CN108117715A - A kind of halogen-free flame-retardant master batch and preparation method thereof - Google Patents

A kind of halogen-free flame-retardant master batch and preparation method thereof Download PDF

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Publication number
CN108117715A
CN108117715A CN201711460205.8A CN201711460205A CN108117715A CN 108117715 A CN108117715 A CN 108117715A CN 201711460205 A CN201711460205 A CN 201711460205A CN 108117715 A CN108117715 A CN 108117715A
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halogen
master batch
free flame
area
retardant
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刘华夏
周侃
翟勇强
唐海兰
田凯丽
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GUANGDONG JUSHI CHEMICAL INDUSTRY Co Ltd
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GUANGDONG JUSHI CHEMICAL INDUSTRY Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention discloses a kind of halogen-free flame-retardant master batch and preparation method thereof, which is made of the raw material of following mass parts：Acrylic resin：8~38 parts；Halogen-free expansion fire retardant：60~90 parts；Antioxidant：0.1~0.4 part；Lubricant：0.5~1.5 part；Anti-dripping agent：0.1~0.5 part.Its preparation method is as follows：1) mixed at high speed of material；2) the mixer plasticizing of material；3) plasticizing of material disperse, squeeze out, pelletizing, sieving.The halogen-free flame-retardant master batch excellent fireproof performance of the present invention, and physical mechanical property is better than powder fire retardant, preparation process is simple, the halogen-free flame-retardant master batch can reduce production cost, improve production efficiency with the direct mixed injection molding of polypropylene, reduce processing dust, improve the dispersiveness of fire retardant.

Description

A kind of halogen-free flame-retardant master batch and preparation method thereof
Technical field
The present invention relates to a kind of halogen-free flame-retardant master batchs and preparation method thereof.
Background technology
Polypropylene (PP) belongs to one of five big general-purpose plastics, is a kind of semicrystalline thermoplastic, possesses good Mechanical property and processing performance, and cost-effective, have to compare and are widely applied in many fields.However, PP is used as one in itself Kind of plastics are as most of plastics there are inflammable defect, it is necessary to carry out flame-retardant modified to meet actual demand.At present, city Fire-retardant PP on face is mostly to be carried out by adding powder fire retardant flame-retardant modified, and is mostly used among these There is halogen fire retardant.The noxious materials such as hydrogen halides can be generated during PP product burns containing halogen fire retardant, and can be given out a large amount of black Color smog, threatens human health, while escape when also fire occurring, rescues and cause obstruction.Therefore, halogen-free environment-friendly flame-proof Agent causes the attention of domestic and international fire retardant developer.
The halogen-free environment-friendlyflame flame retardant of PP is presently used for mainly including following two：1) hydrated magnesium, hydrated alumina, The inorganic compounds such as aqua oxidation tin, inorganic silicon；2) organic compounds such as phosphate, phosphorus nitrogen carbon compound, phosphorus-nitrogen compound. Smoke amount is small during PP product burns containing halogen-free flame retardants and will not generate toxic gas, this is the PP systems containing halogen fire retardant Product cannot than.But there is also great number of issues for existing halogen-free flame retardants：1) the flame retarding efficiency ratio of halogen-free flame retardants has halogen resistance It is low to fire agent, so additive amount bigger, occurs separation of powder and granule, to processed when easily causing powder fire retardant and PP pellet mixing blankings Cheng Zaocheng hinders, meanwhile, more powder can generate more frictions in processing, also more tight to the abrasion of process equipment Weight；2) for the grain size of halogen-free flame retardants mostly below 25 μm, grain size is smaller, and a large amount of airborne dusts can be generated when weighing, process, transporting, Influence to work and production environment is big, and easily reunites during the fire retardant processing of small particle, poor dispersion；3) P-N type is fire-retardant The water solubility of agent is big, thermal stability is poor, and when processing easily reduces foaming, neatly is precipitated.
Halogen-free flame-retardant master batch is by combination, modification and the synergistic effect of a variety of fire-retardant compositions, and combination pair Screw rod or mixer such as are squeezed out, are kneaded, are granulated at a kind of granular product obtained from techniques.Use halogen-free flame-retardant master batch generation Be processed for powder fire retardant, have many advantages, such as not airborne dust, do not reunite, be easily scattered.In addition, halogen-free flame-retardant master batch and PP pellets It will not separate, the friction with equipment is reduced, and equipment attrition accordingly mitigates, and halogen-free flame-retardant master batch can be with changing without fire-retardant The direct mixed injection molding of PP particles of property, avoids stop long in a device and degrades, decomposes, also can directly be molded into Type is eliminated twin-screw extrusion this process carried out using powder fire retardant needs, improves production efficiency, reduce production Cost.
However, existing halogen-free flame-retardant master batch generally existing complex production process, need special process equipment, performance without Method fully meets the defects of actual demand, can not also large-scale industrial production application.
The content of the invention
It is an object of the invention to provide a kind of halogen-free flame-retardant master batchs and preparation method thereof.
The technical solution used in the present invention is：
A kind of halogen-free flame-retardant master batch is made of the raw material of following mass parts：
Acrylic resin：8~38 parts；
Halogen-free expansion fire retardant：60~90 parts；
Antioxidant：0.1~0.4 part；
Lubricant：0.5~1.5 part；
Anti-dripping agent：0.1~0.5 part.
The acrylic resin is at least one in homopolypropylene, block copolymerization polypropylene, atactic copolymerized polypropene Kind, melt index be 25~105g/10min, 230 DEG C/2.16kg.
The halogen-free expansion fire retardant is by acid source, source of the gas and carbon source according to mass ratio (4~6)：(1~2)：(1~2) Composition, acid source are at least one of ammonium polyphosphate, melamine polyphosphate, melamine pyrophosphate, and source of the gas is trimerization Cyanamide, carbon source are at least one of triazine derivative, pentaerythrite, bipentaerythrite, polyol.
The degree of polymerization of the ammonium polyphosphate is 1000~1200, and the mass percentage of phosphorus is 31%~32%, nitrogen Mass percentage is 14.5%~15.5%.
The grain size of the melamine is 4~6 μm, and the mass percentage of phosphorus is 12%~13%, the quality hundred of nitrogen It is 42%~44% to divide content.
The triazine derivative is at least one of formula 1, formula 2 and compound shown in formula 3：
Wherein, R1、R2For-H ,-C6H5、-C6H4OH, morpholine, piperidines ,-CyH2y-O-R3In one kind, 1≤y≤8, R3 For-H, C1~C8Alkyl, C2~C6Alkenyl in one kind, X isIn one Kind, 2≤Z≤6.
The antioxidant is 1,2- double [β-(3,5- di-tert-butyl-hydroxy phenyls) propionyl] hydrazine, four [methyl-(3,5- Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, double [[3- (the dodecane sulphur of 3- (dodecylthio) propionic acid -2,2- Base)-propionyloxy] methyl] -1,3- propylene glycol esters, at least one of three (2,4- di-t-butyls) phenyl-phosphites.
The lubricant is at least one of polyethylene wax, stearic acid, ethylenebisstearamide.
The anti-dripping agent is pure powder type anti-drip agents.
The preparation method of above-mentioned halogen-free flame-retardant master batch, comprises the following steps：
1) acrylic resin, antioxidant, lubricant and anti-dripping agent are added in into high-speed mixer, are uniformly mixed, then by nothing Halogen expansion type flame retardant adds in high-speed mixer, is uniformly mixed；
2) adding pressure type rolling mixing built-in temperature is risen to 140~145 DEG C, the material for adding in step 1) carries out mixing, machine Interior temperature often rises 15 DEG C of exhausts once, and control built-in temperature is no more than 180 DEG C；
3) material in the mixer that rolls is transferred to double screw extruder, fully plasticizing is scattered, using Single screw extrusion Machine conveying cooling, then water ring pelletizing is carried out, it sieves, obtains halogen-free flame-retardant master batch.
The flip angle of the convertible mixer is 135~145 degree, the operating pressure of the hammer that pressurizes is 0.8~ 0.9MPa。
The screw slenderness ratio of the double screw extruder is (30~35)：1, screw diameter is 70~75mm, and screw rod turns Speed is 120~250r/min, no head, and each area's temperature is：One 170~180 DEG C of area, 180~185 DEG C of two-three area, four-five areas 175~180 DEG C, 170~175 DEG C of six-seven area, 160~170 DEG C of 8th area.
The screw slenderness ratio of the single screw extrusion machine is (10~15)：1, screw diameter be 145~155mm, screw rod Rotating speed is 15~30r/min, and each area's temperature is：One 145~155 DEG C of area, 145~155 DEG C of 2nd area, 145~155 DEG C of 3rd area, machine 155~165 DEG C of temperature of head.
The beneficial effects of the invention are as follows：The halogen-free flame-retardant master batch excellent fireproof performance of the present invention, and physical mechanical property is excellent In powder fire retardant, preparation process is simple, which can reduce and be produced into the direct mixed injection molding of polypropylene This, improves production efficiency, reduces processing dust, improve the dispersiveness of fire retardant.
1) for halogen-free flame-retardant master batch of the invention using polypropylene as carrier, effective content is high, avoids carrier to polypropylene system The influence of moral character energy；
2) present invention is tentatively plasticized using mixer, avoids the airborne dust in process, while is avoided follow-up There is separation of powder and granule during twin-screw blanking；
3) present invention ensure that the continuity and uniformity of blanking using bipyramid forced feed machine blanking；
4) mode that the present invention is combined using double screw extruder+single screw extrusion machine ensure that the scattered of fire retardant；
5) present invention carries out pelletizing using the mode of water ring pelletizing, ensure that the good appearance of halogen-free flame-retardant master batch is homogeneous, And not clay；
6) the continuous production mode that the present invention is squeezed out using mixer+bis- ranks, production efficiency is high, it is easy to operate, it can be achieved that Industrialization large-scale production.
Specific embodiment
A kind of halogen-free flame-retardant master batch is made of the raw material of following mass parts：
Acrylic resin：8~38 parts；
Halogen-free expansion fire retardant：60~90 parts；
Antioxidant：0.1~0.4 part；
Lubricant：0.5~1.5 part；
Anti-dripping agent：0.1~0.5 part.
Preferably, the acrylic resin is homopolypropylene, in block copolymerization polypropylene, atactic copolymerized polypropene At least one, melt index be 25~105g/10min, 230 DEG C/2.16kg.
Preferably, the halogen-free expansion fire retardant by acid source, source of the gas and carbon source according to mass ratio (4~6)：(1~ 2)：(1~2) form, acid source is ammonium polyphosphate, melamine polyphosphate, at least one of melamine pyrophosphate, gas Source is melamine, and carbon source is at least one of triazine derivative, pentaerythrite, bipentaerythrite, polyol.
It is further preferred that the halogen-free expansion fire retardant is by ammonium polyphosphate, melamine and triazine derivative According to mass ratio (4~6)：(1~2)：(1~2) form.
Preferably, the degree of polymerization of the ammonium polyphosphate is 1000~1200, the mass percentage of phosphorus for 31%~ 32%, the mass percentage of nitrogen is 14.5%~15.5%.
Preferably, the density of the ammonium polyphosphate is 1.8~1.9g/cm3, (25 DEG C, 10% suspension) of pH value is 7.5 ~9.0, (25 DEG C, 10% suspension) of viscosity is 45~50mPas.
Preferably, the grain size of the melamine is 4~6 μm, and the mass percentage of phosphorus is 12%~13%, nitrogen Mass percentage is 42%~44%.
Preferably, (25 DEG C, 10% suspension) of the pH value of the melamine is 5.0~6.0.
Preferably, the triazine derivative is at least one of formula 1, formula 2 and compound shown in formula 3：
Wherein, R1、R2For-H ,-C6H5、-C6H4OH, morpholine, piperidines ,-CyH2y-O-R3In one kind, 1≤y≤8, R3 For-H, C1~C8Alkyl, C2~C6Alkenyl in one kind, X isIn one Kind, 2≤Z≤6.
Preferably, the antioxidant is 1,2- double [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, four [first Base-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol ester, the double [[3- (ten of 3- (dodecylthio) propionic acid -2,2- Two alkylthio groups)-propionyloxy] methyl] -1,3- propylene glycol esters, at least one of three (2,4- di-t-butyls) phenyl-phosphites.
Preferably, the lubricant is at least one of polyethylene wax, stearic acid, ethylenebisstearamide.
Preferably, the anti-dripping agent is pure powder type anti-drip agents.
The preparation method of above-mentioned halogen-free flame-retardant master batch, comprises the following steps：
1) acrylic resin, antioxidant, lubricant and anti-dripping agent are added in into high-speed mixer, are uniformly mixed, then by nothing Halogen expansion type flame retardant adds in high-speed mixer, is uniformly mixed；
2) adding pressure type rolling mixing built-in temperature is risen to 140~145 DEG C, the material for adding in step 1) carries out mixing, machine Interior temperature often rises 15 DEG C of exhausts once, and control built-in temperature is no more than 180 DEG C；
3) material in the mixer that rolls is transferred to double screw extruder, fully plasticizing is scattered, using Single screw extrusion Machine conveying cooling, then water ring pelletizing is carried out, it sieves, obtains halogen-free flame-retardant master batch.
Preferably, the preparation method of above-mentioned halogen-free flame-retardant master batch, comprises the following steps：
1) acrylic resin, antioxidant, lubricant and anti-dripping agent are added in into high-speed mixer, 1000~1500r/ of rotating speed Min stirs 2~3min, then halogen-free expansion fire retardant added in high-speed mixer, and 1500~2000r/min of rotating speed stirrings 3~ 5min；
2) adding pressure type rolling mixing built-in temperature is risen to 140~145 DEG C, the material for adding in step 1) carries out mixing, control 40~60r/min of rotor speed processed, built-in temperature often rise 15 DEG C of exhausts once, and control built-in temperature is no more than 180 DEG C, mixing 20~25min, until material is tentatively plasticized；
3) material in the mixer that rolls is sent into double screw extruder by bipyramid forced feed machine, controls bipyramid rotating speed 8~15r/min, fully plasticizing are scattered, convey and cool down using single screw extrusion machine, then carry out water ring pelletizing, sieve, obtain nothing Halogen fire-retardant master granule.
Preferably, the flip angle of the convertible mixer is 135~145 degree, and the operating pressure for the hammer that pressurizes is 0.8 ~0.9MPa.
Preferably, the screw slenderness ratio of the double screw extruder is (30~35)：1, screw diameter is 70~75mm, Screw speed is 120~250r/min, and no head, each area's temperature is：One 170~180 DEG C of area, 180~185 DEG C of two-three area, Four-five 175~180 DEG C of areas, 170~175 DEG C of six-seven area, 160~170 DEG C of 8th area.
Preferably, the screw slenderness ratio of the single screw extrusion machine is (10~15)：1, screw diameter for 145~ 155mm, screw speed are 15~30r/min, and each area's temperature is：One 145~155 DEG C of area, 145~155 DEG C of 2nd area, three areas 145 ~155 DEG C, 155~165 DEG C of head temperature.
The present invention is made further explanation and description with reference to specific embodiment.
Embodiment 1：
A kind of halogen-free flame-retardant master batch is made of the raw material of following mass parts：
Block copolymerization polypropylene (BH975MO, Borealis, melt index 38g/10min, 230 DEG C of test condition/ 2.16kg)：38 parts；
(mass ratio of ammonium polyphosphate, melamine and piperidyl triazine is 4 to halogen-free expansion fire retardant:2:1, code name FR- 1)：60 parts；
Antioxidant 1010 (trade mark, Shandong San Feng Chemical Co., Ltd.s)：0.1 part；
Irgasfos 168 (Shandong San Feng Chemical Co., Ltd.s)：0.2 part；
PE waxes (BN-500, Qingdao Bang Ni Chemical Co., Ltd.s)：1 part；
Ethylene bis stearic acid amide (EB-FF, Japanese Kao)：0.5 part；
Pure powder type anti-dripping agent (M532, Daikin)：0.2 part.
The preparation method of above-mentioned halogen-free flame-retardant master batch is as follows：
1) by block copolymerization polypropylene, antioxidant 1010, irgasfos 168, PE waxes, ethylene bis stearic acid amide and pure powder type Anti-dripping agent adds in high-speed mixer, rotating speed 1500r/min stirring 2min, then halogen-free expansion fire retardant is added in mixed at high speed Machine, rotating speed 1500r/min stirrings 5min；
2) adding pressure type rolling mixing built-in temperature is risen to 140~145 DEG C, the material for adding in step 1) carries out mixing, control Rotor speed 50r/min processed, built-in temperature often rise 15 DEG C of exhausts once, and control built-in temperature is no more than 180 DEG C, mixing 20min, until material is tentatively plasticized；
3) material in the mixer that rolls is sent into double screw extruder by bipyramid forced feed machine, controls bipyramid rotating speed 15r/min, fully plasticizing are scattered, convey and cool down using single screw extrusion machine, then carry out water ring pelletizing, sieve, obtain Halogen Fire-retardant master granule.
Note：The screw slenderness ratio of the double screw extruder is 30:1, screw diameter 75mm, screw speed 120 ~250r/min, no head, each area's temperature are：One 180 DEG C of area, 185 DEG C of two-three area, 180 DEG C of four-five area, six-seven areas 175 DEG C, 170 DEG C of 8th area；The screw slenderness ratio of the single screw extrusion machine is 15:1, screw diameter 155mm, screw speed are 15~30r/min, each area's temperature are：One 155 DEG C of area, 155 DEG C of 2nd area, 155 DEG C of 3rd area, 165 DEG C of head temperature.
Embodiment 2：
A kind of halogen-free flame-retardant master batch is made of the raw material of following mass parts：
Block copolymerization polypropylene (BH975MO, Borealis, melt index 38g/10min, 230 DEG C of test condition/ 2.16kg)：28 parts；
(mass ratio of ammonium polyphosphate, melamine and piperidyl triazine is 4 to halogen-free expansion fire retardant:2:1, code name FR- 1)：70 parts；
Antioxidant 1010 (Shandong San Feng Chemical Co., Ltd.s)：0.1 part；
Irgasfos 168 (Shandong San Feng Chemical Co., Ltd.s)：0.2 part；
PE waxes (BN-500, Qingdao Bang Ni Chemical Co., Ltd.s)：1 part；
Ethylene bis stearic acid amide (EB-FF, Japanese Kao)：0.5 part；
Pure powder type anti-dripping agent (M532, Daikin)：0.2 part.
The preparation method of above-mentioned halogen-free flame-retardant master batch is as follows：
1) by block copolymerization polypropylene, antioxidant 1010, irgasfos 168, PE waxes, ethylene bis stearic acid amide and pure powder type Anti-dripping agent adds in high-speed mixer, rotating speed 1500r/min stirring 2min, then halogen-free expansion fire retardant is added in mixed at high speed Machine, rotating speed 1500r/min stirrings 5min；
2) adding pressure type rolling mixing built-in temperature is risen to 140~145 DEG C, the material for adding in step 1) carries out mixing, control Rotor speed 50r/min processed, built-in temperature often rise 15 DEG C of exhausts once, and control built-in temperature is no more than 180 DEG C, mixing 20min, until material is tentatively plasticized；
3) material in the mixer that rolls is sent into double screw extruder by bipyramid forced feed machine, controls bipyramid rotating speed 15r/min, fully plasticizing are scattered, convey and cool down using single screw extrusion machine, then carry out water ring pelletizing, sieve, obtain Halogen Fire-retardant master granule.
Note：The screw slenderness ratio of the double screw extruder is 30:1, screw diameter 75mm, screw speed 120 ~250r/min, no head, each area's temperature are：One 180 DEG C of area, 185 DEG C of two-three area, 180 DEG C of four-five area, six-seven areas 175 DEG C, 170 DEG C of 8th area；The screw slenderness ratio of the single screw extrusion machine is 15:1, screw diameter 155mm, screw speed are 15~30r/min, each area's temperature are：One 155 DEG C of area, 155 DEG C of 2nd area, 155 DEG C of 3rd area, 165 DEG C of head temperature.
Embodiment 3：
A kind of halogen-free flame-retardant master batch is made of the raw material of following mass parts：
Block copolymerization polypropylene (BH975MO, Borealis, melt index 38g/10min, 230 DEG C of test condition/ 2.16kg)：18 parts；
(mass ratio of ammonium polyphosphate, melamine and piperidyl triazine is 4 to halogen-free expansion fire retardant:2:1, code name FR- 1)：80 parts；
Antioxidant 1010 (Shandong San Feng Chemical Co., Ltd.s)：0.1 part；
Irgasfos 168 (Shandong San Feng Chemical Co., Ltd.s)：0.2 part；
PE waxes (BN-500, Qingdao Bang Ni Chemical Co., Ltd.s)：1 part；
Ethylene bis stearic acid amide (EB-FF, Japanese Kao)：0.5 part；
Pure powder type anti-dripping agent (M532, Daikin)：0.2 part.
The preparation method of above-mentioned halogen-free flame-retardant master batch is as follows：
1) by block copolymerization polypropylene, antioxidant 1010, irgasfos 168, PE waxes, ethylene bis stearic acid amide and pure powder type Anti-dripping agent adds in high-speed mixer, rotating speed 1500r/min stirring 2min, then halogen-free expansion fire retardant is added in mixed at high speed Machine, rotating speed 1500r/min stirrings 5min；
2) adding pressure type rolling mixing built-in temperature is risen to 140~145 DEG C, the material for adding in step 1) carries out mixing, control Rotor speed 50r/min processed, built-in temperature often rise 15 DEG C of exhausts once, and control built-in temperature is no more than 180 DEG C, mixing 20min, until material is tentatively plasticized；
3) material in the mixer that rolls is sent into double screw extruder by bipyramid forced feed machine, controls bipyramid rotating speed 15r/min, fully plasticizing are scattered, convey and cool down using single screw extrusion machine, then carry out water ring pelletizing, sieve, obtain Halogen Fire-retardant master granule.
Note：The screw slenderness ratio of the double screw extruder is 30:1, screw diameter 75mm, screw speed 120 ~250r/min, no head, each area's temperature are：One 180 DEG C of area, 185 DEG C of two-three area, 180 DEG C of four-five area, six-seven areas 175 DEG C, 170 DEG C of 8th area；The screw slenderness ratio of the single screw extrusion machine is 15:1, screw diameter 155mm, screw speed are 15~30r/min, each area's temperature are：One 155 DEG C of area, 155 DEG C of 2nd area, 155 DEG C of 3rd area, 165 DEG C of head temperature.
Embodiment 4：
A kind of halogen-free flame-retardant master batch is made of the raw material of following mass parts：
Block copolymerization polypropylene (BH975MO, Borealis, melt index 38g/10min, 230 DEG C of test condition/ 2.16kg)：8 parts；
(mass ratio of ammonium polyphosphate, melamine and piperidyl triazine is 4 to halogen-free expansion fire retardant:2:1, code name FR- 1)：90 parts；
Antioxidant 1010 (Shandong San Feng Chemical Co., Ltd.s)：0.1 part；
Irgasfos 168 (Shandong San Feng Chemical Co., Ltd.s)：0.2 part；
PE waxes (BN-500, Qingdao Bang Ni Chemical Co., Ltd.s)：1 part；
Ethylene bis stearic acid amide (EB-FF, Japanese Kao)：0.5 part；
Pure powder type anti-dripping agent (M532, Daikin)：0.2 part.
The preparation method of above-mentioned halogen-free flame-retardant master batch is as follows：
1) by block copolymerization polypropylene, antioxidant 1010, irgasfos 168, PE waxes, ethylene bis stearic acid amide and pure powder type Anti-dripping agent adds in high-speed mixer, rotating speed 1500r/min stirring 2min, then halogen-free expansion fire retardant is added in mixed at high speed Machine, rotating speed 1500r/min stirrings 5min；
2) adding pressure type rolling mixing built-in temperature is risen to 140~145 DEG C, the material for adding in step 1) carries out mixing, control Rotor speed 50r/min processed, built-in temperature often rise 15 DEG C of exhausts once, and control built-in temperature is no more than 180 DEG C, mixing 20min, until material is tentatively plasticized；
3) material in the mixer that rolls is sent into double screw extruder by bipyramid forced feed machine, controls bipyramid rotating speed 15r/min, fully plasticizing are scattered, convey and cool down using single screw extrusion machine, then carry out water ring pelletizing, sieve, obtain Halogen Fire-retardant master granule.
Note：The screw slenderness ratio of the double screw extruder is 30:1, screw diameter 75mm, screw speed 120 ~250r/min, no head, each area's temperature are：One 180 DEG C of area, 185 DEG C of two-three area, 180 DEG C of four-five area, six-seven areas 175 DEG C, 170 DEG C of 8th area；The screw slenderness ratio of the single screw extrusion machine is 15:1, screw diameter 155mm, screw speed are 15~30r/min, each area's temperature are：One 155 DEG C of area, 155 DEG C of 2nd area, 155 DEG C of 3rd area, 165 DEG C of head temperature.
Comparative example 1：
A kind of halogen-free flame-retardant master batch is made of the raw material of following mass parts：
Block copolymerization polypropylene (BH975MO, Borealis, melt index 38g/10min, 230 DEG C of test condition/ 2.16kg)：28 parts；
(mass ratio of ammonium polyphosphate, melamine and piperidyl triazine is 4 to halogen-free expansion fire retardant:2:1, code name FR- 1)：70 parts；
Antioxidant 1010 (Shandong San Feng Chemical Co., Ltd.s)：0.1 part；
Irgasfos 168 (Shandong San Feng Chemical Co., Ltd.s)：0.2 part；
PE waxes (BN-500, Qingdao Bang Ni Chemical Co., Ltd.s)：1 part；
Ethylene bis stearic acid amide (EB-FF, Japanese Kao)：0.5 part；
Pure powder type anti-dripping agent (M532, Daikin)：0.2 part.
The preparation method of above-mentioned halogen-free flame-retardant master batch is as follows：
1) by block copolymerization polypropylene, antioxidant 1010, irgasfos 168, PE waxes, ethylene bis stearic acid amide and pure powder type Anti-dripping agent adds in high-speed mixer, rotating speed 1500r/min stirring 3min, then halogen-free expansion fire retardant is added in mixed at high speed Machine, rotating speed 2000r/min stirrings 5min；
2) material of step 1) is transferred to screw slenderness ratio 40:1st, the parallel dual-screw extruding machine (south of screw diameter 76mm Jing Keya), squeeze out, extruder temperature be arranged to 170~195 DEG C, 200 revs/min of screw speed, vacuum degree -0.8MPa, pass through The sink cooling that 25 ± 5 DEG C of water temperature, pelletizing obtain halogen-free flame-retardant master batch.
Comparative example 2：
A kind of halogen-free flame-retardant master batch is made of the raw material of following mass parts：
Block copolymerization polypropylene (BH975MO, Borealis, melt index 38g/10min, 230 DEG C of test condition/ 2.16kg)：28 parts；
(mass ratio of ammonium polyphosphate, melamine and piperidyl triazine is 4 to halogen-free expansion fire retardant:2:1, code name FR- 1)：70 parts；
Antioxidant 1010 (Shandong San Feng Chemical Co., Ltd.s)：0.1 part；
Irgasfos 168 (Shandong San Feng Chemical Co., Ltd.s)：0.2 part；
PE waxes (BN-500, Qingdao Bang Ni Chemical Co., Ltd.s)：1 part；
Ethylene bis stearic acid amide (EB-FF, Japanese Kao)：0.5 part；
Pure powder type anti-dripping agent (M532, Daikin)：0.2 part.
The preparation method of above-mentioned halogen-free flame-retardant master batch is as follows：
1) by block copolymerization polypropylene, antioxidant 1010, irgasfos 168, PE waxes, ethylene bis stearic acid amide and pure powder type Anti-dripping agent adds in high-speed mixer, rotating speed 1500r/min stirring 3min, then halogen-free expansion fire retardant is added in mixed at high speed Machine, rotating speed 2000r/min stirrings 5min；
2) adding pressure type rolling mixer is warming up to 140~145 DEG C, the material for adding in step 1) carries out mixing, and control turns Rotor speed 50r/min, built-in temperature often rise 15 DEG C of exhausts once, and control built-in temperature is no more than 180 DEG C, mixing 30min, until Material is plasticized completely；
3) material in elevator is sent into screw slenderness ratio 15 by bipyramid forced feed machine:1st, screw diameter 155mm Single screw extrusion machine, squeeze out, using the mode pelletizing that air-cooled die-surface is fervent, control 1100 revs/min of cutter rotating velocity, cut Particle is screened by two level cyclone separator, and cooling screens into vibrating screen, obtains halogen-free flame-retardant master batch.
Test case：
By Examples 1 to 4 and comparative example 1~2 prepare halogen-free flame-retardant master batch respectively with block copolymerization polypropylene (BH975MO, Borealis) it is uniformly mixed, then material is transferred to horizontal injection press (HS-1200, extra large stone molding machine), it is 180 to set injection temperature ~195 DEG C, be molded into standard batten, 23 DEG C, 50% humidity place 48h, respectively obtain test specimens 1~4 and contrast test sample 1~ 2；By block copolymerization polypropylene, antioxidant 1010, irgasfos 168, PE waxes, ethylene bis stearic acid amide and pure powder type anti-dripping agent High-speed mixer, rotating speed 1500r/min stirring 3min are added in, then commercially available ammonium polyphosphate flame retardant is added in into high-speed mixer, is turned Fast 2000r/min stirs 5min, then material is transferred to screw slenderness ratio 48:1st, the parallel dual-screw extruding machine of screw diameter 36mm (Nanjing section sub-) squeezes out, extruder temperature be arranged to 170~195 DEG C, screw speed be 200 revs/min, vacuum degree for- 0.8MPa is cooled down, pelletizing by 25 ± 5 DEG C of sink of water temperature, then particle is put into blast drier, and 85 DEG C of drying 3h are set 180~195 DEG C of injection temperature, is molded into standard batten, and 23 DEG C, 50% humidity placement 48h obtain contrast test sample 3.Test specimens 1~4 and contrast test sample 1~3 raw material composition it is as shown in the table：
The raw material of 1 test specimens 1~4 of table and contrast test sample 1~3 forms table
1) Mechanics Performance Testing is carried out to test specimens 1~4 and contrast test sample 1~3, test result is as shown in the table：
The mechanical experimental results of 2 test specimens 1~4 of table and contrast test sample 1~3
As shown in Table 2：The halogen-free flame-retardant master batch of Examples 1 to 4 is prepared by " mixing+bis- ranks squeeze out " technique, comparative example 1 Halogen-free flame-retardant master batch prepared by " twin-screw extrusion " technique, the halogen-free flame-retardant master batch of comparative example 2 passes through " mixing+single screw rod Squeeze out " technique preparation, the mechanics of the polypropylene test specimens (test specimens 1~4) of the halogen-free flame-retardant master batch added with Examples 1 to 4 Performance is more excellent, and in addition to bending property is not much different, tensile strength, impact strength and elongation at break are all substantially than adding Added with polypropylene test specimens (contrast test sample 1 and 2) higher of the halogen-free flame-retardant master batch of comparative example 1 or 2.In addition, added with real The polypropylene test specimens (test specimens 1~4) for applying the halogen-free flame-retardant master batch of example 1~4 are fire-retardant with adding commercially available ammonium polyphosphate powder The polypropylene test specimens (contrast test sample 3) of agent are compared, and comprehensive mechanical property is more preferable.
Reason is：
1) using halogen-free flame-retardant master batch prepared by double screw extruder extrusion, there are separation of powder and granule, plasticizing are uneven and difficult merely With scattered situation, using halogen-free flame-retardant master batch prepared by mixing+Single screw extrusion due to only carrying out plasticizing point by mixer It dissipates, it is difficult to reach preferably distribution and dispersity, both halogen-free flame-retardant master batchs and be present with for polypropylene articles fire-retardant Agent disperses uneven or reunites, and the mechanical property final to product causes harmful effect；
2) halogen-free flame-retardant master batch produced using mixer+single screw rod, since the material after plasticizing is presented one State is difficult to realize uniform blanking into single screw rod, and the particle that final production goes out also is present with the phenomenon that not of uniform size, serious shadow Ring appearance；
3) powder fire retardant passes through the shear-mixed of twin-screw, and although fire retardant obtains well scattered, but be distributed Uniformity be still not so good as directly to be molded using the halogen-free flame-retardant master batch of Examples 1 to 4, and also need to volume using powder fire retardant Twin-screw extrusion process of outer increase, adds production cost, reduces production efficiency.
2) flame retardant property test is carried out to test specimens 1~4 and contrast test sample 1~3, test result is as shown in the table：
The flame retardant property test result of 3 test specimens 1~4 of table and contrast test sample 1~3
As shown in Table 3：Polypropylene test specimens (test specimens 1~4) nothing of halogen-free flame-retardant master batch added with Examples 1 to 4 By be compared with the polypropylene test specimens (contrast test sample 1 and 2) of the halogen-free flame-retardant master batch added with comparative example 1~2 or with The polypropylene test specimens (contrast test sample 3) for adding commercially available ammonium polyphosphate powder fire retardant are compared, and flame retardant property is all more It is excellent.
Reason is：
1) halogen-free flame-retardant master batch (comparative example 1) that is prepared by simple twin screw extrusion process and by mixing+single screw rod Halogen-free flame-retardant master batch (comparative example 2) prepared by expressing technique is for after polypropylene, dispersion effect by mixing+bis- ranks not as good as to be squeezed Go out the halogen-free flame-retardant master batch (Examples 1 to 4) of technique preparation；
2) decomposition temperature of ammonium polyphosphate is low, temperature sensitive, by its mixing and is reached PP using mixer and is plasticized completely Temperature when, the actual temperature inside material has reached the preliminary exposition temperature of ammonium polyphosphate, and part fire retardant can be caused to decompose Failure, and mixing+bis- ranks is used to squeeze out, it carries out only needing to reach preliminary plasticizing during mixing, avoiding causes because temperature is excessively high Ammonium polyphosphate is decomposed.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention and from above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (10)

1. a kind of halogen-free flame-retardant master batch, it is characterised in that：It is made of the raw material of following mass parts：
Acrylic resin：8~38 parts；
Halogen-free expansion fire retardant：60~90 parts；
Antioxidant：0.1~0.4 part；
Lubricant：0.5~1.5 part；
Anti-dripping agent：0.1~0.5 part.
2. halogen-free flame-retardant master batch according to claim 1, it is characterised in that：The acrylic resin is homopolymerization poly- third At least one of alkene, block copolymerization polypropylene, atactic copolymerized polypropene, melt index be 25~105g/10min, 230 DEG C/ 2.16kg。
3. halogen-free flame-retardant master batch according to claim 1, it is characterised in that：The halogen-free expansion fire retardant is by acid Source, source of the gas and carbon source are according to mass ratio (4~6)：(1~2)：(1~2) form, acid source is ammonium polyphosphate, melamine polyphosphoric acid At least one of salt, melamine pyrophosphate, source of the gas are melamine, and carbon source is triazine derivative, pentaerythrite, double At least one of pentaerythrite, polyol.
4. halogen-free flame-retardant master batch according to claim 3, it is characterised in that：The degree of polymerization of the ammonium polyphosphate is 1000 ~1200, the mass percentage of phosphorus is 31%~32%, and the mass percentage of nitrogen is 14.5%~15.5%；Described three The grain size of poly cyanamid is 4~6 μm, and the mass percentage of phosphorus is 12%~13%, the mass percentage of nitrogen for 42%~ 44%.
5. halogen-free flame-retardant master batch according to claim 3, it is characterised in that：The triazine derivative is formula 1, formula 2 At least one of with compound shown in formula 3：
Wherein, R1、R2For-H ,-C6H5、-C6H4OH, morpholine, piperidines ,-CyH2y-O-R3In one kind, 1≤y≤8, R3For-H, C1~C8Alkyl, C2~C6Alkenyl in one kind, X isIn one kind, 2≤Z ≤6。
6. halogen-free flame-retardant master batch according to claim 1, it is characterised in that：The antioxidant is the double [β-(3,5- of 1,2- Di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, four [methyl-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, 3- (dodecylthio) propionic acid -2,2- double [[3- (dodecylthio)-propionyloxy] methyl] -1,3- propylene glycol esters, three (2,4- At least one of di-t-butyl) phenyl-phosphite.
7. halogen-free flame-retardant master batch according to claim 1, it is characterised in that：The lubricant is polyethylene wax, tristearin At least one of acid, ethylenebisstearamide；The anti-dripping agent is pure powder type anti-drip agents.
8. the preparation method of the halogen-free flame-retardant master batch in claim 1~7 described in any one, it is characterised in that：Including following Step：
1) acrylic resin, antioxidant, lubricant and anti-dripping agent are added in into high-speed mixer, are uniformly mixed, then Halogen is swollen Swollen type fire retardant adds in high-speed mixer, is uniformly mixed；
2) adding pressure type rolling mixing built-in temperature is risen to 140~145 DEG C, the material for adding in step 1) carries out mixing, temperature in machine Degree often rises 15 DEG C of exhausts once, and control built-in temperature is no more than 180 DEG C；
3) material in the mixer that rolls is transferred to double screw extruder, fully plasticizing is scattered, defeated using single screw extrusion machine Cooling is sent, then carries out water ring pelletizing, sieves, obtains halogen-free flame-retardant master batch.
9. preparation method according to claim 8, it is characterised in that：The flip angle of the convertible mixer is 135~145 degree, the operating pressure for the hammer that pressurizes is 0.8~0.9MPa.
10. preparation method according to claim 8, it is characterised in that：The screw slenderness ratio of the double screw extruder For (30~35)：1, screw diameter is 70~75mm, and screw speed is 120~250r/min, and no head, each area's temperature is：One 170~180 DEG C of area, 180~185 DEG C of two-three area, 175~180 DEG C of four-five area, 170~175 DEG C of six-seven area, eight areas 160~ 170℃；The screw slenderness ratio of the single screw extrusion machine is (10~15)：1, screw diameter is 145~155mm, and screw rod turns Speed is 15~30r/min, and each area's temperature is：One 145~155 DEG C of area, 145~155 DEG C of 2nd area, 145~155 DEG C of 3rd area, head 155~165 DEG C of temperature.
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CN109438804A (en) * 2018-10-09 2019-03-08 河南骏化发展股份有限公司 A kind of flame retardant plastics master batch and preparation method thereof
CN110607029A (en) * 2019-10-09 2019-12-24 江苏万纳普新材料科技有限公司 Special halogen-free flame-retardant synergistic functional master batch for polyolefin resin modification and preparation method thereof
CN110964259A (en) * 2019-09-04 2020-04-07 上海日之升科技有限公司 Efficient halogen-free flame-retardant master batch with polypropylene carrier and preparation method thereof
CN111057316A (en) * 2019-12-23 2020-04-24 清远市普塞呋磷化学有限公司 Non-sticking ammonium polyphosphate flame-retardant modified polypropylene material and preparation method thereof
CN111793270A (en) * 2020-07-30 2020-10-20 厦门翔矽新材料有限公司 Anti-slip agent particle for shoe material and preparation method thereof
CN112265178A (en) * 2020-10-30 2021-01-26 深圳兴旺环保代塑材料开发有限公司 Production line for plastic substitute material
CN112321945A (en) * 2020-11-23 2021-02-05 江苏金发科技新材料有限公司 Precipitation-resistant halogen-free flame-retardant polypropylene composite material and preparation method thereof
CN112590051A (en) * 2020-12-27 2021-04-02 南京天诗新材料科技有限公司 Production method and device of polypropylene anti-dripping master batch
CN112679843A (en) * 2020-12-15 2021-04-20 上海金发科技发展有限公司 Halogen-free flame-retardant polypropylene compound special for new energy automobile and preparation method thereof
CN115216089A (en) * 2022-08-18 2022-10-21 上海安凸塑料添加剂有限公司 Halogen-free flame-retardant master batch, thin-wall halogen-free flame-retardant polypropylene and preparation method thereof

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CN108250573A (en) * 2017-12-28 2018-07-06 清远市普塞呋磷化学有限公司 A kind of halogen-free environment-friendly flame-proof polypropylene material of heat oxygen aging resistance and preparation method thereof
CN108250573B (en) * 2017-12-28 2020-10-27 清远市普塞呋磷化学有限公司 Thermo-oxidative aging resistant halogen-free environment-friendly flame-retardant polypropylene material and preparation method thereof
CN109438804A (en) * 2018-10-09 2019-03-08 河南骏化发展股份有限公司 A kind of flame retardant plastics master batch and preparation method thereof
CN110964259B (en) * 2019-09-04 2022-07-29 上海日之升科技有限公司 Efficient halogen-free flame-retardant master batch with polypropylene carrier and preparation method thereof
CN110964259A (en) * 2019-09-04 2020-04-07 上海日之升科技有限公司 Efficient halogen-free flame-retardant master batch with polypropylene carrier and preparation method thereof
CN110607029A (en) * 2019-10-09 2019-12-24 江苏万纳普新材料科技有限公司 Special halogen-free flame-retardant synergistic functional master batch for polyolefin resin modification and preparation method thereof
CN110607029B (en) * 2019-10-09 2022-12-27 江苏万纳普新材料科技有限公司 Special halogen-free flame-retardant synergistic functional master batch for polyolefin resin modification and preparation method thereof
CN111057316A (en) * 2019-12-23 2020-04-24 清远市普塞呋磷化学有限公司 Non-sticking ammonium polyphosphate flame-retardant modified polypropylene material and preparation method thereof
CN111057316B (en) * 2019-12-23 2022-03-29 清远市普塞呋磷化学有限公司 Non-sticking ammonium polyphosphate flame-retardant modified polypropylene material and preparation method thereof
CN111793270A (en) * 2020-07-30 2020-10-20 厦门翔矽新材料有限公司 Anti-slip agent particle for shoe material and preparation method thereof
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CN112321945A (en) * 2020-11-23 2021-02-05 江苏金发科技新材料有限公司 Precipitation-resistant halogen-free flame-retardant polypropylene composite material and preparation method thereof
CN112679843A (en) * 2020-12-15 2021-04-20 上海金发科技发展有限公司 Halogen-free flame-retardant polypropylene compound special for new energy automobile and preparation method thereof
CN112590051A (en) * 2020-12-27 2021-04-02 南京天诗新材料科技有限公司 Production method and device of polypropylene anti-dripping master batch
CN115216089A (en) * 2022-08-18 2022-10-21 上海安凸塑料添加剂有限公司 Halogen-free flame-retardant master batch, thin-wall halogen-free flame-retardant polypropylene and preparation method thereof
CN115216089B (en) * 2022-08-18 2023-08-08 上海安凸塑料添加剂有限公司 Halogen-free flame-retardant master batch, thin-wall halogen-free flame-retardant polypropylene and preparation methods thereof

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Application publication date: 20180605