CN101100537A - 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 PDFInfo
- Publication number
- CN101100537A CN101100537A CNA2006100287505A CN200610028750A CN101100537A CN 101100537 A CN101100537 A CN 101100537A CN A2006100287505 A CNA2006100287505 A CN A2006100287505A CN 200610028750 A CN200610028750 A CN 200610028750A CN 101100537 A CN101100537 A CN 101100537A
- Authority
- CN
- China
- Prior art keywords
- low
- vinyl acetate
- ethylene
- polyolefine material
- free
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means 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
- B29C48/40—Means 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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
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 1 EVA-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 2 EVA-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 3 EVA-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 4 EVA-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 5 EVA-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 (10)
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, 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.
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 additive is selected from one or more in oxidation inhibitor, lubricant, crosslinking coagent and the Halogen Masterbatch.
5, low-smoke halide-free fireproof composite polyolefine material as claimed in claim 1 is characterized in that this gamma-rays is
60The Co source.
6, as each described low-smoke halide-free fireproof composite polyolefine material of claim 1～5, the consumption that it is characterized in that this compatilizer is 5～15% of a polyolefin substrate weight.
7, 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.
8, low-smoke halide-free fireproof composite polyolefine material as claimed in claim 7, 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.
9, as the preparation method of claim 7 or 8 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 of the present invention.
10, 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 1～5 and 7～8 each described low-smoke halide-free fireproof composite polyolefine materials in preparation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100287505A CN100528954C (en) | 2006-07-07 | 2006-07-07 | Low-smoke halide-free fireproof polyolefine material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100287505A CN100528954C (en) | 2006-07-07 | 2006-07-07 | Low-smoke halide-free fireproof polyolefine material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101100537A true CN101100537A (en) | 2008-01-09 |
| CN100528954C CN100528954C (en) | 2009-08-19 |
Family
ID=39034997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100287505A Active CN100528954C (en) | 2006-07-07 | 2006-07-07 | Low-smoke halide-free fireproof polyolefine material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100528954C (en) |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817952A (en) * | 2010-05-19 | 2010-09-01 | 西安交通大学 | Soft low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
| CN101899183A (en) * | 2010-09-02 | 2010-12-01 | 中国科学技术大学 | Radiation cross-linking waterproof flame retardant polyolefin nano-composite material and preparation method thereof |
| CN101565527B (en) * | 2009-05-26 | 2011-04-27 | 上海凯波特种电缆料厂有限公司 | 125 DEG C irradiated crosslinking low-smoke and halogen-free flame retardant polyolefin jacket material used for oil platform |
| CN102070820A (en) * | 2010-12-01 | 2011-05-25 | 浙江七色鹿色母粒有限公司 | Polyethylene of raised temperature resistance (PE-RT) master batch and preparation method thereof |
| CN102070821A (en) * | 2010-12-14 | 2011-05-25 | 江苏德威新材料股份有限公司 | Irradiation cross-linking oil resistance type soft low smoke zero halogen flame-retardant cable material |
| CN102093626A (en) * | 2010-12-20 | 2011-06-15 | 安徽中鼎密封件股份有限公司 | Non-halogen fire resistant low-temperature shrinkable and heat-shrinkable pipe material and preparation method thereof |
| CN101696299B (en) * | 2009-10-28 | 2011-08-31 | 江苏达胜热缩材料有限公司 | Semiconductor low-voltage double-wall thermal shrinkage pipe and preparation method thereof |
| CN102295797A (en) * | 2010-06-24 | 2011-12-28 | 上海凯波特种电缆料厂有限公司 | Zero-halogen flame-retardant polyolefin material and preparation method as well as application thereof |
| CN102321295A (en) * | 2011-09-29 | 2012-01-18 | 广州凯恒科塑有限公司 | Low smoke zero halogen flame-retardant mould shrinkage sleeve and preparation method as well as application thereof |
| CN101597395B (en) * | 2009-06-24 | 2012-02-29 | 上海至正道化高分子材料有限公司 | Low-smoke halogen-free inflaming-retarding cable material and preparation method thereof |
| CN102432934A (en) * | 2011-09-29 | 2012-05-02 | 广州凯恒科塑有限公司 | Low-smoke halogen-free phosphorus-nitrogen expansion flame-retardant mold shrinkage sleeve and preparation method and application thereof |
| CN102477178A (en) * | 2010-11-23 | 2012-05-30 | 上海杰事杰新材料(集团)股份有限公司 | Low-smoke halogen-free flame-retardant antistatic aging-resistant wire and cable material and preparation method thereof |
| CN102585345A (en) * | 2012-02-27 | 2012-07-18 | 广州凯恒科塑有限公司 | Oil-proof low-smoke halogen-free flame-retardant heat shrinkable label sleeve as well as preparation method and application thereof |
| CN102875947A (en) * | 2012-09-20 | 2013-01-16 | 中国科学院上海应用物理研究所 | Halogen-free flame retardant sheath material for nuclear cable, cable sheath, preparation method and application |
| CN103059390A (en) * | 2013-02-03 | 2013-04-24 | 张关莲 | Method for preparing halogen-free flame retardant polythene (PE) pipe |
| CN103059388A (en) * | 2013-02-03 | 2013-04-24 | 王达 | Halogen-free flame retardant polythene (PE) pipe |
| CN103073775A (en) * | 2013-02-03 | 2013-05-01 | 刘芝英 | Preparation method for environment-friendly anti-flaming anti-static polyethylene pipeline |
| CN103087373A (en) * | 2012-06-11 | 2013-05-08 | 深圳市沃尔核材股份有限公司 | Radiation crosslinked chloroprene rubber heat shrinkable tube and production method thereof |
| CN103087531A (en) * | 2013-01-22 | 2013-05-08 | 辽宁科瑞德电缆有限公司 | Fire retardant foaming material for halogen-free flame retardant cable and preparation method of fire retardant foaming material |
| CN103232628A (en) * | 2013-04-15 | 2013-08-07 | 中国核电工程有限公司 | Halogen free flame retardation thermal contraction material and thermal contraction casing pipe manufacturing method |
| CN102159632B (en) * | 2008-08-21 | 2013-11-06 | 朗盛德国有限责任公司 | Highly flexible, halogen-free and fire-resistant thermoplastic cable mixtures |
| CN103483675A (en) * | 2013-09-25 | 2014-01-01 | 宁波一舟塑胶有限公司 | High-elasticity wear-resistant low-smoke halogen-free flame-retardant cable material |
| CN104672729A (en) * | 2015-02-07 | 2015-06-03 | 山东天汇防水材料有限公司 | Intumescent fire resistant type waterproof roll and preparation method thereof |
| CN104795146A (en) * | 2015-04-22 | 2015-07-22 | 深圳宝兴电线电缆制造有限公司 | Solar photovoltaic cable |
| CN106674715A (en) * | 2016-12-23 | 2017-05-17 | 苏州曙帆信电子科技有限公司 | Flame-retardant EVA color master batch |
| CN107490505A (en) * | 2017-07-28 | 2017-12-19 | 深圳市宏商材料科技股份有限公司 | A kind of heat-shrink tube test specimen and its preparation method and application |
| CN108164798A (en) * | 2016-12-07 | 2018-06-15 | 上海凯波特种电缆料厂有限公司 | A kind of thermoplastic low-smoke halide-free fireproof composite polyolefine material of low-smoke and preparation method thereof |
| CN112143054A (en) * | 2020-10-21 | 2020-12-29 | 常州浩达科技股份有限公司 | Preparation method of damping rubber material |
| CN112175278A (en) * | 2020-10-16 | 2021-01-05 | 青岛汉缆股份有限公司 | Thermoplastic halogen-free flame-retardant polyolefin sheath material for ultrahigh-voltage cable and preparation method and application thereof |
| CN112225982A (en) * | 2020-10-16 | 2021-01-15 | 常州八益电缆股份有限公司 | Rod position reactor top signal cable for nuclear power station |
| CN112225983A (en) * | 2020-10-16 | 2021-01-15 | 常州八益电缆股份有限公司 | Flame-retardant sheath material for nuclear power station cable, preparation method and service life detection method |
| CN114872403A (en) * | 2022-05-11 | 2022-08-09 | 南京喜悦科技股份有限公司 | Double-wall heat-shrinkable tube and outer-layer heat-shrinkable material thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137932C (en) * | 2000-04-07 | 2004-02-11 | 中国科学院上海原子核研究所 | Low-temp thermoshrinking halogen-free polyolefine material with properties of radiation cross-linking, low smoke and flame retardation |
| CN1257513C (en) * | 2002-03-18 | 2006-05-24 | 上海至正企业发展有限公司 | Flame retardant polyolefin cable material with low smoke halogen and its preparing method |
| DE10315631A1 (en) * | 2003-04-04 | 2004-11-11 | Rehau Ag + Co. | Heat shrinkable protective tube |
| CN1187402C (en) * | 2003-05-16 | 2005-02-02 | 上海交通大学 | Smokeless non-halogen retardant polyolefine preparing method |
| CN1241207C (en) * | 2003-08-15 | 2006-02-08 | 北京化工大学 | Halogen-free non-phosphorus flame-retarded cable sheath material |
| CN1796450B (en) * | 2004-12-29 | 2010-05-05 | 上海至正道化高分子材料有限公司 | Low smoky, fire retardant cable material of polyolefin without halogen, and preparation method |
-
2006
- 2006-07-07 CN CNB2006100287505A patent/CN100528954C/en active Active
Cited By (47)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102159632B (en) * | 2008-08-21 | 2013-11-06 | 朗盛德国有限责任公司 | Highly flexible, halogen-free and fire-resistant thermoplastic cable mixtures |
| CN101565527B (en) * | 2009-05-26 | 2011-04-27 | 上海凯波特种电缆料厂有限公司 | 125 DEG C irradiated crosslinking low-smoke and halogen-free flame retardant polyolefin jacket material used for oil platform |
| CN101597395B (en) * | 2009-06-24 | 2012-02-29 | 上海至正道化高分子材料有限公司 | Low-smoke halogen-free inflaming-retarding cable material and preparation method thereof |
| CN101696299B (en) * | 2009-10-28 | 2011-08-31 | 江苏达胜热缩材料有限公司 | Semiconductor low-voltage double-wall thermal shrinkage pipe and preparation method thereof |
| CN101817952B (en) * | 2010-05-19 | 2012-01-04 | 西安交通大学 | Soft low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
| CN101817952A (en) * | 2010-05-19 | 2010-09-01 | 西安交通大学 | Soft low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
| CN102295797B (en) * | 2010-06-24 | 2013-09-18 | 上海凯波特种电缆料厂有限公司 | Zero-halogen flame-retardant polyolefin material and preparation method as well as application thereof |
| CN102295797A (en) * | 2010-06-24 | 2011-12-28 | 上海凯波特种电缆料厂有限公司 | Zero-halogen flame-retardant polyolefin material and preparation method as well as application thereof |
| CN101899183A (en) * | 2010-09-02 | 2010-12-01 | 中国科学技术大学 | Radiation cross-linking waterproof flame retardant polyolefin nano-composite material and preparation method thereof |
| CN101899183B (en) * | 2010-09-02 | 2012-05-23 | 中国科学技术大学 | Irradiation crosslinking water-resistant flame-retardant polyolefin nano composite material and preparation method thereof |
| CN102477178A (en) * | 2010-11-23 | 2012-05-30 | 上海杰事杰新材料(集团)股份有限公司 | Low-smoke halogen-free flame-retardant antistatic aging-resistant wire and cable material and preparation method thereof |
| CN102070820A (en) * | 2010-12-01 | 2011-05-25 | 浙江七色鹿色母粒有限公司 | Polyethylene of raised temperature resistance (PE-RT) master batch and preparation method thereof |
| CN102070820B (en) * | 2010-12-01 | 2012-05-30 | 浙江七色鹿色母粒有限公司 | High-temperature-resistant polyethylene color master batch and preparation method thereof |
| CN102070821A (en) * | 2010-12-14 | 2011-05-25 | 江苏德威新材料股份有限公司 | Irradiation cross-linking oil resistance type soft low smoke zero halogen flame-retardant cable material |
| CN102070821B (en) * | 2010-12-14 | 2013-02-13 | 江苏德威新材料股份有限公司 | Irradiation cross-linking oil resistance type soft low smoke zero halogen flame-retardant cable material |
| CN102093626A (en) * | 2010-12-20 | 2011-06-15 | 安徽中鼎密封件股份有限公司 | Non-halogen fire resistant low-temperature shrinkable and heat-shrinkable pipe material and preparation method thereof |
| CN102432934A (en) * | 2011-09-29 | 2012-05-02 | 广州凯恒科塑有限公司 | Low-smoke halogen-free phosphorus-nitrogen expansion flame-retardant mold shrinkage sleeve and preparation method and application thereof |
| CN102321295A (en) * | 2011-09-29 | 2012-01-18 | 广州凯恒科塑有限公司 | Low smoke zero halogen flame-retardant mould shrinkage sleeve and preparation method as well as application thereof |
| CN102432934B (en) * | 2011-09-29 | 2013-05-29 | 广州凯恒科塑有限公司 | Low-smoke halogen-free phosphorus nitrogen expanding flame-retardant mold shrinkage sleeve and preparation method and application thereof |
| CN102321295B (en) * | 2011-09-29 | 2013-05-08 | 广州凯恒科塑有限公司 | Low smoke zero halogen flame-retardant mould shrinkage sleeve and preparation method as well as application thereof |
| CN102585345B (en) * | 2012-02-27 | 2013-12-25 | 广州凯恒科塑有限公司 | Oil-proof low-smoke halogen-free flame-retardant heat shrinkable label sleeve as well as preparation method and application thereof |
| CN102585345A (en) * | 2012-02-27 | 2012-07-18 | 广州凯恒科塑有限公司 | Oil-proof low-smoke halogen-free flame-retardant heat shrinkable label sleeve as well as preparation method and application thereof |
| CN103087373A (en) * | 2012-06-11 | 2013-05-08 | 深圳市沃尔核材股份有限公司 | Radiation crosslinked chloroprene rubber heat shrinkable tube and production method thereof |
| CN103087373B (en) * | 2012-06-11 | 2015-08-26 | 深圳市沃尔核材股份有限公司 | Radiation crosslinking chloroprene rubber heat-shrink tube and production method thereof |
| CN102875947A (en) * | 2012-09-20 | 2013-01-16 | 中国科学院上海应用物理研究所 | Halogen-free flame retardant sheath material for nuclear cable, cable sheath, preparation method and application |
| CN103087531A (en) * | 2013-01-22 | 2013-05-08 | 辽宁科瑞德电缆有限公司 | Fire retardant foaming material for halogen-free flame retardant cable and preparation method of fire retardant foaming material |
| CN103073775A (en) * | 2013-02-03 | 2013-05-01 | 刘芝英 | Preparation method for environment-friendly anti-flaming anti-static polyethylene pipeline |
| CN103059388A (en) * | 2013-02-03 | 2013-04-24 | 王达 | Halogen-free flame retardant polythene (PE) pipe |
| CN103059390A (en) * | 2013-02-03 | 2013-04-24 | 张关莲 | Method for preparing halogen-free flame retardant polythene (PE) pipe |
| CN103073775B (en) * | 2013-02-03 | 2015-07-08 | 义乌市满旺机械设备有限公司 | Preparation method for environment-friendly anti-flaming anti-static polyethylene pipeline |
| CN103059390B (en) * | 2013-02-03 | 2015-10-28 | 福建省感创精密机械有限公司 | A kind of preparation method of halogen-free flameproof PE pipe |
| CN103232628A (en) * | 2013-04-15 | 2013-08-07 | 中国核电工程有限公司 | Halogen free flame retardation thermal contraction material and thermal contraction casing pipe manufacturing method |
| CN103232628B (en) * | 2013-04-15 | 2015-11-04 | 中国核电工程有限公司 | The manufacture method of a kind of halogen-free flame-retardant thermal shrinkage material and thermal contraction casing tube |
| CN103483675A (en) * | 2013-09-25 | 2014-01-01 | 宁波一舟塑胶有限公司 | High-elasticity wear-resistant low-smoke halogen-free flame-retardant cable material |
| CN103483675B (en) * | 2013-09-25 | 2016-04-13 | 宁波一舟塑胶有限公司 | High-elasticity wear-resistant low-smoke halogen-free flame-retardant cable material |
| CN104672729A (en) * | 2015-02-07 | 2015-06-03 | 山东天汇防水材料有限公司 | Intumescent fire resistant type waterproof roll and preparation method thereof |
| CN104795146A (en) * | 2015-04-22 | 2015-07-22 | 深圳宝兴电线电缆制造有限公司 | Solar photovoltaic cable |
| CN108164798B (en) * | 2016-12-07 | 2021-02-02 | 上海凯波电缆特材股份有限公司 | Low-smoke-amount thermoplastic low-smoke halogen-free flame-retardant polyolefin material and preparation method thereof |
| CN108164798A (en) * | 2016-12-07 | 2018-06-15 | 上海凯波特种电缆料厂有限公司 | A kind of thermoplastic low-smoke halide-free fireproof composite polyolefine material of low-smoke and preparation method thereof |
| CN106674715A (en) * | 2016-12-23 | 2017-05-17 | 苏州曙帆信电子科技有限公司 | Flame-retardant EVA color master batch |
| CN107490505B (en) * | 2017-07-28 | 2020-06-02 | 深圳市宏商材料科技股份有限公司 | Heat-shrinkable tube test sample and preparation method and application thereof |
| CN107490505A (en) * | 2017-07-28 | 2017-12-19 | 深圳市宏商材料科技股份有限公司 | A kind of heat-shrink tube test specimen and its preparation method and application |
| CN112175278A (en) * | 2020-10-16 | 2021-01-05 | 青岛汉缆股份有限公司 | Thermoplastic halogen-free flame-retardant polyolefin sheath material for ultrahigh-voltage cable and preparation method and application thereof |
| CN112225982A (en) * | 2020-10-16 | 2021-01-15 | 常州八益电缆股份有限公司 | Rod position reactor top signal cable for nuclear power station |
| CN112225983A (en) * | 2020-10-16 | 2021-01-15 | 常州八益电缆股份有限公司 | Flame-retardant sheath material for nuclear power station cable, preparation method and service life detection method |
| CN112143054A (en) * | 2020-10-21 | 2020-12-29 | 常州浩达科技股份有限公司 | Preparation method of damping rubber material |
| CN114872403A (en) * | 2022-05-11 | 2022-08-09 | 南京喜悦科技股份有限公司 | Double-wall heat-shrinkable tube and outer-layer heat-shrinkable material thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100528954C (en) | 2009-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100528954C (en) | Low-smoke halide-free fireproof polyolefine material and its preparation method and application | |
| CN101597395B (en) | Low-smoke halogen-free inflaming-retarding cable material and preparation method thereof | |
| CN101914236B (en) | Irradiation crosslinking halogen-free high flame-retardant cable material and preparation method thereof | |
| CN101560314A (en) | Halogen-free phosphorus-free inflaming retarding polyolefine material prepared by radiation grafting technology, preparation method and the application thereof | |
| CN101649081B (en) | Method for manufacturing halogen-free fire-retardant polyethylene material | |
| CN103172918B (en) | A kind of fireproofing cable material without halide and preparation method thereof | |
| CN102993602B (en) | CMP-grade flame-retardant smoke-inhibiting polyvinyl chloride cable sheath material and preparation method thereof | |
| CN104403190A (en) | Ultraviolet cross-linking oil-resistant low-smoke halogen-free flame retardant polyolefin cable material and preparation method thereof | |
| CN102898703B (en) | Flame retardant polyolefin cable material and preparation method thereof | |
| CN101343392B (en) | Halogen-free flame-proof reinforced polypropylene composite material and preparation thereof | |
| CN102532693B (en) | High-performance low-smoke halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| CN103881229A (en) | High-flame-retardant and halogen-free polyolefin cable material and preparation method thereof | |
| CN104693604A (en) | Halogen-free flame retardant glass-fiber reinforced polypropylene composite material and preparation method thereof | |
| CN101225199A (en) | Material used for halogen-free flame retardant heat shrinkable sheathing and cross-linking cable wire and preparation method thereof | |
| CN102276905A (en) | Formulation of radiant cross-linked thermal-shrinked halogen-free fire-retardant identified casing product, and preparation method thereof | |
| CN103951959A (en) | Intumescent flame-retardant reinforced PC (Polycarbonate)/ABS (Acrylonitrile Butadiene Styrene) alloy and preparation method thereof | |
| CN109627568B (en) | Polyolefin cable sheath material and preparation method thereof | |
| CN101143943A (en) | Low-smoke halogen-free flame-proof cable material and its preparation method | |
| CN103897245A (en) | Method for preparing anti-crack low-smoke and halogen-free optical cable flame-retardant sheath material | |
| CN106009585A (en) | Halogen-free flame retardation polycarbonate material and preparation method thereof | |
| CN108164806A (en) | Locomotive engine cable irradiated crosslinking low-smoke and halogen-free flame retardant polyolefin material and preparation method thereof | |
| CN110818997A (en) | Flame-retardant polyethylene cable material and preparation method thereof | |
| CN104356538B (en) | Flame-retardant smoke-eliminating polyvinyl chloride wire and cable material | |
| CN1760997A (en) | Environmental protection type fire retardant thermal shrinkage tube without halogen | |
| CN102952325B (en) | Halogen-free red phosphorus-free flame-retardant heat shrinkage material, heat shrinkage tube and preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SHILONG SCIENCE-TECHNOLOGY CO., LTD., SHANGHAI Free format text: FORMER OWNER: SHANGHAI INST. OF APPLIED PHYSICS CHINESE ACADEMY OF SCIENCES Effective date: 20131230 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20131230 Address after: 201800 No. 1411, Yecheng Road, Jiading Industrial Zone, Shanghai, Jiading District Patentee after: Shilong Science-Technology Co., Ltd., Shanghai Address before: 201800 Shanghai city Jiading District Road No. 2019 Patentee before: Shanghai Inst. of Applied Physics Chinese Academy of Sciences |