CN100528954C - Low-smoke halide-free fireproof polyolefine material and its preparation method and application - Google Patents

Low-smoke halide-free fireproof polyolefine material and its preparation method and application Download PDF

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CN100528954C
CN100528954C CNB2006100287505A CN200610028750A CN100528954C CN 100528954 C CN100528954 C CN 100528954C CN B2006100287505 A CNB2006100287505 A CN B2006100287505A CN 200610028750 A CN200610028750 A CN 200610028750A CN 100528954 C CN100528954 C CN 100528954C
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low
ethylene
vinyl acetate
polyolefine
free
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CNB2006100287505A
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CN101100537A (en
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张聪
谢雷东
陈西良
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中国科学院上海应用物理研究所
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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
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders

Abstract

A low-smoke and non-halogen poly-olefine material with radiant graft maleic anhydride vinyl-vinyl acetate multi-polymer as compatilizer is prepared by dissolving maleic anhydride 1-5 proportion into acetone, mixing with vinyl-vinyl acetate multi-polymer 100 proportion, volatilizing for acetone, granulating in double-screw extruder, and electronic-ray or gamma-ray radiating by electronic accelerator with 5-30KGy. The compatilizer graft rate is greater than or equal to 1%, it has better poly-olefine material performance, more white fire retardant and no need for anti-smoke agent. It can be used to make poly-olefine thermal shrinkage pipe with VW-1 vertical burning performance according to UL224 standard.

Description

Low-smoke halide-free fireproof composite polyolefine material and its production and application
Technical field
The present invention relates to a kind of low-smoke halide-free fireproof composite polyolefine material and its production and application.
Background technology
What European Union in 2002 worked out is " the electronic waste facture " of content with two instructions, one of them instruction for " about in electronic and electrical equipment, banning use of some objectionable impurities instruction " (ROHS).The ROHS command request, the Electrical and Electronic product that on July 1st, 2006 was thrown in European Union market later on must not contain 6 kinds of objectionable impuritiess such as lead, mercury, cadmium, sexavalent chrome, Polybrominated biphenyl and Poly Brominated Diphenyl Ethers.2004 beginning of the years, the Ministry of Information industry is according to relevant rules such as " promotion law on cleaner production ", " prevention and control of environmental pollution by solid wastes methods ", work out " electronics and IT products prevention and cure of pollution management method " (being called for short " way "), " way " regulation, on July 1st, 2006 must not be contained 6 kinds of objectionable impuritiess such as lead, mercury, cadmium, sexavalent chrome, Polybrominated biphenyl and Poly Brominated Diphenyl Ethers in the electronics and IT products, stipulated that simultaneously the electric equipment products that enters China must not contain above 6 kinds of objectionable impuritiess.Therefore development is present focus both domestic and external with the low-smoke halide-free fireproof composite polyolefine material that exploitation does not contain 6 kinds of objectionable impuritiess stipulating in the instruction.
The low-smoke halide-free fireproof composite polyolefine material of present domestic development adopts the ethylene-vinyl acetate copolymer (EVA-g-MAH) of commercially available or fusion-grafting maleic anhydride as compatilizer mostly, this compatilizer percentage of grafting low (≤1%), the graft materials prescription is complicated, the difficult control of graft reaction and quality in the production process, byproduct is many, the materials purification complexity (Yin Jun etc. the grafting modification of ethylene-vinyl acetate copolymer. Chinese plastics, 2001,15 (5): 23-29).Addition is big in the halogen-free low-smoke flame retardant material prescription, the comprehensive cost height.For example the patent No. is 03116976.7 the disclosed a kind of low-smoke halide-free fireproof composite polyolefine material that is used to prepare cable of Chinese patent, and application number is 02111063.8 the disclosed a kind of low smoke halogen-free fire retardant polyolefin cable material of Chinese patent application.
On the other hand, because heat-shrinkable tube is almost blank pipe test during the performance test of VW-1 vertical combustion in carrying out the UL224 standard, and be that metallic conductor coats non-halogen flame-retardant cable outward during the performance test of electric wire vertical combustion, so the heat-shrinkable tube flame retardant properties requires than high many of electric wire flame retardant properties.In other words, will be for the fire-retardant performance requriements that waits of the polyolefine material that is used to prepare heat-shrinkable tube far above the polyolefine material that is used to prepare electric wire.For making the polyolefine collapsible tube by VW-1 vertical combustion performance test in the UL224 standard, existing low-smoke halide-free fireproof composite polyolefine material adopts the inorganic phosphorus of flame retardant effect excellence usually---and red phosphorus (MRP) is as main fire retardant (being disclosed a kind of radiation-crosslinked low smoke no halide flame retaining low temperature shrinkage polyolefine material contracting with heat that is suitable for preparing collapsible tube in 00115353.6 the Chinese patent as the applicant's the patent No.), yet this fire retardant amount of being fuming is big, reach low cigarette and must add a large amount of smoke suppressors, and can only produce black and red two kinds of bittern-free flame-proof materials, limited the use range of material.The same with electric wire, for ease of distinguishing and identification, the collapsible tube of different occasions and purposes needs different colours to come mark.Yet in the market still by VW-1 vertical combustion performance test in the UL224 standard, except the low smoke halogen-free flame-retardant polyolefin collapsible tube of black and red other color.Trace it to its cause and to be: if do not use coloured flame-retardant agent red phosphorus, the white fire retardant effect that has other now is well below red phosphorus (MRP), so for reaching above-mentioned flame-retardant standard, then need add a large amount of white fire retardants, yet existing EVA-g-MAH as compatilizer, its performance fails to make polyolefin substrate and fire retardant fully compatible, and the various performances of the polyolefine material that makes are more impossible to meet above-mentioned standard.
Summary of the invention
Purpose of the present invention promptly addresses the above problem, and provides a kind of performance better low-smoke halogen-free polyolefin material.
For addressing the above problem, the present invention is mainly by preparing new EVA-g-MAH as compatilizer, the percentage of grafting height of this EVA-g-MAH, controlled, and side reaction such as crosslinked is little, can improve the consistency between base material and the fire retardant thus greatly, thereby improves the performance of polyolefine material.
Low-smoke halide-free fireproof composite polyolefine material of the present invention, it comprises the polyolefin substrate that contains ethylene-vinyl acetate copolymer (EVA) at least, halogen-free flame retardants, ethylene-vinyl acetate copolymer and additive as the grafted maleic anhydride of compatilizer, it is characterized in that this ethylene-vinyl acetate copolymer as the grafted maleic anhydride of compatilizer is the ethylene-vinyl acetate copolymer of radiation grafting maleic anhydride, it can be made by following method: 1~5 part maleic anhydride is dissolved in the acetone, after 100 parts of ethylene-vinyl acetate copolymers mix, Deng acetone volatilization back granulation in twin screw extruder, carry out radiation at rumbatron electron rays or gamma-rays again, radiation dose is 5~30KGy.
In fact, low-smoke halogen-free polyolefin material of the present invention is except replacing above-mentioned compatilizer the compatilizer in the existing polyolefine material, and all the other components can same prior art, as disclosed product in the above-mentioned document.
Wherein, said polyolefin substrate can be any existing polyolefin substrate that contains EVA at least, as ethylene-vinyl acetate copolymer, or one or more blended mixtures in ethylene-vinyl acetate copolymer and other polyolefine, for example polyethylene, terpolymer EP rubber and the ethylene-octene copolymer (POE); Melting index MI=2~the 6g/min of preferred ethylene-vinyl acetate copolymer (EVA), wherein vinyl acetate content=14~40%.
And halogen-free flame retardants can be organophosphorus, as ammonium polyphosphate (APP), organophosphorus-nitrogen series, as trimeric cyanamide, and organic fire-retardant such as tetramethylolmethane; Also can be inorganic combustion inhibitor, as borates such as metal hydroxidess such as aluminium hydroxide, magnesium hydroxide and zinc borates; Be generally the increase flame retardant effect, and reduce untoward reaction and select above-mentioned more than one compound flame retardant for use.
Certainly, the present invention also can select additive commonly used in the polyolefine material for use, as oxidation inhibitor, lubricant, crosslinking coagent and Halogen Masterbatch etc.
Source of radiation of the present invention is rumbatron electron rays or gamma-rays, and preferred radiation dose is 15~25KGy.
The radiation graft process for preparing compatilizer EVA-g-MAH of the present invention is the solid phase method for radio-grafting that the present invention initiates, be convenient to suitability for industrialized production, it is processed in forcing machine just grafted monomer and mixed with polymers, do not produce graft reaction, so prescription is simple, complete processing is also simple, percentage of grafting factor affecting of raying source dosage (radiation dose is more accurate unit).Therefore the percentage of grafting of the EVA-g-MAH that makes is controlled, side reaction is little (used radiation dose can not cause side reactions such as crosslinked usually because of the present invention), its percentage of grafting higher (〉=1%).Certainly, select for use low dose of maleic anhydride and little radiation dose also can prepare percentage of grafting less than 1% product, but compare with the existing identical EVA-g-MAH of percentage of grafting, its side reaction is little, so graft product purity height.The percentage of grafting of the above-mentioned EVA-g-MAH that the present invention selects for use generally between 0.4~2%, preferably 1~1.5%.
Each component in the low-smoke halogen-free polyolefin material of the present invention can be with reference to prior art, as above-mentioned patent documentation as the consumption of polyolefin substrate, fire retardant, oxidation inhibitor, lubricant, crosslinking coagent and Halogen Masterbatch etc.Because the consumption of fire retardant is excessive in the prior art, can influence the consistency of itself and polyolefin substrate, further can influence performances such as the outward appearance smooth finish of polyolefine material, fire-retardant, mechanics.So if the consumption of fire retardant is similar with prior art, but then the consumption several times of the above-mentioned compatilizer of the present invention ground reduces, as is 3~5% of polyolefin substrate weight, can guarantee that the finished product performance is suitable, can reduce the comprehensive cost of material thus; On the other hand, when the same prior art of the consumption of compatilizer, as be 10~15% of polyolefin substrate weight, then can increase the consumption of fire retardant, thereby make polyolefine material have better flame retardant properties.Therefore, compatilizer consumption of the present invention can be 5~15% of polyolefin substrate weight.
Because in the present invention, the consumption of fire retardant can strengthen, and this makes and only prepares and can become possibility by the low-smoke halogen-free polyolefin collapsible tube of VW-1 vertical combustion performance test in the UL224 standard with white fire retardant.Particularly, in the present invention, can not use the strong red phosphorus of flame retardant effect, simultaneously need not use smoke suppressor yet, and adopt the white or the colourless fire retardant of multiple big consumption to substitute, low-smoke halogen-free polyolefin that makes thus and collapsible tube are white, or the Masterbatch that adds different colours as required makes the colored low-smoke halogen-free polyolefin material and the collapsible tube of different colours.
In a preferred embodiment of the present invention, this polyolefine material comprises following components by part by weight:
Compatilizer: 5~15 parts of the ethylene-vinyl acetate copolymers of above-mentioned radiation grafting maleic anhydride;
Polyolefin substrate: 5~15 parts of 70~90 parts of ethylene-vinyl acetate copolymers and terpolymer EP rubbers (EPDM);
Oxidation inhibitor: 0.5~4 part of composite antioxidant, wherein Hinered phenols antioxidant: thioesters kind antioxidant (w/w)=0.5: 1~3;
Halogen-free flame retardants: organic fire-retardant: 8~15 parts of 20~40 parts of ammonium polyphosphates, 10~20 parts of tetramethylolmethanes and trimeric cyanamides, and inorganic combustion inhibitor: Al (OH) 3With Mg (OH) 240~80 parts of mixtures, 10~20 parts of zinc borates;
Lubricant: 1~3 part of divalence metallic soap of stearic acid salt, 1~3 part of polyethylene wax;
Crosslinking coagent: 0~3 part of polyfunctional monomer (methyl) acrylate or triallyl isocyanurate (TAIC);
0~5 part of Halogen Masterbatch.
Wherein, described Hinered phenols antioxidant is selected from 1,3,5-trimethylammonium-2,4,6-three (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (antioxidant 330), 1,1,3-three (2-methyl-4-hydroxyl-5-t-butyl-phenyl) butane (antioxidant CA), pentaerythritol ester (antioxidant 1010) and β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid octadecyl ester (antioxidant 1076); Described thioesters kind antioxidant is selected from Tyox B (anti-oxidant DLTP), thio-2 acid (octadecyl ester) (oxidation inhibitor DSTP) and thio-2 acid two (14 ester) (oxidation inhibitor DMTDP); The acrylate cross linked auxiliary agent of described polyfunctional monomer (methyl) is selected from Viscoat 295, three-TRIM and pentaerythritol triacrylate; Described Halogen Masterbatch is the pigment of 6 kinds of objectionable impuritiess such as lead, mercury, cadmium, sexavalent chrome, Polybrominated biphenyl and Poly Brominated Diphenyl Ethers of not containing the ROHS command request, with the conversion shades of colour.
Another object of the present invention provides the preparation method of above-mentioned low-smoke halide-free fireproof composite polyolefine material.
Preparation method of the present invention comprises and adopts the existing machinery production technology with above-mentioned each component blend, extrudes granulation and make above-mentioned low-smoke halide-free fireproof composite polyolefine material.
When the colored low-smoke halide-free fireproof composite polyolefine material of high flame retardant of preparation preferred embodiment of the present invention, this preparation method preferably comprises the following steps: oxidation inhibitor, organic fire-retardant, lubricant divalence metallic soap of stearic acid salt, Halogen Masterbatch, compatilizer and polyolefin substrate behind high speed kneader thorough mixing, extrude air-cooled granulation at twin screw extruder; This particle and inorganic combustion inhibitor, lubricant polyethylene wax and crosslinking coagent further behind high speed kneader thorough mixing, are extruded at twin screw extruder again, and air-cooled granulation gets the colored low-smoke halide-free fireproof composite polyolefine material of the present invention.
Because flame retardant amount is bigger in the preferred embodiment of the present invention, thus adopt reinforced method of two steps, when having avoided once adding dispersion inhomogeneous, the problem of processing difficulties is convenient to suitability for industrialized production, the material property of preparation meets the article of manufacture requirement.
Low-smoke halide-free fireproof composite polyolefine material of the present invention can be used for preparing can be by versicolor the low smoke halogen-free flame-retardant polyolefin electric wire, particularly heat-shrinkable tube of VW-1 vertical combustion performance test.It has not only solved can only produce black and red halogen-free anti-flaming polyolefin heat-shrinkable tube in the past, simultaneously the heat-shrinkable tube of Sheng Chaning be real meaning low-smoke non-halogen flame-retardant, meet the heat-shrinkage material of the environment-friendly type of the ROHS of European Union instruction.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
The preparation of embodiment 1EVA-g-MAH
With maleic anhydride 1kg be dissolved in the 2kg acetone with 100kg ethylene-vinyl acetate copolymer (EVA) after high-speed mixer mixes, Deng the granulation in 100~150 ℃ of temperature ranges of twin screw extruder of acetone volatilization back, radiation 15KGy gets the EVA-g-MAH of percentage of grafting 0.4% in the rumbatron electron rays again.
The preparation of embodiment 2EVA-g-MAH
With maleic anhydride 3kg be dissolved in the 6kg acetone with 100kg ethylene-vinyl acetate copolymer (EVA) after high-speed mixer mixes, wait acetone volatilization back granulation in 100~150 ℃ of temperature ranges of twin screw extruder, exist again 60Radiation 20KGy gets the EVA-g-MAH of percentage of grafting 1% in the gamma-rays of Co source.
The preparation of embodiment 3EVA-g-MAH
With maleic anhydride 5kg be dissolved in the 10kg acetone with 100kg ethylene-vinyl acetate copolymer (EVA) after high-speed mixer mixes, wait acetone volatilization back granulation in 100~150 ℃ of temperature ranges of twin screw extruder, exist again 60Radiation 25KGy gets the EVA-g-MAH of percentage of grafting 1.5% in the gamma-rays of Co source.
The preparation of embodiment 4EVA-g-MAH
With maleic anhydride 2kg be dissolved in the 4kg acetone with 100kg ethylene-vinyl acetate copolymer (EVA) after high-speed mixer mixes, Deng the granulation in 100~150 ℃ of temperature ranges of twin screw extruder of acetone volatilization back, radiation 5KGy gets the EVA-g-MAH of percentage of grafting 0.4% in the rumbatron electron rays again.
The preparation of embodiment 5EVA-g-MAH
With maleic anhydride 4kg be dissolved in the 8kg acetone with 100kg ethylene-vinyl acetate copolymer (EVA) after high-speed mixer mixes, Deng the granulation in 100~150 ℃ of temperature ranges of twin screw extruder of acetone volatilization back, radiation 30KGy gets the EVA-g-MAH of percentage of grafting 1.3% in the rumbatron electron rays again.
The preparation of embodiment 6 low-smoke halide-free fireproof composite polyolefine materials
With the EVA-g-MAH 15kg of the percentage of grafting 1.5% of the foregoing description 3 preparation and commercially available following material composite antioxidant [pentaerythritol ester: thio-2 acid (octadecyl ester)=1: 2 (w/w)] 3kg, ammonium polyphosphate (APP) 40kg, tetramethylolmethane 20kg, trimeric cyanamide 15kg, lubricant divalence metallic soap of stearic acid salt 2.5kg, blue Masterbatch 3kg, ethylene-vinyl acetate copolymer (EVA) 75kg, the terpolymer EP rubber of 10kg (EPDM) twin screw extruder in 100~150 ℃ of intervals behind 500 liters high speed kneader thorough mixing is extruded, air-cooled granulation obtains master batch.Again with master batch and commercially available following substance A l (OH) 3With Mg (OH) 2Mixture 72kg, zinc borate 18kg, lubricant polyethylene wax 2.5kg, crosslinking coagent three-TRIM (TMPTMA) or triallyl isocyanurate (TAIC) 2kg behind 500 liters high speed kneader thorough mixing again the twin screw extruder in 100~150 ℃ of intervals extrude air-cooled granulation De Lanse low-smoke halide-free fireproof composite polyolefine material.
The preparation of embodiment 7 low-smoke halide-free fireproof composite polyolefine materials
With EVA-g-MAH 5kg of the foregoing description 3 and commercially available following material composite antioxidant [pentaerythritol ester: thio-2 acid (octadecyl ester)=1: 2 (w/w)] 2kg, ammonium polyphosphate (APP) 20kg, tetramethylolmethane 10kg, trimeric cyanamide 8kg, lubricant divalence metallic soap of stearic acid salt 1.5kg, green master batch 2kg, ethylene-vinyl acetate copolymer (EVA) 85kg, the terpolymer EP rubber of 10kg (EPDM) twin screw extruder in 100~150 ℃ of intervals behind 500 liters high speed kneader thorough mixing is extruded, air-cooled granulation obtains master batch.With this master batch and commercially available following substance A l (OH) 3With Mg (OH) 2Mixture 58kg, zinc borate 12kg, lubricant polyethylene wax 1.5kg, crosslinking coagent three-TRIM (TMPTMA) or triallyl isocyanurate (TAIC) 2kg behind 500 liters high speed kneader thorough mixing again the twin screw extruder in 100~150 ℃ of intervals extrude, air-cooled granulation gets green low-smoke halide-free fireproof composite polyolefine material.
The preparation of embodiment 8 low-smoke halide-free fireproof composite polyolefine materials
With EVA-g-MAH 10kg of the foregoing description 1 and commercially available following material composite antioxidant (component is the same) 2kg, ammonium polyphosphate (APP) 20kg, tetramethylolmethane 10kg, trimeric cyanamide 8kg, lubricant divalence metallic soap of stearic acid salt 1.5kg, yellow masterbatch 2kg, ethylene-vinyl acetate copolymer (EVA) 85kg, the polyethylene of 10kg (LDPE) twin screw extruder in 100~160 ℃ of intervals behind 500 liters high speed kneader thorough mixing is extruded, and air-cooled granulation obtains master batch.With this master batch and commercially available following substance A l (OH) 3With Mg (OH) 2Mixture 58kg, zinc borate 12kg, lubricant polyethylene wax 1.5kg, crosslinking coagent three-TRIM (TMPTMA) or triallyl isocyanurate (TAIC) 2kg behind 500 liters high speed kneader thorough mixing again the twin screw extruder in 100~150 ℃ of intervals extrude, air-cooled granulation gets yellow low-smoke halide-free fireproof composite polyolefine material.
Except that EVA-g-MAH, surplus raw material is conventional commercially available prod in the foregoing description.
Application Example 1
By existing technology (Zhang Cong: the development of radiation crosslinking 150 ℃ flame-retardant polyolefin heat-shrinkable material, China's plastics 2001, Vol NO.1:44-45) low-smoke halide-free fireproof composite polyolefine material of embodiment 6 being produced blue look low smoke halogen-free flame-retardant polyolefin heat-shrinkable tube carries out flame retardant properties and measures, by 5 vertical combustions, each 15 seconds, 5 burnings of heat-shrink tube all are lower than 60 seconds total time after leaving the burning burning things which may cause a fire disaster, and the result is by VW-1 vertical combustion performance measurement in the UL224 standard.
Application Example 2
The low-smoke halide-free fireproof composite polyolefine material of embodiment 7 is produced green low smoke halogen-free flame-retardant polyolefin heat-shrinkable tube as stated above carry out flame retardant properties and measure, the result is by U.S. army mark SAE-AMS-DTL-23053/5.In contrast, the EVA-g-MAH among the embodiment 7 is replaced to the EVA-g-MAH product (Dupont) that existing method prepares, surplus with embodiment 7, be found to be the polyolefine material that preparation can be passed through the heat-shrinkable tube of this standard, its consumption is at least 10Kg.
Application Example 3
Low-smoke halide-free fireproof composite polyolefine material with the foregoing description 8 preparations, by existing technology (Huang Shuzhen etc., the exploitation of cross-linking radiation polyolefine low-smoke halogen-free inflaming-retarding cable, 1996,04 phase) produces the yellow low-smoke halogen-free flame-retardant polyolefin cable of radiation crosslinking and carry out flame retardant properties mensuration, by the bunchy testing vertical flammability, the result is by the performance test of GB12666.5-90 bunchy vertical combustion.In contrast, the EVA-g-MAH among the embodiment 8 is replaced to the EVA-g-MAH (Dupont) that existing method prepares, surplus with embodiment 8, be found to be the polyolefine material that preparation can be passed through the cable of this standard, its consumption is at least 15Kg.

Claims (9)

1, a kind of low-smoke halide-free fireproof composite polyolefine material, it comprises the polyolefin substrate that contains ethylene-vinyl acetate copolymer at least, halogen-free flame retardants, ethylene-vinyl acetate copolymer and additive as the grafted maleic anhydride of compatilizer, described additive is selected from oxidation inhibitor, lubricant, in crosslinking coagent and the Halogen Masterbatch one or more, it is characterized in that this ethylene-vinyl acetate copolymer as the grafted maleic anhydride of compatilizer is the ethylene-vinyl acetate copolymer of radiation grafting maleic anhydride, it is made by following method: 1~5 part maleic anhydride is dissolved in the acetone, after 100 parts of ethylene-vinyl acetate copolymers mix, Deng acetone volatilization back granulation in twin screw extruder, carry out radiation with rumbatron electron rays or gamma-rays again, radiation dose is 5~30KGy.
2, low-smoke halide-free fireproof composite polyolefine material as claimed in claim 1, it is characterized in that this polyolefin substrate is ethylene-vinyl acetate copolymer or ethylene-vinyl acetate copolymer and other polyolefinic mixture, described other polyolefine is selected from following combination: polyethylene, terpolymer EP rubber and ethylene-octene copolymer.
3, low-smoke halide-free fireproof composite polyolefine material as claimed in claim 1 is characterized in that this halogen-free flame retardants is organic fire-retardant and/or inorganic combustion inhibitor; Described organic fire-retardant is selected from one or more in ammonium polyphosphate, tetramethylolmethane and the trimeric cyanamide, and described inorganic combustion inhibitor is selected from one or more in aluminium hydroxide, magnesium hydroxide and the zinc borate.
4, low-smoke halide-free fireproof composite polyolefine material as claimed in claim 1 is characterized in that this gamma-rays is the 60Co source.
5, as each described low-smoke halide-free fireproof composite polyolefine material of claim 1~4, the consumption that it is characterized in that this compatilizer is 5~15% of a polyolefin substrate weight.
6, low-smoke halide-free fireproof composite polyolefine material as claimed in claim 1 is characterized in that this polyolefine material comprises following components by part by weight:
Compatilizer: 5~15 parts of the ethylene-vinyl acetate copolymers of radiation grafting maleic anhydride;
Polyolefin substrate: 70~90 parts of ethylene-vinyl acetate copolymers, 5~15 parts of terpolymer EP rubbers;
Oxidation inhibitor: 0.5~4 part of composite antioxidant, wherein Hinered phenols antioxidant: thioesters kind antioxidant=0.5: 1~3;
Halogen-free flame retardants: organic fire-retardant: 8~15 parts of 20~40 parts of ammonium polyphosphates, 10~20 parts of tetramethylolmethanes and trimeric cyanamides, and inorganic combustion inhibitor: Al (OH) 3With Mg (OH) 240~80 parts of mixtures, 10~20 parts of zinc borates;
Lubricant: 1~3 part of divalence metallic soap of stearic acid salt, 1~3 part of polyethylene wax;
Crosslinking coagent: 0~3 part of polyfunctional monomer (methyl) acrylate or triallyl isocyanurate;
0~5 part of Halogen Masterbatch.
7, low-smoke halide-free fireproof composite polyolefine material as claimed in claim 6, it is characterized in that described Hinered phenols antioxidant is selected from 1,3,5-trimethylammonium-2,4,6-three (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,1,3-three (2-methyl-4-hydroxyl-5-t-butyl-phenyl) butane, pentaerythritol ester and β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid octadecyl ester; Described thioesters kind antioxidant is selected from Tyox B, thio-2 acid (octadecyl ester) and thio-2 acid two (14 ester); The acrylate cross linked auxiliary agent of described polyfunctional monomer (methyl) is selected from Viscoat 295, three-TRIM and pentaerythritol triacrylate.
8, as the preparation method of claim 6 or 7 described low-smoke halide-free fireproof composite polyolefine materials, it comprises the following steps: oxidation inhibitor, organic fire-retardant, lubricant divalence metallic soap of stearic acid salt, Halogen Masterbatch, compatilizer and polyolefin substrate behind high speed kneader thorough mixing, extrude air-cooled granulation at twin screw extruder; This particle and inorganic combustion inhibitor, lubricant polyethylene wax and crosslinking coagent further behind high speed kneader thorough mixing, are extruded at twin screw extruder again, and air-cooled granulation gets low-smoke halide-free fireproof composite polyolefine material.
9, can pass through application VW-1 vertical combustion in the UL224 standard, in the versicolor low smoke halogen-free flame-retardant polyolefin heat-shrinkable tube as claim 1~4 and 6~7 each described low-smoke halide-free fireproof composite polyolefine materials in preparation.
CNB2006100287505A 2006-07-07 2006-07-07 Low-smoke halide-free fireproof polyolefine material and its preparation method and application CN100528954C (en)

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