CN101759907A - Halogen-free double-wall heat shrinkable tube of flame-retardant properties and preparing method thereof - Google Patents
Halogen-free double-wall heat shrinkable tube of flame-retardant properties and preparing method thereof Download PDFInfo
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Abstract
The present invention relates to a heat shrinkable tube, particularly to a halogen-free double-wall heat shrinkable tube of flame-retardant properties and a preparing method thereof. The tube is prepared from an outer wall material and an inner wall material based on shares by weight. The outer wall material consists of 53 shares of first polyolefin mixed resin, 10 shares of first auxiliaries and 37 shares of flame retardant. The inner wall material consists of 53 shares of second polyolefin mixed resin, 10 shares of second auxiliaries and 37 shares of flame retardant. The preparing method comprises: preparing the inner and the outer wall materials of the double-wall heat shrinkable tube, extruding, irradiating, expanding and molding. Compared with traditional shrinkable tubes, the present invention has the technical characteristics of adoption of special halogen-free flame retardant in raw materials, good product flame-retardant effect, heat resistance, good properties, no pollution during combustion and low cost. The present invention has obvious economic benefit and environmental protection benefit, and is suitable for large-scale popularization and application.
Description
One, technical field:
The present invention relates to a kind of heat-shrinkable tube, be specifically related to a kind of halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties is made up of external wall material and inner wall material, and according to mass fraction, wherein 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; Inner wall material is made up of for 37 parts 53 parts of the second polyolefine hybrid resins, 19 parts of second auxiliary agents and fire retardant;
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 1-10 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 just to 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 kaolin 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties:
A kind of preparation method of halogen-free double-wall heat shrinkable tube of flame-retardant properties is characterized in that:
A. the preparation of external wall material:
Described external wall material is that 10 parts and ignition dope 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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;
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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 just to 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 kaolin 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).
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 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties is made up of external wall material and inner wall material, and according to mass fraction, wherein 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; Inner wall material is made up of for 37 parts 53 parts of the second polyolefine hybrid resins, 19 parts of second auxiliary agents and fire retardant;
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 1-10 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 just to 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 kaolin 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties,
A. the preparation of external wall material:
Described external wall material is that 10 parts and ignition dope 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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;
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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 just to 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 kaolin 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties is made up of external wall material and inner wall material, and according to mass fraction, wherein 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; Inner wall material is made up of for 37 parts 53 parts of the second polyolefine hybrid resins, 19 parts of second auxiliary agents and fire retardant;
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 1-10 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 just to 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 kaolin 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties is characterized in that:
A. the preparation of external wall material:
Described external wall material is that 10 parts and ignition dope 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;
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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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;
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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 just to 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 kaolin 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 3
A kind of halogen-free double-wall heat shrinkable tube of flame-retardant properties is made up of external wall material and inner wall material, and according to mass fraction, wherein 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; Inner wall material is made up of for 37 parts 53 parts of the second polyolefine hybrid resins, 19 parts of second auxiliary agents and fire retardant;
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 1-10 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 just to 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 kaolin 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties is characterized in that:
A. the preparation of external wall material:
Described external wall material is that 10 parts and ignition dope 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 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;
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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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;
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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 just to 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 kaolin 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 4
Embodiment 1,2 and 3 described product material smoke density performances meet ASTM E662, the hydrogen halide content performance meets IEC754-1, over-all properties reaches DL413-91 " 35kV and following power cable thermal contraction type accessory application technical qualification " ', and the cable accessory performance reaches GB11033-89 " voltage rating 26/35kV and following electric cable fitting basic fundamental require ".
Claims (4)
1. halogen-free double-wall heat shrinkable tube of flame-retardant properties, it is characterized in that: be made up of external wall material and inner wall material, according to mass fraction, described external wall material is made up of 53 parts of the first polyolefine hybrid resins, 10 parts and 37 parts fire retardants of first auxiliary agent; Described inner wall material is made up of 53 parts of the second polyolefine hybrid resins, 10 parts and 37 parts fire retardants of second auxiliary agent;
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 1-10 part, antioxidant 0.5-5 part, and 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 just to 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 kaolin 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 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. halogen-free double-wall heat shrinkable tube of flame-retardant properties 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. halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 9 parts of rosin, 4 parts of parts of antioxidant, and surplus is a DEDB.
4. the preparation method of a halogen-free double-wall heat shrinkable tube of flame-retardant properties is characterized in that:
A. the preparation of external wall material:
Described external wall material is that 10 parts and ignition dope 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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;
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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 halogen-free double-wall heat shrinkable tube of flame-retardant properties 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 just to 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 kaolin 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 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 |
|---|---|---|---|
| CN200910185053A CN101759907A (en) | 2009-10-28 | 2009-10-28 | Halogen-free double-wall heat shrinkable tube of flame-retardant properties and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910185053A CN101759907A (en) | 2009-10-28 | 2009-10-28 | Halogen-free double-wall heat shrinkable tube of flame-retardant properties and preparing method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558657A (en) * | 2010-12-27 | 2012-07-11 | 深圳市宏商材料科技股份有限公司 | Formula and production process of dual-layer thermal shrinkage-chilling shrinkage composite sleeve |
| CN112778620A (en) * | 2020-12-31 | 2021-05-11 | 长园电子（东莞）有限公司 | Heat-shrinkable sleeve and preparation method thereof |
-
2009
- 2009-10-28 CN CN200910185053A patent/CN101759907A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558657A (en) * | 2010-12-27 | 2012-07-11 | 深圳市宏商材料科技股份有限公司 | Formula and production process of dual-layer thermal shrinkage-chilling shrinkage composite sleeve |
| CN102558657B (en) * | 2010-12-27 | 2016-03-30 | 深圳市宏商材料科技股份有限公司 | A kind of formula of dual-layer thermal shrinkage-chilling shrinkage composite sleeve and production technique thereof |
| CN112778620A (en) * | 2020-12-31 | 2021-05-11 | 长园电子（东莞）有限公司 | Heat-shrinkable sleeve and preparation method thereof |
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