicate Nutrition 0.000 claims description 20
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 238000004132 cross linking Methods 0.000 claims description 18
- 239000003381 stabilizer Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 206010070834 Sensitisation Diseases 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 230000008313 sensitization Effects 0.000 claims description 16
- 239000012188 paraffin wax Substances 0.000 claims description 15
- 235000019260 propionic acid Nutrition 0.000 claims description 14
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 14
- 239000000779 smoke Substances 0.000 claims description 12
- FJRUWRJAJNEIKD-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-6,7-diamine Chemical compound O1CCOC2=C1C=C(N)C(N)=C2 FJRUWRJAJNEIKD-UHFFFAOYSA-N 0.000 claims description 11
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 11
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 11
- 230000003179 granulation Effects 0.000 claims description 11
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 235000019241 carbon black Nutrition 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 229940059574 pentaerithrityl Drugs 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 8
- RQFLGKYCYMMRMC-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O RQFLGKYCYMMRMC-UHFFFAOYSA-N 0.000 description 8
- 229920002545 silicone oil Polymers 0.000 description 8
- 239000006084 composite stabilizer Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003446 memory effect Effects 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a heat-shrinkable tube, in particular to a semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube and a preparation method thereof. The tube consists of an external wall material and an internal wall material. The external wall material comprises the following raw materials in part by mass: first polyolefin mixed resin 40, conductive black 10, first assistant 10, fire retardant 30 and auxiliary fire retardant 10. The internal wall material comprises the following raw materials in part by mass: second polyolefin mixed resin 50, second assistant 10, fire retardant 30 and auxiliary fire retardant 10. The preparation method comprises the preparation of the internal and external wall materials of the double-wall heat-shrinkable tube, extrusion, radiation and expansion forming. Compared with the traditional heat-shrinkable tube, the heat-shrinkable tube has the technical characteristics that: the raw materials include the fire retardant and the auxiliary fire retardant; and the product has high fire-retarding effect, high-temperature resistance, high performance, low cost and obvious economic and environmental protection benefits, avoids pollution even in burning and is suitable to be promoted and used in large scale.
Description
One, technical field:
The present invention relates to a kind of heat-shrinkable tube, be specifically related to a kind of semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube and preparation method thereof.
Two, background technology
The thermal contraction double-walled pipe of Xiao Shouing has inside and outside double-layer structure in the market, by by shape memory function through heating can radial shrinkage flame-retardant high-molecular outer and under shrinkage temperature the inside glue-line of melt-flowable form, after heating, inner glue-line melt-flow is filled, can be widely used in Aeronautics and Astronautics, boats and ships, automobile, household electrical appliances, communication, field of petrochemical industry, electric wire junction and bifurcation be played the effect such as anticorrosion, against shock dislocation of fire-retardant, sealed damp-proof, waterproof, circuit.What use in the prescription of layered material outside routine is halogen-containing fire retardant, the time has the height highly toxic drawback of being fuming in burning, causes the secondary disaster of fire easily.Current country is more and more higher to requirement on environmental protection, has adopted not halogen-containing fire retardant in a lot of fields, and the environmental protection organization of EU member country has also delivered the decree that the plastics of forbidding halogen-containing flame retardant enter the European market.But there is shortcoming of low quality, that cost is high or flame retardant effect is bad in the twin wall emitter lateral for halogen-free flame-retardant in the prior art more.
Three, summary of the invention:
Technical purpose
The purpose of this invention is to provide a kind of semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube and preparation method thereof; adopt halogen-free flame retardants in the raw material; the good flame retardation effect of product; high temperature resistant, have a good performance; even it is also pollution-free during burning; cost reduces, and has remarkable economic efficiency and environmental protection benefit, is fit to apply on a large scale.
Technical scheme
The present invention has following technical scheme to finish: a kind of semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube is made up of external wall material and inner wall material, according to mass fraction, wherein external wall material is that 10 parts, 30 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 40 parts of the first polyolefine hybrid resins, 10 parts of graphitized carbon blacks, first auxiliary agent; Inner wall material is made up of for 10 parts 50 parts of the second polyolefine hybrid resins, 10 parts of second auxiliary agents, 30 parts of fire retardants and auxiliary flame retardant; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
By mass percentage: the described first 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 first 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;
The described second polyolefine hybrid resin is that EVA110 and two kinds of polyolefine materials of EVA220 are according to the polyolefine hybrid resin that makes than melt blending arbitrarily.
Rosin 1-5 part in described second auxiliary agent, antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.5-5 part, surplus is a DEDB.
Described fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for ultra-fine aluminum silicon powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described four kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
A kind of preparation method of semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube:
A kind of preparation method of semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube is characterized in that:
A. the preparation of external wall material:
Described external wall material is that 10 parts, 30 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 40 parts of the first polyolefine hybrid resins, 10 parts of graphitized carbon blacks, first auxiliary agent; The first 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 by mass percentage; First auxiliary agent is that antioxidant is 1-3 part, anti copper agent 0.5-1 part, and processing stabilizers 0.02-2 part, smoke suppressor 2-4 part, sensitization crosslinking coagent 1-2 part, surplus is a paraffin; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
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-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube then through the tablets press granulation, standby;
B. the preparation of inner wall material:
According to mass fraction, the described second polyolefine hybrid resin is EVA110 and two kinds of polyolefine materials of EVA220 according to 53 parts of the polyolefine hybrid resins that makes than melt blending arbitrarily; 10 parts of described second auxiliary agents, rosin 1-5 part wherein, antioxidant is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.5-5 part, surplus is a DEDB; Fire retardant is 30 parts; 10 parts of auxiliary flame retardants; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
Above-mentioned raw materials is added height stir in the machine, stirred 10-20 minute; Add the twin-screw mixer machine then and carry out fully mixingly, screw speed is 100rpm, and melting temperature is 115 ℃, causes particle through tablets press again; In order to make each component mixing evenly, the particle of making is added in the twin-screw mixer machine, mixing once more, screw speed 100rpm, 110～135 ℃ of melting temperatures, the semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube inner wall material is made in granulation then, and is standby;
C. 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 inner wall material: 1: 1～3: 1;
D. 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;
E. expansion:
The semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable 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-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube finished product then;
Wherein said fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for ultra-fine aluminum silicon powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described four kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
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, adopt special halogen-free flame retardants in the raw material, the good flame retardation effect of product, high temperature resistant, have good performance, even also pollution-free during burning, cost reduces, and has remarkable economic efficiency and environmental protection benefit, is fit to apply on a large scale.
2, outer wall materials: because the outer main insulation protection effect that plays.So when the outer pipe wall material prescription designed, we had selected intensity higher, the polyolefine that softening temperature is 120～130 ℃ is cooked major ingredient, adds other auxiliary agents of corresponding proportion simultaneously.
3, inner wall material: inner wall material mainly has been the waterproof sealing effect, and therefore certain stripping strength and well mobile will be arranged.The softening temperature of glue will be lower than the heat shrink temperature of external wall material simultaneously, could satisfy production requirement like this.
The softening temperature of inner wall material is 70～80 ℃ among the present invention.
4, the technical characterstic internal layer thermosol of the more traditional collapsible tube of this product can waterproof sealing, and outer layered material has kept characteristics such as ordinary hot draw good electrical properties and chemical property, so Application Areas is more extensive.
5, 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.
6, this product satisfies the environmental requirement of state R O H S 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-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube is made up of external wall material and inner wall material, according to mass fraction, wherein external wall material is that 10 parts, 30 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 40 parts of the first polyolefine hybrid resins, 10 parts of graphitized carbon blacks, first auxiliary agent; Inner wall material is made up of for 10 parts 50 parts of the second polyolefine hybrid resins, 10 parts of second auxiliary agents, 30 parts of fire retardants and auxiliary flame retardant; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
By mass percentage: the described first 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 first 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;
The described second polyolefine hybrid resin is that EVA110 and two kinds of polyolefine materials of EVA220 are according to the polyolefine hybrid resin that makes than melt blending arbitrarily.
Rosin 1-5 part in described second auxiliary agent, antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.5-5 part, surplus is a DEDB.
Described fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for ultra-fine aluminum silicon powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described four kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
A kind of preparation method of semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube,
A. the preparation of external wall material:
Described external wall material is that 10 parts, 30 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 40 parts of the first polyolefine hybrid resins, 10 parts of graphitized carbon blacks, first auxiliary agent; The first 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 by mass percentage; First auxiliary agent is that antioxidant is 1-3 part, anti copper agent 0.5-1 part, and processing stabilizers 0.02-2 part, smoke suppressor 2-4 part, sensitization crosslinking coagent 1-2 part, surplus is a paraffin; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
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-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube then through the tablets press granulation, standby;
B. the preparation of inner wall material:
According to mass fraction, the described second polyolefine hybrid resin is EVA110 and two kinds of polyolefine materials of EVA220 according to 53 parts of the polyolefine hybrid resins that makes than melt blending arbitrarily; 10 parts of described second auxiliary agents, rosin 1-15 part wherein, antioxidant is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.5-5 part, surplus is a DEDB; Fire retardant is 30 parts; 10 parts of auxiliary flame retardants; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
Above-mentioned second polyolefine hybrid resin and second auxiliary agent adding height are stirred in the machine, stirred 10-20 minute; Add the twin-screw mixer machine then and carry out fully mixingly, screw speed is 100rpm, and melting temperature is 115 ℃, causes particle through tablets press again; In order to make each component mixing evenly, the particle of making is added in the twin-screw mixer machine, mixing once more, screw speed 100rpm, 110～135 ℃ of melting temperatures, the semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube inner wall material is made in granulation then, and is standby;
C. 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 inner wall material: 1: 1～3: 1;
D. 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;
E. expansion:
The semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable 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-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube finished product then;
Wherein said fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for ultra-fine aluminum silicon powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described three kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
Embodiment 2
A kind of semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube is made up of external wall material and inner wall material, according to mass fraction, wherein external wall material is that 10 parts, 30 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 40 parts of the first polyolefine hybrid resins, 10 parts of graphitized carbon blacks, first auxiliary agent; Inner wall material is made up of 50 parts of the second polyolefine hybrid resins, 10 parts of second auxiliary agents, 30 parts of fire retardants and auxiliary flame retardant; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
By mass percentage: the described first 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%EVA2200 make;
Described first 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;
The described second polyolefine hybrid resin is that EVA110 and two kinds of polyolefine materials of EVA220 are according to the polyolefine hybrid resin that makes than melt blending arbitrarily.
Rosin 1-5 part in described second auxiliary agent, antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.5-5 part, surplus is a DEDB.
Described fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for ultra-fine aluminum silicon powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described four kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
A kind of preparation method of semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube is characterized in that:
A. the preparation of external wall material:
Described external wall material is that 10 parts and fire retardant are formed for 37 parts by 53 parts of the first polyolefine hybrid resins, first auxiliary agent; The polyolefine hybrid resin that the first 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; First auxiliary agent is that antioxidant is 1-3 part, anti copper agent 0.5-1 part, and processing stabilizers 0.02-2 part, smoke suppressor 2-4 part, sensitization crosslinking coagent 1-2 part, surplus is a paraffin; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
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-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube then through the tablets press granulation, standby;
B. the preparation of inner wall material:
According to mass fraction, the described second polyolefine hybrid resin is EVA110 and two kinds of polyolefine materials of EVA220 according to 53 parts of the polyolefine hybrid resins that makes than melt blending arbitrarily; 10 parts of described second auxiliary agents, rosin 1-10 part wherein, antioxidant is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.5-5 part, surplus is a DEDB; Fire retardant is 37 parts; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
Above-mentioned second polyolefine hybrid resin and second auxiliary agent adding height are stirred in the machine, stirred 10-20 minute; Add the twin-screw mixer machine then and carry out fully mixingly, screw speed is 100rpm, and melting temperature is 115 ℃, causes particle through tablets press again; In order to make each component mixing evenly, the particle of making is added in the twin-screw mixer machine, mixing once more, screw speed 100rpm, 110～135 ℃ of melting temperatures, the semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube inner wall material is made in granulation then, and is standby;
C. 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 inner wall material: 1: 1～3: 1;
D. 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;
E. expansion:
The semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable 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-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube finished product then;
Wherein said fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for ultra-fine aluminum silicon powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described four kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
Embodiment 3
A kind of semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube is made up of external wall material and inner wall material, according to mass fraction, wherein external wall material is that 10 parts, 30 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 40 parts of the first polyolefine hybrid resins, 10 parts of graphitized carbon blacks, first auxiliary agent; Inner wall material is made up of for 10 parts 53 parts of the second polyolefine hybrid resins, 10 parts of second auxiliary agents, 30 parts of fire retardants and auxiliary flame retardant; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
By mass percentage: the described first 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;
Described first 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;
The described second polyolefine hybrid resin is that EVA110 and two kinds of polyolefine materials of EVA220 are according to the polyolefine hybrid resin that makes than melt blending arbitrarily.
Rosin 1-5 part in described second auxiliary agent, antioxidant four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.5-5 part, surplus is a DEDB.
Described fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for ultra-fine aluminum silicon powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described three kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
A kind of preparation method of semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube is characterized in that:
A. the preparation of external wall material:
Described external wall material is that 10 parts, 30 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 40 parts of the first polyolefine hybrid resins, 10 parts of graphitized carbon blacks, first auxiliary agent; The polyolefine hybrid resin that the first polyolefine hybrid resin makes for 30%EVA630,20%EVA421,40%EVA283 and four kinds of polyolefine material melt blendings of 10%EVA220 by mass percentage; First auxiliary agent is that antioxidant is 1-3 part, anti copper agent 0.5-1 part, and processing stabilizers 0.02-2 part, smoke suppressor 2-4 part, sensitization crosslinking coagent 1-2 part, surplus is a paraffin; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
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-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube then through the tablets press granulation, standby;
B. the preparation of inner wall material:
According to mass fraction, the described second polyolefine hybrid resin is EVA110 and two kinds of polyolefine materials of EVA220 according to 53 parts of the polyolefine hybrid resins that makes than melt blending arbitrarily; 10 parts of described second auxiliary agents, rosin 1-5 part wherein, antioxidant is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.5-5 part, surplus is a DEDB; Fire retardant is 37 parts; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;
Above-mentioned second polyolefine hybrid resin and second auxiliary agent adding height are stirred in the machine, stirred 10-20 minute; Add the twin-screw mixer machine then and carry out fully mixingly, screw speed is 100rpm, and melting temperature is 115 ℃, causes particle through tablets press again; In order to make each component mixing evenly, the particle of making is added in the twin-screw mixer machine, mixing once more, screw speed 100rpm, 110～135 ℃ of melting temperatures, the semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube inner wall material is made in granulation then, and is standby;
C. 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 inner wall material: 1: 1～3: 1;
D. 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;
E. expansion:
The semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable 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-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube finished product then;
Wherein said fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for ultra-fine aluminum silicon powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described three kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant.
Described coupling agent A is a silane coupling agent 550, and coupling agent B is dimethyl silicone oil (a line style polydimethylsiloxane), and coupling agent C is stearic acid (octadecanoic acid), and coupling agent D is titanate coupling agent TC-114 (a tetra-sodium type monoalkoxy class titanic acid ester).
Claims (4)
1. semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube, it is characterized in that: form by external wall material and inner wall material, according to mass fraction, described external wall material is made up of for 10 parts 40 parts of the first polyolefine hybrid resins, 10 parts of graphitized carbon blacks, 10 parts, 30 parts fire retardants of first auxiliary agent and auxiliary flame retardant; Described inner wall material is made up of for 10 parts 50 parts of the second polyolefine hybrid resins, 10 parts, 30 parts fire retardants of second auxiliary agent and auxiliary flame retardant; The described first 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 by mass percentage; Described first auxiliary agent is that antioxidant is 1-3 part, anti copper agent 0.5-1 part, and processing stabilizers 0.02-2 part, smoke suppressor 2-4 part, sensitization crosslinking coagent 1-2 part, surplus is a paraffin;
The described second polyolefine hybrid resin is that EVA110 and two kinds of polyolefine materials of EVA220 are according to the polyolefine hybrid resin that makes than melt blending arbitrarily; Described second auxiliary agent is rosin 1-5 part, antioxidant 0.5-5 part, and surplus is a DEDB; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide; Described fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for ultra-fine aluminum silicon powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described four kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant,
Described coupling agent A is a silane coupling agent 550, and coupling agent B is the line style polydimethylsiloxane, and coupling agent C is an octadecanoic acid, and coupling agent D is a tetra-sodium type monoalkoxy class titanic acid ester.
2. semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube according to claim 1 is characterized in that: 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).
3. semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube according to claim 1 and 2 is characterized in that: the described first polyolefine hybrid resin is the polyolefine hybrid resin that makes of 15%EVA630,20%EVA421,45%EVA283 and four kinds of polyolefine material melt blendings of 20%EVA220 by mass percentage; Described first auxiliary agent is that antioxidant is 1 part, 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; The described second polyolefine hybrid resin is that EVA110 and two kinds of polyolefine materials of EVA220 are according to the polyolefine hybrid resin that makes than melt blending arbitrarily; Described second auxiliary agent is 5 parts of rosin, 4 parts of antioxidants, and surplus is a DEDB.
4. the preparation method of a semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube is characterized in that:
A. the preparation of external wall material:
Described external wall material is that 10 parts and fire retardant are formed for 37 parts by 53 parts of the first polyolefine hybrid resins, first auxiliary agent; The first 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 by mass percentage; First auxiliary agent is that antioxidant is 1-3 part, anti copper agent 0.5-1 part, and processing stabilizers 0.02-2 part, smoke suppressor 2-4 part, sensitization crosslinking coagent 1-2 part, surplus is a paraffin;
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-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube then through the tablets press granulation, standby;
B. the preparation of inner wall material:
According to mass fraction, the second polyolefine hybrid resin is EVA110 and two kinds of polyolefine materials of EVA220 according to 53 parts of the polyolefine hybrid resins that makes than melt blending arbitrarily; 10 parts of second auxiliary agents, rosin 1-5 part wherein, antioxidant is four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester 0.5-5 part, surplus is a DEDB; Fire retardant is 37 parts;
Above-mentioned second polyolefine hybrid resin and second auxiliary agent adding height are stirred in the machine, stirred 10-20 minute; Add the twin-screw mixer machine then and carry out fully mixingly, screw speed is 100rpm, and melting temperature is 115 ℃, causes particle through tablets press again; In order to make each component mixing evenly, the particle of making is added in the twin-screw mixer machine, mixing once more, screw speed 100rpm, 110～135 ℃ of melting temperatures, the semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube inner wall material is made in granulation then, and is standby;
C. 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 inner wall material: 1: 1～3: 1;
D. irradiation:
All rotating disks are put on the pay off rack, through the adjustable tension bracket of overtension, in the introducing radiation chamber, adopt irradiation device for electronic accelerator, irradiation dose is 12Mrad, to the twin wall emitter lateral work in-process of making circulate irradiation and cooling, be 30～60 circles at the number of times of exposure cell's internal recycle irradiation, through the wire coiler rolling on all rotating disks;
E. expansion:
The semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable 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-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube finished product then; Wherein said fire retardant is prepared by following method:
A inserts the super fine magnesium hydroxide powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent A that adopts spray method will account for magnesium hydroxide grain weight amount 3% adds in the powder, makes the abundant coupling modification of powder, makes composition No. 1;
B ultra fine aluminium hydroxide body is inserted in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent B that adopts spray method will account for aluminium hydrate powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 2;
C inserts the ultrafine kaolin powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent C that adopts spray method will account for kaolin powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 3;
D inserts ultra-fine aluminum silicon powder powder in the homogenizer, evenly stirs and be heated to 105～120 ℃, and the coupling agent D that adopts spray method will account for ultra-fine aluminum silicon powder weight 3% adds in the powder, makes the abundant coupling of powder, makes composition No. 4;
E is composite with described No. 1 composition, No. 2 compositions, No. 3 compositions and No. 4 components in certain proportion, and the consumption of described four kinds of compositions is, according to mass fraction: 55 parts of No. 1 compositions, 50 parts of No. 2 compositions, 10 parts of No. 3 compositions, 10 parts of No. 4 compositions; And evenly stir, make fire retardant,
Described coupling agent A is a silane coupling agent 550, and coupling agent B is the line style polydimethylsiloxane, and coupling agent C is an octadecanoic acid, and coupling agent D is a tetra-sodium type monoalkoxy class titanic acid ester.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101850549A CN101698718B (en) | 2009-10-28 | 2009-10-28 | Semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101850549A CN101698718B (en) | 2009-10-28 | 2009-10-28 | Semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
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| CN101698718A CN101698718A (en) | 2010-04-28 |
| CN101698718B true CN101698718B (en) | 2011-07-13 |
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| CN2009101850549A Expired - Fee Related CN101698718B (en) | 2009-10-28 | 2009-10-28 | Semi-conductive high-strength halogen-free fire-retarding double-wall heat-shrinkable tube and preparation method thereof |
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| Country | Link |
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| CN (1) | CN101698718B (en) |
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