CN105623180A - Halogen-free flame retardant thermoplastic elastomer material for electric wires and cables and preparation method thereof - Google Patents
Halogen-free flame retardant thermoplastic elastomer material for electric wires and cables and preparation method thereof Download PDFInfo
- Publication number
- CN105623180A CN105623180A CN201610021557.2A CN201610021557A CN105623180A CN 105623180 A CN105623180 A CN 105623180A CN 201610021557 A CN201610021557 A CN 201610021557A CN 105623180 A CN105623180 A CN 105623180A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- halogen
- thermoplastic elastomer
- free flame
- district
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- 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
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/442—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from aromatic vinyl compounds
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
Abstract
The invention discloses a halogen-free flame retardant thermoplastic elastomer material for electric wires and cables. The thermoplastic elastomer material comprises the following raw materials in parts by weight: 25-45 parts of thermoplastic elastomer, 25-40 parts of halogen-free flame retardant, 15-30 parts of polyphenyl ether, 8-15 parts of extending oil and 0.1-0.5 part of antioxidant, wherein the thermoplastic elastomer consists of a hydrogenated styrene block copolymer and a thermoplastic vulcanization elastomer; the hydrogenated styrene block copolymer accounts for 60-80% of the weight of the thermoplastic elastomer; the thermoplastic vulcanization elastomer accounts for 20-40% of the weight of the thermoplastic elastomer; the halogen-free flame retardant consists of a primary flame retardant and a secondary flame retardant; the primary flame retardant consists of organic phosphate salt/ester and melamine polyphosphate; and the secondary flame retardant is polyphosphate. The thermoplastic elastomer material disclosed by the invention is resistant to high temperature, has good processability and good flame retardant property and is halogen-free, low-toxic and environment-friendly.
Description
Technical field
The present invention relates to electric wire and cable material technical field, particularly to a kind of halogen-free flame retardant thermoplastic elastomer material for electric wire and preparation method thereof.
Background technology
Along with problem of environmental pollution is more and more prominent, nowadays people's attaching importance to environmental protection gradually, wires and cables industry is no exception, necessarily faces the requirement to environmental protection. The environmental protection of wires and cables industry is exactly mainly cable material environmental protection, produces electric wire at present and uses the macromolecule chemical industry materials such as rubber, polrvinyl chloride, polyethylene in a large number, produces a large amount of toxic and harmful in process of production. In addition elastomeric material processed complex, leftover pieces can not reclaim and easily cause secondary pollution. Wherein, the advantage of polyvinyl chloride resin is in that have cost advantage, but easily tacky, loss of properties on aging and non-environmental protection under easy to crack, high temperature under the cable low temperature that becomes of this materials processing; The combination properties such as mechanical property, environmental stress cracking resistance, chemical resistance and the electrical property that the cable goods that cross-linking polyethylene materials is processed into impart, there is problems of anti-weather-aging property difference, processing characteristics deficiency etc.; Therefore, except considering the feature performance benefit of material, also want active development ep-type material, produce environment-friendly type electric wire.
Thermoplastic elastomer (TPE) achieves significant progress in recent years, market is proposed polytype thermoplastic elastomer (TPE), but the thermoplastic elastic material being applied to electric wire aspect still also exists various problem, the application of polyphenylene oxide provides good fire-retardant and electrical insulation capability, but polyphenylene oxide is due to shortcomings such as viscosity are big, poor processability, color inhibition are not enough, limits its application at wires and cables industry. Patent publication No. is that CN102414274A Chinese patent application discloses based on thermoplastic elastomer (TPE) and adds the method for polyphenylene oxide and fire retardant and be prepared for a kind of wire cable material, this method is obtained in that superior fire resistance, but but has considerable restraint for preparing more resistant to elevated temperatures fire proofing; Patent publication No. is the method that halogen-free flame-retardant wire CABLE MATERIALS is prepared in CN102414274A Chinese patent application announcement, although also adding polyphenylene oxide to improve flame retardant effect, but the EP rubbers owing to adding crosslinking is difficult to dispersion in whole system, and especially extrusion grade electric wire surface flatness is extremely difficult to requirement.
Summary of the invention
Based on Problems existing in background technology, the present invention proposes a kind of halogen-free flame retardant thermoplastic elastomer material for electric wire and preparation method thereof, and thus preparation-obtained thermoplastic elastic material is high temperature resistant, processability is good, while there is good flame-retardance energy, and Halogen, low toxicity, environmental protection.
A kind of halogen-free flame retardant thermoplastic elastomer material for electric wire that the present invention proposes, its raw material includes by weight: thermoplastic elastomer (TPE) 25-45 part, halogen-free flame retardants 25-40 part, polyphenylene oxide 15-30 part, fill oil 8-15 part, antioxidant 0.1-0.5 part, styrene resin 2-5 part;
Wherein, described thermoplastic elastomer (TPE) is made up of hydrogenated styrene block copolymers and thermoplastic vulcanizates elastomer, described hydrogenated styrene block copolymers is the 60-80% of described thermoplastic elastic body weight, and described thermoplastic vulcanizates elastomer is the 20-40% of thermoplastic elastic body weight;
Described halogen-free flame retardants is made up of main flame retardant and secondary fire retardant, and wherein, main flame retardant is made up of organic phosphate/ester and melamine polyphosphate, and secondary fire retardant is poly phosphate.
In a specific embodiment, the weight portion of thermoplastic elastomer (TPE) can be 27,29,32,34,36,38,39,41,43,44; The weight portion of halogen-free flame retardants can be 26,27,28,29,32,34,36,37,38,39; The weight portion of polyphenylene oxide can be 16,17,18,19,21,23,25,27,28,29; The weight portion filling oil can be 8.7,9.3,9.8,10.1,11.5,12.6,13.7,14.8; The weight portion of antioxidant can be 0.12,0.15,0.17,0.22,0.23,0.25,0.28,0.32,0.36,0.38,0.42,0.45,0.47; The weight portion of styrene resin can be 2.2,2.5,2.7,2.9,3.2,3.3,3.5,3.7,3.9,4.2,4.5,4.7 parts.
Preferably, in the middle part of the polystyrene end block of described hydrogenated styrene block copolymers and polyolefin, the weight proportion of block is 0.72-1.38:1; Preferably, described hydrogenated styrene block copolymers is that styrene-ethylene-butylene-styrene polymer, styrene ethylene-propylene-styrene polymer be a kind of or the combination of two kinds.
Preferably, described thermoplastic vulcanizates elastomer is that the olefinic rubber of the vistanex by 20-35% and 65-80% is through dynamic vulcanization generation by weight percentage; Preferably, described vistanex is acrylic resin or polyvinyl resin, and described olefinic rubber is EP rubbers or Ethylene-octene rubber.
Preferably, described halogen-free flame retardants is made up of the secondary fire retardant of the main flame retardant of 66-84% and 16-34% by weight percentage; Described organic phosphate/ester is the 45-65% of described main flame retardant weight, and described melamine polyphosphate is the 35-55% of described main flame retardant weight.
Preferably, described organophosphorus ester is chitin modified phosphate ester, and its preparation method includes: will stir in phosphorus oxychloride, tetramethylolmethane addition anhydrous acetonitrile, when nitrogen protection, it is warming up to 50-60 DEG C, stirs 0.5-1h, after adding aluminum trichloride (anhydrous), it is continuously heating to 80-90 DEG C, stirring 1-2h, after solvent is distilled off, washing, dry, obtain tetramethylolmethane spiro-phosphate diacid chloride; Described tetramethylolmethane spiro-phosphate diacid chloride is added in methanesulfonic acid, adds chitosan and stir, when nitrogen protection, be warming up to 40-60 DEG C, stir 2-4h, washing, dry, obtain described chitin modified phosphate ester; Preferably, phosphorus oxychloride, tetramethylolmethane, aluminum chloride, chitosan weight proportion be: 4-6:1-3:0.05-0.08:0.8-1.2;
Preferably, described organic phosphate is n-trimethyl chitosan chloride modified phosphate, and its preparation method includes: added by described chitin modified phosphate ester in isopropanol, drips sodium hydroxide solution under stirring condition, drip ether agent of CTA again, heating, to 30-50 DEG C, stirs 2-4h, and acid adding regulates to neutrality, sucking filtration, washing, dry, obtain described n-trimethyl chitosan chloride modified phosphate; Preferably, described chitin modified phosphate ester, CTA weight proportion be: 1:1.5-3.
Preferably; described poly phosphate is resorcinol oligomeric phosphate; its preparation method includes: added by DOPO in dimethylbenzene, and when nitrogen protection, heating is to 80-100 DEG C; the lower dropping of stirring is dissolved with the xylene solution of paraformaldehyde; in 1-3h, complete dropping, be heated to reflux 4-6h, filter; washing, obtains DOPO-CH2OH, by described DOPO-CH2OH addition dichloromethane stirs, when nitrogen protection, adds phosphorus oxychloride, be warming up to 40-60 DEG C, stir 1-2h, after solvent is removed in distillation, wash, dry, obtain performed polymer; Adding resorcinol in described performed polymer, when nitrogen protection, heating, to 40-60 DEG C, adds aluminum trichloride (anhydrous) under stirring, it is continuously heating to 80-90 DEG C, stirs 1-3h, after solvent is removed in distillation, washing, dry, obtain described resorcinol oligomeric phosphate; Preferably, DOPO, paraformaldehyde, phosphorus oxychloride, resorcinol weight proportion be 1:0.1-0.2:0.5-0.8:0.4-0.6.
Preferably, the intrinsic viscosity of described polyphenylene oxide is 0.1-0.5dl/g; Preferably, described polyphenylene oxide is poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene) ether.
Preferably, described filling oil is paraffin oil or naphthenic oil; Described antioxidant is four [��-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester or three [2,4-di-tert-butyl-phenyl] phosphite esters; Described styrene resin is impact-resistant polystyrene.
Preferably, described halogen-free flame retardant thermoplastic elastomer material also includes one or more combination of uvioresistant photo etching, coloring agent, lubricant, processing aid;
Preferably, described uvioresistant photo etching includes UV powder; Described lubricant is one or more combination of ethylene bis stearic acid amide, the double; two oleamide of ethylene, zinc stearate, calcium stearate, PE wax, dimethicone; Described coloring agent is that oxidized black, iron oxide red, iron oxide yellow, titanium be Dracocephalum moldabium, one or more combination of chrome green; Described processing aid is one or more combination of calcium carbonate, Pulvis Talci, kieselguhr, mica powder, silicon dioxide.
A kind of preparation method of the halogen-free flame retardant thermoplastic elastomer material for electric wire, including: by thermoplastic elastomer (TPE), fill oil, styrene resin, antioxidant addition high-speed mixer and mixing 0.2-0.4h, obtain masterbatch; Described masterbatch and polyphenylene oxide, halogen-free flame retardants are added in double screw extruder and plasticates, tie rod, cooling, pelletizing, obtaining the described halogen-free flame retardant thermoplastic elastomer material for electric wire, wherein, screw slenderness ratio is 55-64, screw speed is 300-500rpm, and processing temperature is 200-260 DEG C; Preferably, described processing temperature is particularly as follows: district's temperature 200 DEG C, two district's temperature 220 DEG C, three district's temperature 225 DEG C, four district's temperature 230 DEG C, five district's temperature 235 DEG C, six district's temperature 240 DEG C, seven district's temperature 245 DEG C, eight district's temperature 250 DEG C, nine district's temperature 255 DEG C, ten district's temperature 260 DEG C, 11 district's temperature 260 DEG C, No.12 District temperature 260 DEG C, 13 district's temperature 255 DEG C.
In the present invention, described thermoplastic elastic material adds the thermoplastic elastomer (TPE) being made up of hydrogenated styrene block copolymers and thermoplastic vulcanizates elastomer, hydrogenated styrene block copolymers wherein introduces the styrene block copolymer of styrene-content at high proportion, the Miscibility with polyphenylene oxide can be increased, while performance polyphenylene oxide is effectively improved material resistance to elevated temperatures, the mechanical mechanics property of thermoplastic elastic material and processing characteristics will not be produced impact, by adding thermoplastic vulcanizates elastomer, it has and significantly improves described elastic properties of materials, reduces the effect of hardness, in order to improve the fire resistance of described material, in the present invention on the basis of thermoplastic elastomer (TPE), it is additionally added the highly efficiency compositional flame retardant system being made up of main flame retardant and secondary fire retardant, wherein, main flame retardant is made up of organic phosphate/ester and melamine polyphosphate, organic phosphate/ester is by preparing intermediate tetramethylolmethane spiro-phosphate diacid chloride and chitosan reaction obtains a kind of fire-retardant and synergistic in the polymer-based fire retardant of efficient natural of one, wherein the structure of tetramethylolmethane volution and chitosan is as good carbon forming agent, at hot stage, there is significantly high neat coal amout, carbon-coating can be formed rapidly at material surface, there is excellent self-extinguishment function, and the structure of chitosan can play the function served as bridge connecting organic facies and inorganic phase, considerably increase the dispersive property of organic phosphate/ester, and the dispersive property of this excellence, can effectively be combined with matrix, will not bringing precipitation problem, its prominent advantage all meets the environmental requirement of society, in addition melamine polyphosphate pyrolysis deamination in the process heated up, generate non-flame properties gaseous product ammonia, oxygen concentration in surrounding is declined, alleviate the thermal oxidation of thermoplastic elastomer (TPE), therefore, described organic phosphate/ester and melamine polyphosphate, as main flame retardant, define and a kind of collect acid source, the gentle natural polymer subbase expansion type flame retardant coming from one in charcoal source, described secondary fire retardant is made up of poly phosphate, its by by after DOPO and polyformaldehyde reaction with phosphorus oxychloride reaction, at the oligomer being generated a kind of phosphate ester by resorcinol, it is while having the heat stability of excellence, composite with above-mentioned main flame retardant, can further improve the fire resistance of described material, and can as a kind of plasticizer so that described thermoplastic elastomer (s) has good processing characteristics, the present invention is also added into the impact-resistant polystyrene of specific proportioning in addition, while improving the toughness of thermoplastic elastomehc material, the plasticizer of certain content, antioxidant and the processing aids etc. added, also make thermoplastic elastic material have good processing characteristics and ageing resistace.
Detailed description of the invention
Below by specific embodiment, technical scheme is described in detail.
Embodiment 1
A kind of halogen-free flame retardant thermoplastic elastomer material for electric wire, its raw material includes by weight: thermoplastic elastomer (TPE) 25 parts, halogen-free flame retardants 40 parts, polyphenylene oxide 15 parts, fills oil 15 parts, 0.1 part of antioxidant, styrene resin 2 parts;
Wherein, described thermoplastic elastomer (TPE) is made up of the styrene-ethylene-butylene-styrene polymer of 60wt% and the thermoplastic vulcanizates elastomer of 40wt%; In the middle part of the polystyrene end block of described styrene-ethylene-butylene-styrene polymer and polyolefin, the weight proportion of block is 0.72:1; Described thermoplastic vulcanizates elastomer be by weight percentage the acrylic resin by 20% and 80% EP rubbers through dynamic vulcanization generate;
Described halogen-free flame retardants is made up of the main flame retardant of 66wt% and the secondary fire retardant of 34wt%, and wherein main flame retardant is made up of the organophosphorus ester of 45wt% and the melamine polyphosphate of 55wt%, and secondary fire retardant is poly phosphate;
Described organophosphorus ester is chitin modified phosphate ester, its preparation method includes: by stirring in phosphorus oxychloride, tetramethylolmethane addition anhydrous acetonitrile, when nitrogen protection, be warming up to 50 DEG C, stirring 1h, after adding aluminum trichloride (anhydrous), it is continuously heating to 80 DEG C, stirs 2h, after solvent is distilled off, washing, dry, obtain tetramethylolmethane spiro-phosphate diacid chloride; Described tetramethylolmethane spiro-phosphate diacid chloride is added in methanesulfonic acid, add chitosan to stir, when nitrogen protection, it is warming up to 40 DEG C, stirs 4h, washing, dry, obtain described chitin modified phosphate ester, wherein, phosphorus oxychloride, tetramethylolmethane, aluminum chloride, chitosan weight proportion be: 4:3:0.05:1.2;
Described poly phosphate is resorcinol oligomeric phosphate; its preparation method includes: added by DOPO in dimethylbenzene; when nitrogen protection; heating is to 80 DEG C, and the lower dropping of stirring, dissolved with the xylene solution of paraformaldehyde, completes dropping in 3h; it is heated to reflux 4h; filter, washing, obtain DOPO-CH2OH, by described DOPO-CH2OH addition dichloromethane stirs, when nitrogen protection, adds phosphorus oxychloride, be warming up to 60 DEG C, stir 1h, after solvent is removed in distillation, wash, dry, obtain performed polymer; Resorcinol is added in described performed polymer, when nitrogen protection, heating, to 60 DEG C, adds aluminum trichloride (anhydrous) under stirring, it is continuously heating to 80 DEG C, stirring 3h, after solvent is removed in distillation, washing, dry, obtain described resorcinol oligomeric phosphate, wherein, DOPO, paraformaldehyde, phosphorus oxychloride, resorcinol weight proportion be 1:0.1:0.8:0.4;
The intrinsic viscosity of described polyphenylene oxide is 0.1dl/g, and described polyphenylene oxide is poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene) ether; Described filling oil is paraffin oil; Described antioxidant is four [��-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester; Described styrene resin is impact-resistant polystyrene.
Embodiment 2
A kind of halogen-free flame retardant thermoplastic elastomer material for electric wire, its raw material includes by weight: thermoplastic elastomer (TPE) 45 parts, halogen-free flame retardants 25 parts, polyphenylene oxide 30 parts, fills oil 8 parts, 0.5 part of antioxidant, styrene resin 5 parts;
Wherein, described thermoplastic elastomer (TPE) is made up of the styrene ethylene-propylene-styrene polymer of 80wt% and the thermoplastic vulcanizates elastomer of 20wt%; In the middle part of the polystyrene end block of described styrene ethylene-propylene-styrene polymer and polyolefin, the weight proportion of block is 1.38:1; Described thermoplastic vulcanizates elastomer be by weight percentage the polyvinyl resin by 35% and 65% Ethylene-octene rubber through dynamic vulcanization generate;
Described halogen-free flame retardants is made up of the main flame retardant of 84wt% and the secondary fire retardant of 16wt%, and wherein, main flame retardant is made up of the organophosphorus ester of 65wt% and the melamine polyphosphate of 35wt%, and secondary fire retardant is poly phosphate;
Described organophosphorus ester is chitin modified phosphate ester, its preparation method includes: by stirring in phosphorus oxychloride, tetramethylolmethane addition anhydrous acetonitrile, when nitrogen protection, be warming up to 60 DEG C, stirring 0.5h, after adding aluminum trichloride (anhydrous), it is continuously heating to 90 DEG C, stirs 1h, after solvent is distilled off, washing, dry, obtain tetramethylolmethane spiro-phosphate diacid chloride; Described tetramethylolmethane spiro-phosphate diacid chloride is added in methanesulfonic acid, adds chitosan and stir, when nitrogen protection, be warming up to 60 DEG C, stir 2h, washing, dry, obtain described chitin modified phosphate ester; Preferably, phosphorus oxychloride, tetramethylolmethane, aluminum chloride, chitosan weight proportion be: 6:1:0.08:0.8;
Described poly phosphate is resorcinol oligomeric phosphate; its preparation method includes: added by DOPO in dimethylbenzene; when nitrogen protection; heating is to 100 DEG C, and the lower dropping of stirring, dissolved with the xylene solution of paraformaldehyde, completes dropping in 1h; it is heated to reflux 6h; filter, washing, obtain DOPO-CH2OH, by described DOPO-CH2OH addition dichloromethane stirs, when nitrogen protection, adds phosphorus oxychloride, be warming up to 40 DEG C, stir 2h, after solvent is removed in distillation, wash, dry, obtain performed polymer; Adding resorcinol in described performed polymer, when nitrogen protection, heating, to 40 DEG C, adds aluminum trichloride (anhydrous) under stirring, is continuously heating to 90 DEG C, stirs 1h, after solvent is removed in distillation, and washing, dry, obtain described resorcinol oligomeric phosphate; Preferably, DOPO, paraformaldehyde, phosphorus oxychloride, resorcinol weight proportion be 1:0.2:0.5:0.6;
The intrinsic viscosity of described polyphenylene oxide is 0.5dl/g, and described polyphenylene oxide is poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene) ether; Described filling oil is naphthenic oil; Described antioxidant is three [2,4-di-tert-butyl-phenyl] phosphite ester; Described styrene resin is impact-resistant polystyrene; Described halogen-free flame retardant thermoplastic elastomer material also includes uvioresistant photo etching, coloring agent, lubricant and processing aid; Wherein, described uvioresistant photo etching includes UV powder; Described lubricant is ethylene bis stearic acid amide; Described coloring agent is oxidized black; Described processing aid is calcium carbonate.
Embodiment 3
A kind of halogen-free flame retardant thermoplastic elastomer material for electric wire, its raw material includes by weight: thermoplastic elastomer (TPE) 35 parts, halogen-free flame retardants 32 parts, polyphenylene oxide 22 parts, fills oil 11 parts, 0.3 part of antioxidant, styrene resin 3 parts;
Wherein, described thermoplastic elastomer (TPE) is made up of the hydrogenated styrene block copolymers of 70wt% and the thermoplastic vulcanizates elastomer of 30wt%; In the middle part of the polystyrene end block of described hydrogenated styrene block copolymers and polyolefin, the weight proportion of block is 1.05:1; Described hydrogenated styrene block copolymers is styrene-ethylene-butylene-styrene polymer and the compositions of styrene ethylene-propylene-styrene polymer; Described thermoplastic vulcanizates elastomer be by weight percentage the acrylic resin by 25% and 75% EP rubbers through dynamic vulcanization generate;
Described halogen-free flame retardants is made up of the main flame retardant of 75wt% and the secondary fire retardant of 25wt%, and wherein, main flame retardant is made up of the organic phosphate of 55wt% and the melamine polyphosphate of 45wt%, and secondary fire retardant is poly phosphate;
Described organic phosphate is n-trimethyl chitosan chloride modified phosphate, its preparation method includes: by stirring in phosphorus oxychloride, tetramethylolmethane addition anhydrous acetonitrile, when nitrogen protection, be warming up to 55 DEG C, stirring 0.7h, after adding aluminum trichloride (anhydrous), it is continuously heating to 85 DEG C, stirs 1.5h, after solvent is distilled off, washing, dry, obtain tetramethylolmethane spiro-phosphate diacid chloride; Described tetramethylolmethane spiro-phosphate diacid chloride is added in methanesulfonic acid, adds chitosan and stir, when nitrogen protection, be warming up to 50 DEG C, stir 3h, washing, dry, obtain described chitin modified phosphate ester; Being added by described chitin modified phosphate ester in isopropanol, drip sodium hydroxide solution, then drip ether agent of CTA under stirring condition, heating is to 30 DEG C, stirring 4h, acid adding regulates to neutrality, sucking filtration, washing, dry, obtain described n-trimethyl chitosan chloride modified phosphate; Wherein, phosphorus oxychloride, tetramethylolmethane, aluminum chloride, chitosan weight proportion be: 5:2:0.06:1; Described chitin modified phosphate ester, CTA weight proportion be: 1:1.5;
Described poly phosphate is resorcinol oligomeric phosphate; its preparation method includes: added by DOPO in dimethylbenzene; when nitrogen protection; heating is to 90 DEG C, and the lower dropping of stirring, dissolved with the xylene solution of paraformaldehyde, completes dropping in 2h; it is heated to reflux 5h; filter, washing, obtain DOPO-CH2OH, by described DOPO-CH2OH addition dichloromethane stirs, when nitrogen protection, adds phosphorus oxychloride, be warming up to 50 DEG C, stir 1.5h, after solvent is removed in distillation, wash, dry, obtain performed polymer; Resorcinol is added in described performed polymer, when nitrogen protection, heating, to 50 DEG C, adds aluminum trichloride (anhydrous) under stirring, it is continuously heating to 85 DEG C, stirring 2h, after solvent is removed in distillation, washing, dry, obtain described resorcinol oligomeric phosphate, wherein, DOPO, paraformaldehyde, phosphorus oxychloride, resorcinol weight proportion be 1:0.15:0.65:0.5;
The intrinsic viscosity of described polyphenylene oxide is 0.3dl/g; Described filling oil is paraffin oil; Described antioxidant is four [��-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester; Described styrene resin is impact-resistant polystyrene; Described halogen-free flame retardant thermoplastic elastomer material also includes uvioresistant photo etching, coloring agent, lubricant and processing aid; Described uvioresistant photo etching includes UV powder; Described lubricant is the combination of the double; two oleamide of ethylene, zinc stearate and calcium stearate; Described coloring agent is that iron oxide red, iron oxide yellow, titanium be Dracocephalum moldabium and the combination of chrome green; Described processing aid is the combination of Pulvis Talci, kieselguhr and mica powder.
Embodiment 4
A kind of halogen-free flame retardant thermoplastic elastomer material for electric wire, its raw material includes by weight: thermoplastic elastomer (TPE) 30 parts, halogen-free flame retardants 35 parts, polyphenylene oxide 25 parts, fills oil 12 parts, 0.4 part of antioxidant, styrene resin 4 parts;
Wherein, described thermoplastic elastomer (TPE) is made up of the hydrogenated styrene block copolymers of 65wt% and the thermoplastic vulcanizates elastomer of 35wt%; In the middle part of the polystyrene end block of described hydrogenated styrene block copolymers and polyolefin, the weight proportion of block is 1.1:1; Described hydrogenated styrene block copolymers is styrene-ethylene-butylene-styrene polymer; Described thermoplastic vulcanizates elastomer be by weight percentage the polyvinyl resin by 22% and 78% ethylene/octene rubber through dynamic vulcanization generate;
Described halogen-free flame retardants is made up of the main flame retardant of 70wt% and the secondary fire retardant of 30wt%, and wherein, main flame retardant is made up of the organic phosphate of 50wt% and the melamine polyphosphate of 50wt%, and secondary fire retardant is poly phosphate;
Described organic phosphate is n-trimethyl chitosan chloride modified phosphate, its preparation method includes: by stirring in phosphorus oxychloride, tetramethylolmethane addition anhydrous acetonitrile, when nitrogen protection, be warming up to 52 DEG C, stirring 0.8h, after adding aluminum trichloride (anhydrous), it is continuously heating to 86 DEG C, stirs 1.2h, after solvent is distilled off, washing, dry, obtain tetramethylolmethane spiro-phosphate diacid chloride; Described tetramethylolmethane spiro-phosphate diacid chloride is added in methanesulfonic acid, adds chitosan and stir, when nitrogen protection, be warming up to 55 DEG C, stir 2.5h, washing, dry, obtain described chitin modified phosphate ester; Being added by described chitin modified phosphate ester in isopropanol, drip sodium hydroxide solution, then drip ether agent of CTA under stirring condition, heating is to 45 DEG C, stirring 3h, acid adding regulates to neutrality, sucking filtration, washing, dry, obtain described n-trimethyl chitosan chloride modified phosphate; Wherein, phosphorus oxychloride, tetramethylolmethane, aluminum chloride, chitosan weight proportion be: 5:2:0.06:1.1; Described chitin modified phosphate ester, CTA weight proportion be: 1:2.5;
Described poly phosphate is resorcinol oligomeric phosphate; its preparation method includes: added by DOPO in dimethylbenzene; when nitrogen protection; heating is to 95 DEG C, and the lower dropping of stirring, dissolved with the xylene solution of paraformaldehyde, completes dropping in 2h; it is heated to reflux 5h; filter, washing, obtain DOPO-CH2OH, by described DOPO-CH2OH addition dichloromethane stirs, when nitrogen protection, adds phosphorus oxychloride, be warming up to 45 DEG C, stir 1.8h, after solvent is removed in distillation, wash, dry, obtain performed polymer; Resorcinol is added in described performed polymer, when nitrogen protection, heating, to 55 DEG C, adds aluminum trichloride (anhydrous) under stirring, it is continuously heating to 85 DEG C, stirring 2h, after solvent is removed in distillation, washing, dry, obtain described resorcinol oligomeric phosphate, wherein, DOPO, paraformaldehyde, phosphorus oxychloride, resorcinol weight proportion be 1:0.15:0.7:0.5;
The intrinsic viscosity of described polyphenylene oxide is 0.2dl/g, and described polyphenylene oxide is poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene) ether; Described filling oil is naphthenic oil; Described antioxidant is three [2,4-di-tert-butyl-phenyl] phosphite ester; Described styrene resin is high impact polystyrene; Described halogen-free flame retardant thermoplastic elastomer material also includes lubricant and processing aid; Described uvioresistant photo etching includes UV powder; Described lubricant is PE wax and dimethicone; Described processing aid is silicon dioxide.
The preparation method of the halogen-free flame retardant thermoplastic elastomer material being used for electric wire described in above-described embodiment 1-4 includes: by thermoplastic elastomer (TPE), fills oil, styrene resin, antioxidant addition high-speed mixer and mixing 0.2-0.4h, obtains masterbatch; Described masterbatch and polyphenylene oxide, halogen-free flame retardants are added in double screw extruder and plasticates, tie rod, cooling, pelletizing, obtaining the described halogen-free flame retardant thermoplastic elastomer material for electric wire, wherein, screw slenderness ratio is 55-64, screw speed is 300-500rpm, and processing temperature is 200-260 DEG C; Wherein, described processing temperature is particularly as follows: district's temperature 200 DEG C, two district's temperature 220 DEG C, three district's temperature 225 DEG C, four district's temperature 230 DEG C, five district's temperature 235 DEG C, six district's temperature 240 DEG C, seven district's temperature 245 DEG C, eight district's temperature 250 DEG C, nine district's temperature 255 DEG C, ten district's temperature 260 DEG C, 11 district's temperature 260 DEG C, No.12 District temperature 260 DEG C, 13 district's temperature 255 DEG C.
The halogen-free flame retardant thermoplastic elastomer material being used for electric wire described in above-described embodiment 1-4 is carried out performance test, and result is as shown in the table:
According to upper table analysis, the halogen-free flame retardant thermoplastic elastomer material being obtained in that by the scheme of above-described embodiment 1-4 after 136 DEG C of * 168h hot air agings stretching strength retentivity more than 75% and elongation at break conservation rate more than 75%, the 1.6mm thickness fire-retardant UL94 standard VO grade of burning, and UL1581VW-1 testing vertical flammability can be passed through;
The above; it is only the present invention preferably detailed description of the invention; but protection scope of the present invention is not limited thereto; any those familiar with the art is in the technical scope that the invention discloses; it is equal to replacement according to technical scheme and inventive concept thereof or is changed, all should be encompassed within protection scope of the present invention.
Claims (10)
1. the halogen-free flame retardant thermoplastic elastomer material for electric wire, it is characterised in that its raw material includes by weight: thermoplastic elastomer (TPE) 25-45 part, halogen-free flame retardants 25-40 part, polyphenylene oxide 15-30 part, fill oil 8-15 part, antioxidant 0.1-0.5 part, styrene resin 2-5 part;
Wherein, described thermoplastic elastomer (TPE) is made up of hydrogenated styrene block copolymers and thermoplastic vulcanizates elastomer, described hydrogenated styrene block copolymers is the 60-80% of described thermoplastic elastic body weight, and described thermoplastic vulcanizates elastomer is the 20-40% of thermoplastic elastic body weight;
Described halogen-free flame retardants is made up of main flame retardant and secondary fire retardant, and wherein, main flame retardant is made up of organic phosphate/ester and melamine polyphosphate, and secondary fire retardant is poly phosphate.
2. the halogen-free flame retardant thermoplastic elastomer material for electric wire according to claim 1, it is characterised in that in the middle part of the polystyrene end block of described hydrogenated styrene block copolymers and polyolefin, the weight proportion of block is 0.72-1.38:1; Preferably, described hydrogenated styrene block copolymers is the combination of styrene-ethylene-butylene-styrene polymer, styrene ethylene-propylene-styrene polymer a kind of or two kinds.
3. the halogen-free flame retardant thermoplastic elastomer material for electric wire according to claims 1 or 2, it is characterized in that, the olefinic rubber that described thermoplastic vulcanizates elastomer is the vistanex by 20-35% and 65-80% by weight percentage generates through dynamic vulcanization; Preferably, described vistanex is acrylic resin or polyvinyl resin, and described olefinic rubber is EP rubbers or Ethylene-octene rubber.
4. the halogen-free flame retardant thermoplastic elastomer material for electric wire according to any one of claim 1-3, it is characterised in that described halogen-free flame retardants is made up of the secondary fire retardant of the main flame retardant of 66-84% and 16-34% by weight percentage; Described organic phosphate/ester is the 45-65% of described main flame retardant weight, and described melamine polyphosphate is the 35-55% of described main flame retardant weight.
5. the halogen-free flame retardant thermoplastic elastomer material for electric wire according to any one of claim 1-4, it is characterized in that, described organophosphorus ester is chitin modified phosphate ester, its preparation method includes: will stir in phosphorus oxychloride, tetramethylolmethane addition anhydrous acetonitrile, when nitrogen protection, it is warming up to 50-60 DEG C, stirring 0.5-1h, after adding aluminum trichloride (anhydrous), it is continuously heating to 80-90 DEG C, stirs 1-2h, after solvent is distilled off, washing, dry, obtain tetramethylolmethane spiro-phosphate diacid chloride; Described tetramethylolmethane spiro-phosphate diacid chloride is added in methanesulfonic acid, adds chitosan and stir, when nitrogen protection, be warming up to 40-60 DEG C, stir 2-4h, washing, dry, obtain described chitin modified phosphate ester; Preferably, phosphorus oxychloride, tetramethylolmethane, aluminum chloride, chitosan weight proportion be: 4-6:1-3:0.05-0.08:0.8-1.2;
Preferably, described organic phosphate is n-trimethyl chitosan chloride modified phosphate, and its preparation method includes: added by described chitin modified phosphate ester in isopropanol, drips sodium hydroxide solution under stirring condition, drip ether agent of CTA again, heating, to 30-50 DEG C, stirs 2-4h, and acid adding regulates to neutrality, sucking filtration, washing, dry, obtain described n-trimethyl chitosan chloride modified phosphate; Preferably, described chitin modified phosphate ester, CTA weight proportion be: 1:1.5-3.
6. the halogen-free flame retardant thermoplastic elastomer material for electric wire according to any one of claim 1-5; it is characterized in that, described poly phosphate is resorcinol oligomeric phosphate, and its preparation method includes: added by DOPO in dimethylbenzene; when nitrogen protection; heating is to 80-100 DEG C, and the lower dropping of stirring, dissolved with the xylene solution of paraformaldehyde, completes dropping in 1-3h; it is heated to reflux 4-6h; filter, washing, obtain DOPO-CH2OH, by described DOPO-CH2OH addition dichloromethane stirs, when nitrogen protection, adds phosphorus oxychloride, be warming up to 40-60 DEG C, stir 1-2h, after solvent is removed in distillation, wash, dry, obtain performed polymer; Adding resorcinol in described performed polymer, when nitrogen protection, heating, to 40-60 DEG C, adds aluminum trichloride (anhydrous) under stirring, it is continuously heating to 80-90 DEG C, stirs 1-3h, after solvent is removed in distillation, washing, dry, obtain described resorcinol oligomeric phosphate; Preferably, DOPO, paraformaldehyde, phosphorus oxychloride, resorcinol weight proportion be 1:0.1-0.2:0.5-0.8:0.4-0.6.
7. the halogen-free flame retardant thermoplastic elastomer material for electric wire according to any one of claim 1-6, it is characterised in that the intrinsic viscosity of described polyphenylene oxide is 0.1-0.5dl/g; Preferably, described polyphenylene oxide is poly-(2,6-dimethyl-Isosorbide-5-Nitrae-phenylene) ether.
8. the halogen-free flame retardant thermoplastic elastomer material for electric wire according to any one of claim 1-7, it is characterised in that described filling oil is paraffin oil or naphthenic oil; Described antioxidant is four [��-(3,5-di-tert-butyl-hydroxy phenyl) propanoic acid] pentaerythritol ester or three [2,4-di-tert-butyl-phenyl] phosphite esters; Described styrene resin is impact-resistant polystyrene.
9. the halogen-free flame retardant thermoplastic elastomer material for electric wire according to any one of claim 1-8, it is characterized in that, described halogen-free flame retardant thermoplastic elastomer material also includes one or more combination of uvioresistant photo etching, coloring agent, lubricant, processing aid;
Preferably, described uvioresistant photo etching includes UV powder; Described lubricant is one or more combination of ethylene bis stearic acid amide, the double; two oleamide of ethylene, zinc stearate, calcium stearate, PE wax, dimethicone; Described coloring agent is that oxidized black, iron oxide red, iron oxide yellow, titanium be Dracocephalum moldabium, one or more combination of chrome green; Described processing aid is one or more combination of calcium carbonate, Pulvis Talci, kieselguhr, mica powder, silicon dioxide.
10. the preparation method of the halogen-free flame retardant thermoplastic elastomer material for electric wire according to any one of claim 1-9, it is characterized in that, including: by thermoplastic elastomer (TPE), fill oil, styrene resin, antioxidant addition high-speed mixer and mixing 0.2-0.4h, obtain masterbatch; Described masterbatch and polyphenylene oxide, halogen-free flame retardants are added in double screw extruder and plasticates, tie rod, cooling, pelletizing, obtaining the described halogen-free flame retardant thermoplastic elastomer material for electric wire, wherein, screw slenderness ratio is 55-64, screw speed is 300-500rpm, and processing temperature is 200-260 DEG C; Preferably, described processing temperature is particularly as follows: district's temperature 200 DEG C, two district's temperature 220 DEG C, three district's temperature 225 DEG C, four district's temperature 230 DEG C, five district's temperature 235 DEG C, six district's temperature 240 DEG C, seven district's temperature 245 DEG C, eight district's temperature 250 DEG C, nine district's temperature 255 DEG C, ten district's temperature 260 DEG C, 11 district's temperature 260 DEG C, No.12 District temperature 260 DEG C, 13 district's temperature 255 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610021557.2A CN105623180B (en) | 2016-01-12 | 2016-01-12 | Halogen-free flame retardant thermoplastic elastomer material and preparation method thereof for electric wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610021557.2A CN105623180B (en) | 2016-01-12 | 2016-01-12 | Halogen-free flame retardant thermoplastic elastomer material and preparation method thereof for electric wire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105623180A true CN105623180A (en) | 2016-06-01 |
| CN105623180B CN105623180B (en) | 2018-10-09 |
Family
ID=56038552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610021557.2A Active CN105623180B (en) | 2016-01-12 | 2016-01-12 | Halogen-free flame retardant thermoplastic elastomer material and preparation method thereof for electric wire |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105623180B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117788A (en) * | 2016-06-30 | 2016-11-16 | 中广核高新核材集团（东莞）祈富新材料有限公司 | A kind of frosted electrification line thermoplastic elastomer (TPE) and preparation method thereof |
| CN106674734A (en) * | 2016-12-14 | 2017-05-17 | 天长市康宁甘油科技有限公司 | Flame-retardant and smoke-suppressant type wood-plastic composite material |
| CN106675041A (en) * | 2016-12-26 | 2017-05-17 | 上海至正道化高分子材料股份有限公司 | Thermoplastic elastomer material for 125-DEG C new energy automobile cable and preparation method thereof |
| CN106751028A (en) * | 2016-12-14 | 2017-05-31 | 天长市康宁甘油科技有限公司 | A kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material and preparation method thereof |
| CN106751664A (en) * | 2016-12-14 | 2017-05-31 | 天长市康宁甘油科技有限公司 | A kind of wear resistant and impact resistant thermoplastic compounds and preparation method thereof |
| CN107674408A (en) * | 2017-11-08 | 2018-02-09 | 安徽省瑞发复合材料制造有限公司 | A kind of high tenacity high flame-retardant polyurethane circuit board material |
| CN107778836A (en) * | 2017-11-08 | 2018-03-09 | 安徽省瑞发复合材料制造有限公司 | A kind of special compound polyurethane material of circuit board |
| CN108395729A (en) * | 2018-02-01 | 2018-08-14 | 天津科创复兴科技咨询有限公司 | A kind of high temperature resistant TPE material and its preparation method and application |
| CN109401321A (en) * | 2018-09-27 | 2019-03-01 | 唐山师范学院 | Expandable flame retardant room temperature vulcanized silicone rubber formula and expandable flame retardant room temperature vulcanized silicone rubber |
| CN109762108A (en) * | 2018-12-20 | 2019-05-17 | 上海新上化高分子材料有限公司 | Permanent polyolefin flame-retardant CABLE MATERIALS of environment-friendly type and preparation method thereof |
| CN110029513A (en) * | 2019-04-18 | 2019-07-19 | 宝应县科达电缆料有限公司 | A kind of preparation method of the wire and cable netted gasket for packing of PP |
| EP3540000A1 (en) | 2018-03-16 | 2019-09-18 | Stutz, Felix Benjamin | Flame retardant polyamide 6 master batch and fibers made thereof |
| CN115594188A (en) * | 2022-11-08 | 2023-01-13 | 赢胜节能集团股份有限公司（Cn） | Aerogel-based heat-preservation and heat-insulation composite material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5294654A (en) * | 1991-08-12 | 1994-03-15 | General Electric Company | Flame-retarded, conductive compositions which include polyphenylene ether and polystyrene resins |
| CN1930230A (en) * | 2004-01-07 | 2007-03-14 | 通用电气公司 | Flexible poly(arylene ether) composition and articles thereof |
| CN1961042A (en) * | 2004-04-01 | 2007-05-09 | 通用电气公司 | Flame retardant composition |
| CN101309970A (en) * | 2005-11-16 | 2008-11-19 | 通用电气公司 | Thermoplastic method, composition, and article |
| CN101679740A (en) * | 2007-05-25 | 2010-03-24 | 沙伯基础创新塑料知识产权有限公司 | Flame retardant thermoplastic composition and articles comprising the same |
| CN101838538A (en) * | 2009-07-17 | 2010-09-22 | 大连理工大学 | Poly-phosphate flame retardant containing DOPO side-chain structure and preparation method thereof |
| CN103897324A (en) * | 2012-12-27 | 2014-07-02 | 中纺投资发展股份有限公司 | Halogen-free flame-retardant polyphenyl ether composition and preparation method thereof |
-
2016
- 2016-01-12 CN CN201610021557.2A patent/CN105623180B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5294654A (en) * | 1991-08-12 | 1994-03-15 | General Electric Company | Flame-retarded, conductive compositions which include polyphenylene ether and polystyrene resins |
| CN1930230A (en) * | 2004-01-07 | 2007-03-14 | 通用电气公司 | Flexible poly(arylene ether) composition and articles thereof |
| CN1961042A (en) * | 2004-04-01 | 2007-05-09 | 通用电气公司 | Flame retardant composition |
| CN101309970A (en) * | 2005-11-16 | 2008-11-19 | 通用电气公司 | Thermoplastic method, composition, and article |
| CN101679740A (en) * | 2007-05-25 | 2010-03-24 | 沙伯基础创新塑料知识产权有限公司 | Flame retardant thermoplastic composition and articles comprising the same |
| CN101838538A (en) * | 2009-07-17 | 2010-09-22 | 大连理工大学 | Poly-phosphate flame retardant containing DOPO side-chain structure and preparation method thereof |
| CN103897324A (en) * | 2012-12-27 | 2014-07-02 | 中纺投资发展股份有限公司 | Halogen-free flame-retardant polyphenyl ether composition and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 范瑞兰，王利生，李弥异: "磷氮阻燃剂的合成及其应用", 《化工新型材料》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106117788A (en) * | 2016-06-30 | 2016-11-16 | 中广核高新核材集团（东莞）祈富新材料有限公司 | A kind of frosted electrification line thermoplastic elastomer (TPE) and preparation method thereof |
| CN106117788B (en) * | 2016-06-30 | 2018-07-31 | 中广核高新核材集团（东莞）祈富新材料有限公司 | A kind of frosted electrification line thermoplastic elastomer (TPE) and preparation method thereof |
| CN106674734A (en) * | 2016-12-14 | 2017-05-17 | 天长市康宁甘油科技有限公司 | Flame-retardant and smoke-suppressant type wood-plastic composite material |
| CN106751028A (en) * | 2016-12-14 | 2017-05-31 | 天长市康宁甘油科技有限公司 | A kind of high-efficiency environment friendly flame-proofed thermoplastic vulcanized rubber material and preparation method thereof |
| CN106751664A (en) * | 2016-12-14 | 2017-05-31 | 天长市康宁甘油科技有限公司 | A kind of wear resistant and impact resistant thermoplastic compounds and preparation method thereof |
| CN106675041A (en) * | 2016-12-26 | 2017-05-17 | 上海至正道化高分子材料股份有限公司 | Thermoplastic elastomer material for 125-DEG C new energy automobile cable and preparation method thereof |
| CN107674408A (en) * | 2017-11-08 | 2018-02-09 | 安徽省瑞发复合材料制造有限公司 | A kind of high tenacity high flame-retardant polyurethane circuit board material |
| CN107778836A (en) * | 2017-11-08 | 2018-03-09 | 安徽省瑞发复合材料制造有限公司 | A kind of special compound polyurethane material of circuit board |
| CN108395729A (en) * | 2018-02-01 | 2018-08-14 | 天津科创复兴科技咨询有限公司 | A kind of high temperature resistant TPE material and its preparation method and application |
| EP3540000A1 (en) | 2018-03-16 | 2019-09-18 | Stutz, Felix Benjamin | Flame retardant polyamide 6 master batch and fibers made thereof |
| WO2019175421A1 (en) | 2018-03-16 | 2019-09-19 | Stutz Felix Benjamin | Flame retardant master batch for polyamide 6 and fibers made thereof |
| CN109401321A (en) * | 2018-09-27 | 2019-03-01 | 唐山师范学院 | Expandable flame retardant room temperature vulcanized silicone rubber formula and expandable flame retardant room temperature vulcanized silicone rubber |
| CN109762108A (en) * | 2018-12-20 | 2019-05-17 | 上海新上化高分子材料有限公司 | Permanent polyolefin flame-retardant CABLE MATERIALS of environment-friendly type and preparation method thereof |
| CN109762108B (en) * | 2018-12-20 | 2021-04-30 | 上海新上化高分子材料有限公司 | Environment-friendly permanent polyolefin flame-retardant cable material and preparation method thereof |
| CN110029513A (en) * | 2019-04-18 | 2019-07-19 | 宝应县科达电缆料有限公司 | A kind of preparation method of the wire and cable netted gasket for packing of PP |
| CN115594188A (en) * | 2022-11-08 | 2023-01-13 | 赢胜节能集团股份有限公司（Cn） | Aerogel-based heat-preservation and heat-insulation composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105623180B (en) | 2018-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105623180A (en) | Halogen-free flame retardant thermoplastic elastomer material for electric wires and cables and preparation method thereof | |
| CN101845197B (en) | High-performance halogen-free flame retardant ABS modified resin and preparation method thereof | |
| CN105860412B (en) | Halogen-free flame retardant thermoplastic elastomer material and preparation method thereof for wire and cable | |
| CN101824182B (en) | Halogen-free expansion type flame-retardant thermoplastic elastomer composition | |
| CN102030978B (en) | Halogen-free flame retardant polyphenylene oxide polyphenyl ether (PPE) cable material composition and preparation method thereof | |
| CN105907019B (en) | Halogen-free flame retardant thermoplastic elastomer material and preparation method thereof for wire and cable | |
| CN108276659B (en) | High-flame-retardance high-heat-resistance MPP (modified Polypropylene) pipe and preparation method thereof | |
| CN102585428A (en) | Flexible halogen-free flame-retardant polyphenyl ether electric wire cable shield material and preparation method thereof | |
| CN103910990B (en) | A kind of thermoplastic halogen-free flame retarding polyphenylene oxide elastomer cable material and preparation method thereof | |
| KR101512508B1 (en) | Polyphenyl ether elastomer composition | |
| CA2796084C (en) | Styrenic block copolymer-based composition with enhanced flame-retardant properties | |
| KR101466277B1 (en) | Thermoplastic resin composition and article including same | |
| KR20130108094A (en) | Halogen-free, flame retardant composition comprising crosslinked silane-g-eva | |
| CN109206829B (en) | High-yellowing-resistance precipitation-resistance halogen-free flame-retardant thermoplastic elastomer composition and preparation method thereof | |
| US9938401B2 (en) | Fire retardant systems for polymers that enable flexibility and strength | |
| CN102786764A (en) | Scraping resistance halogen-free flame retardant thermoplastic elastomer composition and preparation method of composition | |
| CN105273352A (en) | Halogen-free flame-retardant TPE material and preparation method thereof | |
| CN103897324A (en) | Halogen-free flame-retardant polyphenyl ether composition and preparation method thereof | |
| CN102617972A (en) | Halogen-free flame-retardant styrene-series resin composition and preparation method thereof | |
| CN112250985B (en) | Halogen-free flame-retardant ABS composition and preparation method and application thereof | |
| CN109503941A (en) | Halogen-free anti-flaming polypropylene material and preparation method thereof | |
| CN103450549A (en) | Expansive type halogen-free flame-retardant cable material | |
| CN107987516B (en) | TPU/terpolymer nylon composite halogen-free flame-retardant cable material and preparation method thereof | |
| CN101161719B (en) | Special material for injection grade non-halogen flame-retardant wire plug and preparation method thereof | |
| CN106046651A (en) | High-temperature-resistant polymer composite and preparing method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190731 Address after: 242300 Anhui province Xuancheng City Dongcheng Road, Ningguo economic and Technological Development Zone No. 81 Lek River Park Patentee after: Anhui Zhonghan Polymer Technology Co Ltd Address before: 242300 Anhui province Xuancheng City Dongcheng Road, Ningguo economic and Technological Development Zone No. 81 Lek River Park Patentee before: Anhui Zhongding Rubber & Plastic Products Co., Ltd. |