CN101759902A - High-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube and preparation method thereof - Google Patents

Abstract

The invention relates to a heat-shrinkable tube, in particular to a high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube and a preparation method thereof; the high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube is composed of a wall, the wall material is composed of 80 parts of polyolefin mixed resin, 10 parts of single-wall heat-shrinkable tube, 20 parts of anti-inflaming agents and 10 parts of auxiliary anti-inflaming agents by mass percentage; the preparation method comprises the following steps: the preparation of the inner wall material of the single-wall heat-shrinkable tube, extrusion, radiation and expansion molding; compared with the traditional heat-shrinkable tube, the heat-shrinkable tube has the technical characteristics that in the raw materials, the halogen-free anti-inflaming agents are adapted, the anti-inflaming effect of the product is good, the tube is high temperature resistance, and the tube has no pollution even if the tube is burned, the cost is reduced, the heat-shrinkable tube is suitable for working at a 35-kV high-voltage state, has remarkable economic and environmental-protection benefits and is suitable for large-scale popularization and application.

Description

High-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube and preparation method thereof

One, technical field:

The present invention relates to a kind of heat-shrinkable tube, be specifically related to a kind of high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube and preparation method thereof.

Two, background technology

The thermal contraction single-walled pipe of Xiao Shouing in the market, 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 high-pressure halogen-free anti-inflaming single-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 high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube is made up of the wall material, and according to mass fraction, its mesospore material is that 10 parts, 20 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 80 parts of polyolefine hybrid resins, auxiliary agent;

By mass percentage: described polyolefine hybrid resin is the polyolefine hybrid resin that 1～30%EVA630,1～20%EVA421,20～50%EVA283 and four kinds of polyolefine material melt blendings of 10～30%EVA220 make;

Described auxiliary agent is made up of paraffin, antioxidant, anti copper agent, processing stabilizers and sensitization crosslinking coagent, antioxidant four (β-(3 wherein, the 5-di-tert-butyl-hydroxy phenyl) tetramethylolmethane 1-3 part propionic acid), anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part, processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part, sensitization crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part, surplus is a paraffin;

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 high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube is characterized in that:

A. the preparation of wall material:

Described wall material is that 10 parts, 20 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 80 parts of polyolefine hybrid resins, auxiliary agent; The 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; 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 wall material of described high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube then through the tablets press granulation, standby;

B. extrude:

The wall material of steps A preparation is added in the forcing machine, and through extrusion moulding from extruder head behind the fuselage heating and melting, through the tank cooling, wind-force dries up then, behind the surperficial lettering, receives on all rotating disks through tractor;

C. irradiation:

All rotating disks are put on the pay off rack,, introduce in the radiation chamber through the adjustable tension bracket of overtension, the present invention adopts irradiation device for electronic accelerator, irradiation dose is 12Mrad, to the single-walled pipe work in-process of making circulate irradiation and cooling, is 30～60 circles at the number of times of exposure cell's internal recycle irradiation.Passing through the wire coiler rolling on all rotating disks;

D. expansion:

The high-pressure halogen-free anti-inflaming single-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 single-walled pipe 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 high-pressure halogen-free anti-inflaming single-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 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, being suitable for the 35kV high pressure conditions uses down.

3, 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.

4, 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.

5, 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 high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube is made up of the wall material, and according to mass fraction, its mesospore material is that 10 parts, 20 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 80 parts of polyolefine hybrid resins, auxiliary agent; Auxiliary flame retardant is aluminium hydroxide or magnesium hydroxide;

By mass percentage: described polyolefine hybrid resin is the polyolefine hybrid resin that 1～30%EVA630,1～20%EVA421,20～50%EVA283 and four kinds of polyolefine material melt blendings of 10～30%EVA220 make;

Described auxiliary agent is made up of paraffin, antioxidant, anti copper agent, processing stabilizers and sensitization crosslinking coagent, antioxidant four (β-(3 wherein, the 5-di-tert-butyl-hydroxy phenyl) tetramethylolmethane 1-3 part propionic acid), anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part, processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part, sensitization crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part, surplus is a paraffin;

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 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 high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube,

A. the preparation of wall material:

Described wall material is that 10 parts, 20 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 80 parts of polyolefine hybrid resins, auxiliary agent; The 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; 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 wall material of described high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube then through the tablets press granulation, standby;

B. extrude:

The wall material of steps A preparation is added in the forcing machine, and through extrusion moulding from extruder head behind the fuselage heating and melting, through the tank cooling, wind-force dries up then, behind the surperficial lettering, receives on all rotating disks through tractor;

C. irradiation:

All rotating disks are put on the pay off rack,, introduce in the radiation chamber through the adjustable tension bracket of overtension, the present invention adopts irradiation device for electronic accelerator, irradiation dose is 12Mrad, to the single-walled pipe work in-process of making circulate irradiation and cooling, is 30～60 circles at the number of times of exposure cell's internal recycle irradiation.Passing through the wire coiler rolling on all rotating disks;

D. expansion:

The high-pressure halogen-free anti-inflaming single-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 single-walled pipe 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 high-pressure halogen-free anti-inflaming single-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 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 high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube is made up of the wall material, and according to mass fraction, its mesospore material is that 10 parts, 20 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 80 parts of polyolefine hybrid resins, auxiliary agent; The olefin 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 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;

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 high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube is characterized in that:

A. the preparation of wall material:

Described wall material is that 10 parts and ignition dope are formed for 37 parts by 53 parts of polyolefine hybrid resins, auxiliary agent; The polyolefine hybrid resin that the 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; 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 wall material of described high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube then through the tablets press granulation, standby;

B. extrude:

The wall material of steps A preparation is added in the forcing machine, and through extrusion moulding from extruder head behind the fuselage heating and melting, through the tank cooling, wind-force dries up then, behind the surperficial lettering, receives on all rotating disks through tractor;

C. irradiation:

All rotating disks are put on the pay off rack,, introduce in the radiation chamber through the adjustable tension bracket of overtension, the present invention adopts irradiation device for electronic accelerator, irradiation dose is 12Mrad, to the single-walled pipe work in-process of making circulate irradiation and cooling, is 30～60 circles at the number of times of exposure cell's internal recycle irradiation.Passing through the wire coiler rolling on all rotating disks;

D. expansion:

The high-pressure halogen-free anti-inflaming single-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 single-walled pipe 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 high-pressure halogen-free anti-inflaming single-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 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 high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube is made up of the wall material, and according to mass fraction, its mesospore material is that 10 parts, 20 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 80 parts of polyolefine hybrid resins, auxiliary agent;

By mass percentage: described polyolefine hybrid resin is the polyolefine hybrid resin that 30%EVA630,20%EVA421,40%EVA283 and four kinds of polyolefine material melt blendings of 10%EVA220 make;

Described auxiliary agent is made up of paraffin, antioxidant, anti copper agent, processing stabilizers and sensitization crosslinking coagent, antioxidant four (β-(3 wherein, the 5-di-tert-butyl-hydroxy phenyl) tetramethylolmethane 1-3 part propionic acid), anti copper agent MDA-1024 (hydroxy-terminated polybutadienes vinyl cyanide fluid rubber) 0.5-1 part, processing stabilizers rare earth composite stabilizer (REC-LS-D or REC-LS-F) 0.02-2 part; Smoke suppressor zinc borate 2-4 part, sensitization crosslinking coagent TMP (TriMethylolPropane(TMP)) 1-2 part, surplus is a paraffin;

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 high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube is characterized in that:

A. the preparation of wall material:

Described wall material is that 10 parts, 20 parts of fire retardants and auxiliary flame retardant are formed for 10 parts by 80 parts of polyolefine hybrid resins, auxiliary agent; The polyolefine hybrid resin that the 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; 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 wall material of described high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube then through the tablets press granulation, standby;

B. extrude:

The wall material of steps A preparation is added in the forcing machine, and through extrusion moulding from extruder head behind the fuselage heating and melting, through the tank cooling, wind-force dries up then, behind the surperficial lettering, receives on all rotating disks through tractor;

C. irradiation:

All rotating disks are put on the pay off rack,, introduce in the radiation chamber through the adjustable tension bracket of overtension, the present invention adopts irradiation device for electronic accelerator, irradiation dose is 12Mrad, to the single-walled pipe work in-process of making circulate irradiation and cooling, is 30～60 circles at the number of times of exposure cell's internal recycle irradiation.Passing through the wire coiler rolling on all rotating disks;

D. expansion:

The high-pressure halogen-free anti-inflaming single-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 single-walled pipe 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 high-pressure halogen-free anti-inflaming single-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 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).

Claims (4)

1. high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube, it is characterized in that: be made up of the wall material, according to mass fraction, described wall material is made up of for 10 parts 80 parts of polyolefine hybrid resins, 10 parts of auxiliary agents, 20 parts of fire retardants and auxiliary flame retardant; Auxiliary flame retardant is magnesium hydroxide or aluminium hydroxide;

Described polyolefine hybrid resin is the polyolefine hybrid resin that 1～30%EVA630,1～20%EVA421,20～50%EVA283 and four kinds of polyolefine material melt blendings of 10～30%EVA220 make by mass percentage; Described 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;

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. high-pressure halogen-free anti-inflaming single-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. high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube according to claim 1 and 2 is characterized in that: described 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 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.

4. the preparation method of a high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube is characterized in that:

A. the preparation of wall material:

Described wall material is that 10 parts and ignition dope are formed for 37 parts by 53 parts of polyolefine hybrid resins, auxiliary agent; The 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; 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 wall material of described high-pressure halogen-free anti-inflaming single-wall heat-shrinkable tube then through the tablets press granulation, standby;

B. extrude:

The wall material of steps A preparation is added in the forcing machine, and through extrusion moulding from extruder head behind the fuselage heating and melting, through the tank cooling, wind-force dries up then, behind the surperficial lettering, receives on all rotating disks through tractor;

C. irradiation:

All rotating disks are put on the pay off rack,, introduce in the radiation chamber through the adjustable tension bracket of overtension, the present invention adopts irradiation device for electronic accelerator, irradiation dose is 12Mrad, to the single-walled pipe work in-process of making circulate irradiation and cooling, is 30～60 circles at the number of times of exposure cell's internal recycle irradiation.Passing through the wire coiler rolling on all rotating disks;

D. expansion:

The high-pressure halogen-free anti-inflaming single-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 single-walled pipe 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 high-pressure halogen-free anti-inflaming single-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 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.