CN102093626B - Non-halogen fire resistant low-temperature shrinkable and heat-shrinkable pipe material and preparation method thereof - Google Patents

Non-halogen fire resistant low-temperature shrinkable and heat-shrinkable pipe material and preparation method thereof Download PDF

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CN102093626B
CN102093626B CN2010105954925A CN201010595492A CN102093626B CN 102093626 B CN102093626 B CN 102093626B CN 2010105954925 A CN2010105954925 A CN 2010105954925A CN 201010595492 A CN201010595492 A CN 201010595492A CN 102093626 B CN102093626 B CN 102093626B
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parts
temperature
antioxidant
shrinkable
preparation
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CN102093626A (en
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徐国永
严江威
陈晋阳
章于川
李爱民
陈恩军
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Anhui Zhongding Sealing Parts Co Ltd
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Anhui Zhongding Sealing Parts Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001Combinations of extrusion moulding with other shaping operations
    • B29C48/0022Combinations of extrusion moulding with other shaping operations combined with cutting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing

Abstract

The invention discloses a non-halogen fire resistant low-temperature shrinkable and heat-shrinkable pipe material and a preparation method thereof. The preparation method of the material comprises the following steps: using ethylene-vinylacetate copolymer as base material to add nitrogen and phosphorus series fire retardant, inorganic fire retardant and other additives, and performing mixing granulation, extrusion moulding, irradiation crosslinking, extension forming and other working procedures to obtain the finished product. By adopting the preparation method of the invention, the defects of the prior art such as high response temperature of heat-shrinkable pipe and poor fire resistance can be overcome; and the product has good performance, meets the requirements of environmental protection and is suitable for the cables and components in war industry, aviation and aerospace, civil high-end electrical and electronic equipment and the like.

Description

A kind of halogen-free flameproof low-temperature shrink thermal shrinkage pipe material and preparation method thereof
Technical field
The present invention relates to organic and inorganic functional high molecule material technical field, more specifically, is a kind of halogen-free flameproof low-temperature shrink thermal shrinkage pipe material and preparation method thereof.
Background technology
Functional high molecule material is that a coverage is extensive; the emerging frontier branch of science relevant to numerous subjects; relating to content and include chemical machine, inorganic chemistry, optics, electricity, structural chemistry, biological chemistry, electronics, numerous subjects such as medical science even, is a research field of Showed Very Brisk both at home and abroad at present.Why functional high molecule material can become one of important research focus of domestic and international material subject, topmost reason is that they have unique " function ", can be used for substituting other functional materialss, and improve or improve its performance, make it become the functional materials with brand-new character.Along with the in-depth to macromolecular structure and characteristic understanding, and the development of macromolecule synthesising technology, make macromolecular material obtain expected structure by molecular designing and performance becomes a reality.Shapememory polymer is exactly to utilize modern Polymer Physics theory and Polymer Synthesizing the commodity polymer material to be carried out a family macromolecule material of molecular combinations and modification acquisition, as the macromolecular materials such as polyethylene, polyisoprene, polyester, copolyesters, polymeric amide, copolyamide, urethane being carried out the adjustment of polymer design and molecular structure, make them under certain condition, be endowed certain shape (playing primary state), but when external conditions changed, it can correspondingly change shape and be fixed (deformation states).If outside atmosphere changes again with rule in a particular manner, just their reversible primary states that returned to.This specific character of macromolecular material is called the memory effect of material.The outside atmosphere of impelling them to complete above-mentioned circulation has the chemical factors such as the physical factors such as heat energy, luminous energy, electric energy, acoustic energy and phase transformation and potential of hydrogen, chelatropic reaction.
Heat-shrink tube is to develop the earliest and most widely used shape memory high molecule material.So-called heat-shrink tube refers to can occur the pipe of radial shrinkage when heating.Take the polyethylene heat-shrinkable tube as example, its making method is after first polymkeric substance and linking agent and other additive being prepared burden on request, make the tubing of requirement with suitable moulding process, then make the goods internal structure produce partial cross-linking by high-energy radiation, play memory tubing shape.Then the tubing with heating carries out radial swelling with mechanical process, differential pressure method or other method, and quick cooling curing.During application with this casing pipe sleeve needs coat or the object that connects on (cable that connects as wish), more than with well heater, the pipe that expands being heated to softening temperature (lower than the once shaped temperature), expansion pipe just is retracted to original shape, tightly is coated on by on the bag object.Heat-shrinkable tube is widely used, and is mainly used in insulation, sealing, the aspect such as anticorrosion, as the connection of high-tension bus-bar, cable, and end part seal, oil and gas pipeline anticorrosion etc.At present, all there are the defectives such as the thermal contraction response temperature is high, flame retardant properties is not good in these heat-shrink tubes.
Summary of the invention
The object of the invention is to provide halogen-free flameproof low-temperature shrink thermal shrinkage pipe material that a kind of response temperature is low, flame retardant properties is good and preparation method thereof.
The present invention realizes by following technique means: for ethylene-vinyl acetate copolymer have good flexibility, as rubber elasticity and the transparency and surface luster property is good, chemical stability is good, anti-aging and anti-ozone intensity is good, nontoxicity, with the characteristics that miscibility is good, painted and moulding processability is good of filler, take it as base-material, add fire retardant and other auxiliary agents, the halogen-free flameproof low-temperature shrink that a kind of response temperature is low, flame retardant properties is good thermal shrinkage pipe material is provided.
Halogen-free flameproof low-temperature shrink thermal shrinkage pipe material of the present invention is take ethylene-vinyl acetate copolymer as base-material, and interpolation nitrogen phosphorus flame retardant, inorganic combustion inhibitor and other auxiliary agents form, and wherein, contain by weight following component:
100 parts of ethylene-vinyl acetate copolymers (EVA);
30~60 parts of nitrogen phosphorus flame retardants;
15~40 parts of inorganic combustion inhibitors;
1~5 part of compatilizer;
0.5~1.5 part of composite antioxidant;
1~2.5 part of lubricant;
1~3 part of sensitizing agent;
2~8 parts of colour batches.
In heat shrinkable pipe material of the present invention, base-material is ethylene-vinyl acetate copolymer, and wherein, the melting index MI of described ethylene-vinyl acetate copolymer is 1.5~8g/10min, and vinyl acetate between to for plastic shared weight percent in multipolymer is 12~30%.
In heat shrinkable pipe material of the present invention, the nitrogen phosphorus flame retardant is selected from one or both the mixture in melmac coated ammonium polyphosphate, resol encapsulated red phosphorus, wherein, in described mixture, the weight ratio of resol encapsulated red phosphorus and melmac coated ammonium polyphosphate is 1: 1~5.
In heat shrinkable pipe material of the present invention, inorganic combustion inhibitor is selected from one or both the mixture in zinc borate, magnesium hydroxide, and wherein, the weight ratio of described mixture mesoboric acid zinc and magnesium hydroxide is 1: 1~4.
In heat shrinkable pipe material of the present invention, composite antioxidant is that the efficient auxiliary antioxidant allotment of hindered phenol primary antioxidant and thioether forms, wherein, the hindered phenol primary antioxidant comprises four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) and β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid (antioxidant 1076); The efficient auxiliary antioxidant of thioether comprises Tyox B (DLTP) and the two octadecyl esters (DSTP) of thio-2 acid; The weight ratio of hindered phenol primary antioxidant and the efficient auxiliary antioxidant of thioether is 1: 1~4.
State lubricant in heat shrinkable pipe material of the present invention and be selected from one or more in stearic acid, Zinic stearas, calcium stearate, polyethylene wax.
In heat shrinkable pipe material of the present invention, sensitizing agent is selected from one or more in Viscoat 295 (TMPTA), tetramethylol methane tetraacrylate (PETEA), triallyl isocyanate (TAIC).
Further, in order to guarantee the quality of heat shrinkable pipe material, the granularity of described resol encapsulated red phosphorus is greater than 300 orders.
Again further, in order to guarantee the quality of heat shrinkable pipe material, described magnesium hydroxide is for carrying out the ultrafine magnesium hydroxide powder end of surface active through coupling agent, wherein, described coupling agent is selected from one or more mixtures that mix with arbitrary proportion in hexadecanol and/or stearyl alcohol, oleic acid, stearic acid, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-methacryloxy Trimethoxy silane.
For guaranteeing quality product and satisfy environmental requirement, all not containing metal lead, cadmium, mercury and sexavalent chrome in described organic fire-retardant and inorganic combustion inhibitor.
The preparation method of halogen-free flameproof low-temperature shrink thermal shrinkage pipe material of the present invention comprises the steps:
(1) mixing granulator: get the raw materials ready by above-mentioned formula, the raw material of getting ready is added in homogenizer, mixed 4~10 minutes lower than 80 ℃ of lower high-speed stirring in temperature, then extrude under 110~160 ℃ through the screw mixing forcing machine, then through wire drawing, water-cooled, air-cooled and cut to draw and obtain bulk goods;
(2) extrusion moulding: above-mentioned bulk goods further is placed in twin screw extruder extrudes under 110~160 ℃ and obtain tubular material;
(3) cross-linking radiation: with above-mentioned tubular material rumbatron cross-linking radiation, wherein, irradiation dose is 4~8Mrad;
(4) expansion typing: the tubing after cross-linking radiation through cooling, the typing after 2~3 times of the temperature range intramedullary expansions of 110~180 ℃ of vacuum expansion device, is namely obtained finished product after cutting.
Preferably, halogen-free flameproof low-temperature shrink thermal shrinkage pipe material of the present invention, wherein contain following component by weight:
100 parts of ethylene-vinyl acetate copolymers (EVA);
25~40 parts of melmac coated ammonium polyphosphates;
8~20 parts of resol encapsulated red phosphorus;
5~10 parts of zinc borates;
12~40 parts, the ultrafine magnesium hydroxide powder end of surface activation process;
1~5 part of compatilizer;
0.5~1.5 part of composite antioxidant;
1~2.5 part of lubricant;
1~3 part of sensitizing agent;
2~8 parts of colour batches.
Prepare halogen-free flameproof low-temperature shrink thermal shrinkage pipe material according to formula of the present invention and preparation method, raw material is easy to get, method is simple and easy, cheap, saves cost and is suitable for suitability for industrialized production; The heat-shrinkable tube response temperature that products obtained therefrom has overcome prior art is the deficiency of higher (〉=120 ℃) generally, realized the fully contraction of heat-shrink tube under lesser temps (≤90 ℃), and its over-all properties is good, satisfy environmental requirement, be applicable to cable and components and parts equipment in military project, space flight and aviation, communication information, electric power, automobile and other industries and civilian high-end electronics, electrical equipment.
Embodiment
Below describe several preferred implementation of the present invention, but be not to limit the present invention.
Embodiment 1:
Get the raw materials ready according to following formula:
100 parts of ethylene-vinyl acetate copolymers (EVA);
30 parts of melmac coated ammonium polyphosphates;
10 parts of resol encapsulated red phosphorus;
8 parts of zinc borates;
Last 30 parts of the ultrafine magnesium hydroxide powder of surface activation process;
2 parts of compatilizers;
0.5 part of primary antioxidant pentaerythritol ester (antioxidant 1010);
The auxiliary antioxidant Tyox B
0.5 part;
(DLTP)
1 part of lubricant stearic acid calcium;
1.5 parts, lubricant polyethylene wax;
2 parts of sensitizing agent triallyl isocyanates (TAIC);
5 parts of black masterbatch,
Wherein, the melting index MI of described ethylene-vinyl acetate copolymer (EVA) is 3.6g/10min, and vinyl acetate between to for plastic shared weight percent in multipolymer is 14%, the granularity of described resol encapsulated red phosphorus is 1000 orders, surface active is carried out through vinyl three ('beta '-methoxy oxyethyl group) silane in described ultrafine magnesium hydroxide powder end, wherein, the consumption of described vinyl three ('beta '-methoxy oxyethyl group) silane is 1.5% of magnesium hydroxide weight; Above-mentioned raw materials is added in homogenizer, mixed 8 minutes lower than 80 ℃ of lower high-speed stirring in temperature, then mixture is extruded under 110~160 ℃ through the screw mixing forcing machine, then through wire drawing, water-cooled, air-cooled and cut to draw and obtain bulk goods;
Above-mentioned bulk goods further being placed in the twin screw extruder that mouthful mould and core are installed extrudes under 110~160 ℃ and obtains tubular material;
With above-mentioned tubular material rumbatron cross-linking radiation, wherein, irradiation dose is 5Mrad;
Tubing after cross-linking radiation through cooling, the typing after 2 times of the temperature range intramedullary expansions of 110~180 ℃ of vacuum expansion device, is namely obtained finished product after cutting.
Embodiment 2:
Get the raw materials ready according to following formula:
100 parts of ethylene-vinyl acetate copolymers (EVA);
35 parts of melmac coated ammonium polyphosphates;
8 parts of resol encapsulated red phosphorus;
8 parts of zinc borates;
Last 25 parts of the ultrafine magnesium hydroxide powder of surface activation process;
1.5 parts of compatilizers;
0.5 part of primary antioxidant pentaerythritol ester (antioxidant 1010);
The auxiliary antioxidant Tyox B
1 part;
(DLTP)
1.5 parts 1.5 parts, lubricant polyethylene wax;
2 parts of sensitizing agent triallyl isocyanates (TAIC);
4 parts of black masterbatch,
Wherein, the melting index MI of described ethylene-vinyl acetate copolymer (EVA) is 3.6g/10min, and vinyl acetate between to for plastic shared weight percent in multipolymer is 14%, the granularity of described resol encapsulated red phosphorus is 1000 orders, surface active is carried out through vinyl three ('beta '-methoxy oxyethyl group) silane in described ultrafine magnesium hydroxide powder end, wherein, the consumption of described vinyl three ('beta '-methoxy oxyethyl group) silane is 1.5% of magnesium hydroxide weight; Above-mentioned raw materials is added in homogenizer, mixed 8 minutes lower than 80 ℃ of lower high-speed stirring in temperature, then mixture is extruded under 110~160 ℃ through the screw mixing forcing machine, then through wire drawing, water-cooled, air-cooled and cut to draw and obtain bulk goods;
Above-mentioned bulk goods further being placed in the twin screw extruder that mouthful mould and core are installed extrudes at 110~160 times and obtains tubular material;
With above-mentioned tubular material rumbatron cross-linking radiation, wherein, irradiation dose is 5Mrad;
Tubing after cross-linking radiation through cooling, the typing after 2 times of 110~180 temperature range intramedullary expansions of vacuum expansion device, is namely obtained finished product after cutting.
Embodiment 3:
Get the raw materials ready according to following formula:
100 parts of ethylene-vinyl acetate copolymers (EVA);
35 parts of melmac coated ammonium polyphosphates;
15 parts of resol encapsulated red phosphorus;
5 parts of zinc borates;
Last 20 parts of the ultrafine magnesium hydroxide powder of surface activation process;
4 parts of compatilizers;
0.5 part of primary antioxidant pentaerythritol ester (antioxidant 1010);
The auxiliary antioxidant Tyox B
0.5 part;
(DLTP)
1.5 parts of lubricant stearic acid calcium;
1 part, lubricant polyethylene wax;
2 parts of sensitizing agent tetramethylol methane tetraacrylates (PETEA);
4 parts of black masterbatch,
Wherein, the melting index MI of described ethylene-vinyl acetate copolymer (EVA) is 1.5g/10min, and vinyl acetate between to for plastic shared weight percent in multipolymer is 15%, the granularity of described resol encapsulated red phosphorus is 1000 orders, surface active is carried out through vinyl three ('beta '-methoxy oxyethyl group) silane in described ultrafine magnesium hydroxide powder end, wherein, the consumption of described vinyl three ('beta '-methoxy oxyethyl group) silane is 1.5% of magnesium hydroxide weight; Above-mentioned raw materials is added in homogenizer, mixed 8 minutes lower than 80 ℃ of lower high-speed stirring in temperature, then mixture is extruded under 110~160 ℃ through the screw mixing forcing machine, then through wire drawing, water-cooled, air-cooled and cut to draw and obtain bulk goods;
Above-mentioned bulk goods further being placed in the twin screw extruder that mouthful mould and core are installed extrudes under 110~160 ℃ and obtains tubular material;
With above-mentioned tubular material rumbatron cross-linking radiation, wherein, irradiation dose is 6Mrad;
Tubing after cross-linking radiation through cooling, the typing after 2 times of the temperature range intramedullary expansions of 110~180 ℃ of vacuum expansion device, is namely obtained finished product after cutting.
Embodiment 4:
Get the raw materials ready according to following formula:
100 parts of ethylene-vinyl acetate copolymers (EVA);
40 parts of melmac coated ammonium polyphosphates;
15 parts of resol encapsulated red phosphorus;
10 parts of zinc borates;
Last 15 parts of the ultrafine magnesium hydroxide powder of surface activation process;
3 parts of compatilizers;
0.5 part of primary antioxidant pentaerythritol ester (antioxidant 1010);
The auxiliary antioxidant Tyox B
1 part;
(DLTP)
1 part 1 part of lubricant stearic acid calcium;
1 part, lubricant polyethylene wax;
2 parts of sensitizing agent tetramethylol methane tetraacrylates (PETEA);
5 parts of black masterbatch,
Wherein, the melting index MI of described ethylene-vinyl acetate copolymer (EVA) is 3.6g/10min, and vinyl acetate between to for plastic shared weight percent in multipolymer is 14%, the granularity of described resol encapsulated red phosphorus is 1000 orders, surface active is carried out through vinyl three ('beta '-methoxy oxyethyl group) silane in described ultrafine magnesium hydroxide powder end, wherein, the consumption of described vinyl three ('beta '-methoxy oxyethyl group) silane is 1.5% of magnesium hydroxide weight; Above-mentioned raw materials is added in homogenizer, mixed 8 minutes lower than 80 ℃ of lower high-speed stirring in temperature, then mixture is extruded under 110~160 ℃ through the screw mixing forcing machine, then through wire drawing, water-cooled, air-cooled and cut to draw and obtain bulk goods;
Above-mentioned bulk goods further being placed in the twin screw extruder that mouthful mould and core are installed extrudes under 110~160 ℃ and obtains tubular material;
With above-mentioned tubular material rumbatron cross-linking radiation, wherein, irradiation dose is 6Mrad;
Tubing after cross-linking radiation through cooling, the typing after 3 times of the temperature range intramedullary expansions of 110~180 ℃ of vacuum expansion device, is namely obtained finished product after cutting.
Embodiment 5:
Get the raw materials ready according to following formula:
100 parts of ethylene-vinyl acetate copolymers (EVA);
40 parts of melmac coated ammonium polyphosphates;
20 parts of resol encapsulated red phosphorus;
10 parts of zinc borates;
Last 12 parts of the ultrafine magnesium hydroxide powder of surface activation process;
3 parts of compatilizers;
0.5 part of primary antioxidant pentaerythritol ester (antioxidant 1010);
The auxiliary antioxidant Tyox B
1 part;
(DLTP)
0.5 part of lubricant stearic acid calcium;
1 part of polyethylene wax;
3 parts of sensitizing agent triallyl isocyanates (TAIC);
5 parts of black masterbatch,
Wherein, the melting index MI of described ethylene-vinyl acetate copolymer (EVA) is 3.6g/10min, and vinyl acetate between to for plastic shared weight percent in multipolymer is 14%, the granularity of described resol encapsulated red phosphorus is 1000 orders, surface active is carried out through vinyl three ('beta '-methoxy oxyethyl group) silane in described ultrafine magnesium hydroxide powder end, wherein, the consumption of described vinyl three ('beta '-methoxy oxyethyl group) silane is 1.5% of magnesium hydroxide weight; Above-mentioned raw materials is added in homogenizer, mixed 8 minutes lower than 80 ℃ of lower high-speed stirring in temperature, then mixture is extruded under 110~160 ℃ through the screw mixing forcing machine, then through wire drawing, water-cooled, air-cooled and cut to draw and obtain bulk goods;
Above-mentioned bulk goods further being placed in the twin screw extruder that mouthful mould and core are installed extrudes under 110~160 ℃ and obtains tubular material;
With above-mentioned tubular material rumbatron cross-linking radiation, wherein, irradiation dose is 6Mrad;
Tubing after cross-linking radiation through cooling, the typing after 2 times of the temperature range intramedullary expansions of 110~180 ℃ of vacuum expansion device, is namely obtained finished product after cutting.
Performance test
Get respectively above-mentioned 5 embodiment and prepare sample, according to ASTM D2671-98 (electronic apparatus with the testing standard of heat-shrink tube) standard, its performance is detected, flame retardant properties is tested according to UL1581 standard (electric wire flame retardant test).
Can the UL1581 standard testing only needs a bit of sample to test just can learn the fire-retardant requirement that reach VW-1.When carrying out combustion testing, only need with burning sample vertical place and three faces add metal sheet around, place some cottons in the sample bottom and test.Test summary: first laboratory sample kept vertical and use Bunsen burner ignition combustion 15 seconds, then Bunsen burner is moved apart 15 seconds, burning respectively 5 times.Judging criterion: 1, flame need be from putting out in 60 seconds; 2, more than burning part must not reach more than 25% of sample; 3, be placed on the bottom cotton incombustible.
Test result is as shown in table 1, table 2:
Table 1
Figure BSA00000390965000131
Table 2
Figure BSA00000390965000132
Figure BSA00000390965000141
Facts have proved, halogen-free flameproof low-temperature shrink thermal shrinkage pipe material of the present invention has good over-all properties, overcome the too high problem of heat-shrinkable tube response temperature of prior art, and raw material is easy to get, production method is simple and easy, with low cost, extensively satisfy the demand of cable and components and parts equipment in military project, space flight and aviation, communication information, electric power, automobile and other industries and civilian high-end electronics, electrical equipment.

Claims (2)

1. halogen-free flameproof low-temperature shrink thermal shrinkage pipe material, wherein contain following component by weight:
Figure FSB00001086353500011
The melting index MI of described ethylene-vinyl acetate copolymer is 1.5~8g/10min, and vinyl acetate between to for plastic shared weight percent in multipolymer is 12~30%;
Described composite antioxidant is that the efficient auxiliary antioxidant allotment of hindered phenol primary antioxidant and thioether forms, wherein, the hindered phenol primary antioxidant comprises four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) positive octadecyl ester of propionic acid; The efficient auxiliary antioxidant of thioether comprises Tyox B and the two octadecyl esters of thio-2 acid; The weight ratio of hindered phenol primary antioxidant and the efficient auxiliary antioxidant of thioether is 1: 1~4;
Described lubricant is selected from one or more in stearic acid, Zinic stearas, calcium stearate, polyethylene wax;
Described sensitizing agent is selected from one or more in Viscoat 295, tetramethylol methane tetraacrylate, triallyl isocyanate;
The granularity of described resol encapsulated red phosphorus is greater than 300 orders;
Described magnesium hydroxide is for carrying out the ultrafine magnesium hydroxide powder end of surface active through coupling agent, wherein, described coupling agent is selected from one or more mixtures that mix with arbitrary proportion in hexadecanol and/or stearyl alcohol, oleic acid, stearic acid, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-methacryloxy Trimethoxy silane.
2. a method for preparing halogen-free flameproof low-temperature shrink thermal shrinkage pipe material claimed in claim 1, is characterized in that comprising the steps:
(1) mixing granulator: get the raw materials ready by proportioning claimed in claim 1, the raw material of getting ready is added in homogenizer, mixed 4~10 minutes lower than 80 ℃ of lower high-speed stirring in temperature, then extrude under 110~160 ℃ through the screw mixing forcing machine, then through wire drawing, water-cooled, air-cooled and cut to draw and obtain bulk goods;
(2) extrusion moulding: above-mentioned bulk goods further is placed in twin screw extruder extrudes under 110~160 ℃ and obtain tubular material;
(3) cross-linking radiation: with above-mentioned tubular material rumbatron cross-linking radiation, wherein, irradiation dose is 4~8Mrad;
(4) expansion typing: the tubing after cross-linking radiation through cooling, the typing after 2~3 times of the temperature range intramedullary expansions of 110~180 ℃ of vacuum expansion device, is namely obtained finished product after cutting.
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