CN102993677A - Process for manufacturing flame-retardant microencapsulation acrylonitrile butadiene styrene (ABS)/ polycarbonate (PC) alloy - Google Patents

Process for manufacturing flame-retardant microencapsulation acrylonitrile butadiene styrene (ABS)/ polycarbonate (PC) alloy Download PDF

Info

Publication number
CN102993677A
CN102993677A CN201210558539XA CN201210558539A CN102993677A CN 102993677 A CN102993677 A CN 102993677A CN 201210558539X A CN201210558539X A CN 201210558539XA CN 201210558539 A CN201210558539 A CN 201210558539A CN 102993677 A CN102993677 A CN 102993677A
Authority
CN
China
Prior art keywords
abs
flame retardant
microcapsule
alloy
manufacturing process
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.)
Pending
Application number
CN201210558539XA
Other languages
Chinese (zh)
Inventor
陈刚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao Vland Biotech Group Co Ltd
Original Assignee
Qingdao Vland Biotech Group Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Qingdao Vland Biotech Group Co Ltd filed Critical Qingdao Vland Biotech Group Co Ltd
Priority to CN201210558539XA priority Critical patent/CN102993677A/en
Publication of CN102993677A publication Critical patent/CN102993677A/en
Pending legal-status Critical Current

Links

Landscapes

  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a process for manufacturing a flame-retardant microencapsulation acrylonitrile butadiene styrene (ABS)/polycarbonate (PC) alloy. The process comprises the following steps: a, putting 56-60 parts by weight of ammonium polyphosphate, 26-30 parts by weight of carbon forming agents and 4-6 parts by weight of coordinate synergistic agents into a stirring kettle to stir for 5-10 minutes in a mixed mode; b, spraying atomized polysiloxane diluents into the stirring kettle for 5-10 minutes until the stirring is finished and the mixture stands for 10 minutes to form a microencapsulation flame retardant; and c, adding ABS and PC granules to fully stir so that the microencapsulation flame retardant is adhered to the ABS and PC granules, and discharging and drying the materials.

Description

A kind of manufacturing process of flame retardant microcapsule ABS/PC alloy
Technical field
The present invention relates to a kind of manufacturing process of flame retardant microcapsule ABS/PC alloy, further, relate to a kind of manufacturing process of flame retardant microcapsule ABS/PC alloy.
Background technology
ABS resin is the terpolymer of vinyl cyanide (A), divinyl (B), vinylbenzene (S), high-performance in conjunction with three kinds of components, have higher resistance to impact shock, good processing characteristics and chemical stability, be easy to molded, goods are rich in gloss, and having toughness concurrently, is a kind of general thermoplastic engineering plastic of superior performance.Polycarbonate (PC) resin is a kind of thermoplastic engineering plastic of excellent property, has outstanding impact resistance, anti-creep and good stability of the dimension, heat-resisting, water-intake rate is low, nontoxic, dielectric properties are good.ABS resin and the two consistency of PC resin are good, prepare the ABS/PC alloy in conjunction with the two advantage and are widely used in the industries such as automotive industry, electronic apparatus industry, light industry household electrical appliances, weaving and building with its superior over-all properties.Because the two all is inflammable material, and discharge a large amount of toxic gases and black smoke during burning, not only cause serious property damage, return people's life security and living environment and bring great threat, so the ABS/PC alloy need to carry out fire-retardant and but cigarette processing in a lot of Application Areass.
The halogenated flame retardant application and development is the widest, the technology comparative maturity, flame retarding efficiency is high, but the halogenated flame retardant goods amount of being fuming increases, produce hydrogen halide after the burning and have severe corrosive, hiding secondary harm may make in the electronic and electrical equipment key part impaired and cause whole plant malfunctioning, and environmental pollution is serious in the recycling process, produces the “ dioxin " etc. carcinogenic gas.According to the RoHS Directive requirement, the Electrical and Electronic product that on July 1st, 2006 was thrown in later on EU market must not contain 6 kinds of objectionable impuritiess such as lead, mercury, cadmium, sexavalent chrome, Polybrominated biphenyl and Poly Brominated Diphenyl Ethers.China has also put into effect corresponding rules " electronics and IT products pollution control management way ", and execution in 1 day March in 2007.Environmental regulation for the reply RoSH of European Union instruction and various countries' promulgation, the continuous upgrading that, Halogen nontoxic to fire retardant, environmental protection etc. require, various countries research and develop multiple fire retardant in succession, wherein so that phosphorus, nitrogen are desirable as chemically expansible fire retardant (IFR) the flame-retardant system flame retardant effect of main body, complete processing is simple, cheap, be subject to people's extensive concern.
Most of IFR are by ammonium polyphosphate (APP, acid source), tetramethylolmethane (PER, charcoal source), the composite formation of trimeric cyanamide (MEL, source of the gas) three components, are mainly used in PE, PP, EVA and elastomeric fire-retardant.When amount of flame-retardant agent was 25-30wt%, the material oxygen index can reach the difficult combustion of 30%, UL-94 rank can reach the V-0 level, and almost with not fire retardant material is identical to give birth to the cigarette amount, did not increase living cigarette amount or gave birth to cigarette speed and reduce, and density only improves 10-15% than fire retardant material not.The initial heat decomposition temperature of APP and the compound IFR of PER is between 160-180 ℃, so this system is multiplex in fire retardant polyolefin and thermoplastic elastomer, and is not used in fire-resistant engineering plastics; Simultaneously, exist the ammonium radical ion to decompose instability problem among the APP, under the strong shearing action of the course of processing, easily deviate from NH 3, the sample part that processes is reddened, the unsettled phenomenon of processing appears in the extruding pelletization process when serious.There is the water absorbability problem in IFR, causes the poor problem of anti-moving out property, can not adapt to open air and humid climate, PER can because of be rich in-wetting ability of OH produces the moisture absorption, transport phenomena, makes product surface " frosting ", generation hickie or tarnish, move out when serious, can cause fire retardant to lose efficacy.Add IFR and will reach the difficult combustion of fire-retardant UL-94 test rank V-0 level and need addition large, and and resin between consistency poor, difficulties in dispersion can cause the IFR flame retarding efficiency to descend, and ABS/PC alloy physics mechanical property is worsened serious.
Number of patent application: CN200410051777, disclose a kind of novel flame-retardant PC/ABS alloy, according to weight percent meter, this alloy comprises the brominated polycarbonate oligopolymer of ABS, 1%-30% of PC, the 10%-80% of 10%-80%, the Sb2O3 of 1%-10%, the tetrafluoroethylene of 0.1%-5% and optional stabilizer, toughener, pigment, other additive such as weighting material.During manufacturing, at first raw material was toasted 4-6 hour under 90-100 ℃, then drop in proportion in the high-speed mixer and mixed 5-10 minute, then carry out mixing granulation in dual-screw-stem machine, prilling temperature is 240-260 ℃.This novel PC/ABS alloy has good mechanical property, thermal property and flame retardant resistance.Its shortcoming is that the flame retardant brominated polycarbonate oligomer that adopts still contains halogen, collaborative and the usefulness with Sb2O3 still can cause the PC/ABS alloy system amount of being fuming to increase, and the hydrogen halide that produces after the burning has severe corrosive, hiding secondary harm is unfavorable for MAT'L recycling.
Number of patent application: CN201010125980, disclose a kind of electric works flame-proof ABS/PC alloy material and preparation method thereof, the various components of described alloy and content are expressed as with weight part: 55~63 parts of acrylonitrile-butadiene-styrene copolymers (ABS), 21~34 parts of polycarbonate (PC), 2~7 parts of maleic anhydride grafted ABS compatilizers, 7~15 parts of organophosphate based flame retardants, 1.0~3.0 parts of 0.1~0.5 part of anti-dripping agent FA500B, organosilicon Dymgard, 0.2~0.5 part of composite antioxidant.The preparation method is for adopting the production of the disposable mixing plasticizing of twin screw/single screw rod two steps type forcing machine extruding pelletization, and the product over-all properties satisfies the storage battery dedicated shell performance requriements in subway engineering, electric locomotive and mobile base station.Its shortcoming is that the socle girder notched Izod impact strength of the finished product is at 12.1-17.1kJ/m 2Between, do not give full play to the outstanding impact resistance of PC, because the ABS addition is higher than PC, PC is not external phase, it is lower to impact the relative PC resin of intensity.
Number of patent application: CN200710074852 discloses a kind of halogen-free phosphorus-free inflaming retarding PC/ABS alloy material, and its component and content are: polycarbonate 65.5%-91.2%; Acrylonitrile-butadiene-styrene terpolymer 6%-17%; Compatilizer 1%-4%; Fire retardant tetrafluoroethylene 0.3%-1.5%; Organic silicon fibre retardant 1.0%-8.0%; Sulfobenzide sulfonate 0.1%-1.0%; Oxidation inhibitor 0.1%-1.0%; Lubricant 0.2%-2.0%; Above percentage ratio is weight percent.This patent also proposes the preparation method of described alloy material.Described alloy material can be widely used in the high automotive industry of environmental requirement, electric industry, mechanical industry.Its shortcoming is that the fire retardant sulfobenzide sulfonate that adopts is relatively poor for the PC stability to hydrolysis, generally is not used in to make the thin-walled original paper.
Summary of the invention
Technical problem to be solved by this invention is preparation a kind of micro encapsulation flame-proof ABS/PC alloy, this alloy has Heat stability is good, course of processing fluidity of molten is good, flame retarding efficiency is high simultaneously, be difficult for the moisture absorption, be difficult for migration, the characteristics that product size stability is high can be applicable to injection molding and make electric appliance casing, automobile instrument panel, fan, secondary battery etc.
Micro encapsulation flame-proof ABS of the present invention/PC alloy contain following component and mass percent:
Acrylonitrile-butadiene-styrene (ABS) (ABS) 10%-40%
Polycarbonate (PC) 40%-70%
Microcapsule flame retardant 10%-14%
Phenyl-boron dihydroxide compound 0%-4%
Nano imvite 0%-4%.
Described microcapsule flame retardant is that each component with following mass parts dropped in stirring tank mix and blend 5-10 minute: ammonium polyphosphate 56-60, char-forming agent 26-30, synergetic effect additive 4-6, liquid organopolysiloxane (being commonly called as silicone oil) dilution through spraying atomizing 5-10 minute, after stirring end, leave standstill to open in 10 minutes and stir the kettle cover exhaust, then add ABS and the PC pellet fully stirs for some time, microcapsule stick on ABS and the PC pellet, then discharge compound, oven dry is 2 hours in 60-80 ℃ of baking oven.
Described microcapsule flame retardant component ammonium polyphosphate, nonpoisonous and tasteless, do not produce corrosive gases, thermostability is high, water absorbability is little, preferably adopts the II type APP of polymerization degree n>1500, and initial heat decomposition temperature reaches more than 275 ℃, solubleness is reduced to 0.2g/100mL in the water, and pH value (10% suspension) is between 6-7.
Described microcapsule flame retardant component char-forming agent is that tetramethylolmethane (PER), dipentaerythritol (DPER), starch etc. contain more polyhydric organism, preferred DPER.
Described microcapsule flame retardant component synergetic effect additive is the metal oxides such as the Nano-class zinc oxide (ZnO) of particle diameter below 100nm, silicon-dioxide (SiO2), titanium dioxide (TiO2), have and promote IFR to become the effect of charcoal, and more densification and the high resilience of charcoal layer structure that forms, this structure is difficult for breaking, preferred ZnO.Described synergetic effect additive has played the synergy fire retardation, the zn cpds that a small amount of ZnO and APP reaction produce forms bridged bond between APP, make the model that is similar to " track " that forms ordering between the APP molecular chain, this in order regular " track " promoted the esterification of char-forming agent and APP, reduce reaction activity, phosphoric acid ester model compound defective is tailed off, and the final charcoal layer that forms is finer and close, regular, and we claim that this effect is " track " effect.
Described microcapsule flame retardant component fluids organopolysiloxane is polydimethylsiloxane, poly-aminosiloxane, silicone resin etc., and viscosity (25 ℃) is 2000-3500 (mPa.s), flash-point 〉=310 ℃.Liquid organopolysiloxane addition accounts for the 6%-8% of microcapsule flame retardant total amount, is dissolved in preparation silicone oil diluent in a certain amount of acetone or the dehydrated alcohol.Adopt atomizing nozzle to spray atomized liquid organopolysiloxane diluent to the composite expansion flame-retardant agent in stirring, after the solvent evaporates to be diluted, organopolysiloxane evenly is coated on composite expansion flame-retardant agent surface, and with the APP bonding, have stronger bonding force, microcapsule have high thermal stability.Organopolysiloxane is water insoluble, forms the microcapsule of surface hydrophobicity, makes its humidity environment, is difficult for migration.
Described phenyl-boron dihydroxide compound is the phenyl-boron dihydroxide of aligning structure, is mainly the condensed phase fire retardant mechanism, can change the direction of polymer unwinds reaction, promotes to form surface protection charcoal layer, reduces the burst size of giving birth to cigarette amount and CO and CO2.After described phenyl-boron dihydroxide compound added PC, at a certain temperature dehydration formed network structure, and when material combustion decomposed, this structure formed layer protective layer at material surface, played the heat insulation oxygen effect that presses down, and stoped material to burn away, and reduced the cigarette amount of giving birth to.When its interpolation content was 4%, the charring rate of PC was 30%, and heat decomposition temperature can reach 450 ℃.Can replace the phenyl-boron dihydroxide compound with nano imvite, nano imvite and microcapsule composite flame-retardant agent have synergy, mainly play the heat insulation oxygen effect that presses down by nanoscale twins to the material surface migration, have simultaneously the effect that promotes PC one-tenth charcoal, reduce the cigarette amount of giving birth to, comparatively speaking, the independent time spent of nano imvite can effectively be reduced living cigarette amount, increase neat coal amout, but oxygen index is not high, vertical combustion test grade does not reach the V-0 level; The microcapsule composite flame-retardant agent uses separately, and charring rate is low, and charcoal layer structure is easily destroyed, vertical combustion test grade does not reach the V-0 level yet, and the two is with having synergy, and mechanical property improves, shock strength is brought up to 45.7kJ/m-2 from 39.2kJ/m-2, and flame retardant properties is almost constant.
Described flame-proof ABS/PC alloy course of processing is with blended under agitation such as the ABS of above-mentioned adhesion microcapsule flame retardant and PC pellet and other auxiliary material auxiliary agents, be added in the twin screw extruder, 200 ℃ of-240 ℃ of lower blend granulations, the flame-retardant alloy particle descended dry 6-8 hour at 80 ℃-100 ℃.
Embodiment
The present invention prepares a kind of micro encapsulation flame-proof ABS/PC alloy, and this alloy fire retardant good thermal stability does not decompose in the course of processing, and granulation is extracted out smooth and easy, and surface hydrophobicity is easily dry; Product surface is smooth, and fire retardant humidity environment is difficult for migration precipitation, and physical and mechanical properties is good, particularly has good shock resistance; Flame retardant properties is good, and oxygen index can reach more than 37%, and the vertical combustion grade can reach the V-0 level of UL-94 standard, and the increase of carbon residue amount, gives birth to the cigarette amount and more is conducive to reduce less fire hazard.
The oxygen index test execution GB/T2406 of the embodiment of the invention; Vertical combustion test execution standard GB/T/T2508-1996 " Plastics Combustion performance test method-horizontal and vertical method " or U.S. UL-94 testing standard; Give birth to cigarette test (PSPR) and carry out ISO 5660 standards " Reaction-to-fire tests--Heat release, smoke production and mass loss rate ", CR is final carbon residue amount; Socle girder notched Izod impact strength operative norm GB/T1843; Tensile strength operative norm GB/T1040; Melt mass flow rate operative norm GB/T3682-2000.
Embodiment 1
A kind of method for preparing micro encapsulation flame-proof ABS/PC alloy may further comprise the steps:
A dropped into each component of following mass parts in stirring tank mix and blend 5-10 minute: ammonium polyphosphate 56, char-forming agent 26, synergetic effect additive 4;
B sprays organopolysiloxane diluent 5-10 minute of atomizing in the stirring tank, leaves standstill 10 minutes after finishing wait stirring, and forms microcapsule flame retardant;
C adds ABS and the PC pellet fully stirs, and microcapsule flame retardant is sticked on ABS and the PC pellet, and then discharge is dried.
Above-mentioned ammonium polyphosphate is the II type APP of polymerization degree n=2000; Above-mentioned char-forming agent is tetramethylolmethane; Above-mentioned synergetic effect additive is the Nano-class zinc oxide of particle diameter below 100nm; Above-mentioned organopolysiloxane is polydimethylsiloxane, and its addition accounts for the 6%-8% of microcapsule flame retardant total amount, is dissolved in and forms the silicone oil diluent in the acetone.ABS after the step c oven dry and PC pellet are added in the twin screw extruder 230 ℃ of lower blend granulations, with obtain flame-proof ABS/the PC alloy particle is lower dry 7 hours at 90 ℃.Described micro encapsulation flame-proof ABS/PC alloy contains following component and mass percent:
Acrylonitrile-butadiene-styrene (ABS) (ABS) 20%
Polycarbonate (PC) 70%
Microcapsule flame retardant 10%.
Embodiment 2
Repeat embodiment 1, difference is that each constituent mass part of microcapsule flame retardant is ammonium polyphosphate 60, char-forming agent 30, synergetic effect additive 6; In step c, also add the phenyl-boron dihydroxide compound; Described char-forming agent is dipentaerythritol; Described synergetic effect additive is the nanometer grade silica of particle diameter below 100nm; Described organopolysiloxane is poly-aminosiloxane, is dissolved in the dehydrated alcohol.
Described micro encapsulation flame-proof ABS/PC alloy contains following component and mass percent:
Acrylonitrile-butadiene-styrene (ABS) (ABS) 70%
Polycarbonate (PC) 13%
Microcapsule flame retardant 14%
Phenyl-boron dihydroxide compound 3%.
Embodiment 3
Repeat embodiment 1, difference is that each constituent mass part of microcapsule flame retardant is ammonium polyphosphate 58, char-forming agent 28, synergetic effect additive 5; In step c, also add nano imvite; Described char-forming agent is starch; Described synergetic effect additive is the Nano titanium dioxide of particle diameter below 100nm; Described organopolysiloxane is the silicone resin, is dissolved in the dehydrated alcohol.
Described micro encapsulation flame-proof ABS/PC alloy contains following component and mass percent:
Acrylonitrile-butadiene-styrene (ABS) (ABS) 25%
Polycarbonate (PC) 60%
Microcapsule flame retardant 12%
Nano imvite 3%.

Claims (10)

1. the manufacturing process of a flame retardant microcapsule ABS/PC alloy may further comprise the steps:
A dropped into each component of following mass parts in stirring tank mix and blend 5-10 minute: ammonium polyphosphate 56-60, char-forming agent 26-30, synergetic effect additive 4-6;
B sprays organopolysiloxane diluent 5-10 minute of atomizing in the stirring tank, leaves standstill 10 minutes after finishing wait stirring, and forms microcapsule flame retardant;
C adds ABS and the PC pellet fully stirs, and microcapsule flame retardant is sticked on ABS and the PC pellet, and then discharge is dried.
2. the manufacturing process of described a kind of flame retardant microcapsule ABS/PC alloy according to claim 1 is characterized in that, also adds phenyl-boron dihydroxide compound or nano imvite among the described step c.
3. the manufacturing process of described a kind of flame retardant microcapsule ABS/PC alloy according to claim 2 is characterized in that described micro encapsulation flame-proof ABS/PC alloy contains following component and mass percent
Acrylonitrile-butadiene-styrene (ABS) (ABS) 10%-40%
Polycarbonate (PC) 40%-70%
Microcapsule flame retardant 10%-14%
Phenyl-boron dihydroxide compound 0%-4%
Nano imvite 0%-4%.
4. the manufacturing process of described a kind of flame retardant microcapsule ABS/PC alloy according to claim 1, it is characterized in that described ammonium polyphosphate is the II type APP of polymerization degree n>1500, initial heat decomposition temperature is higher than 275 ℃, solubleness 0.2g/100mL in the water, the pH value of 10% suspension are 6-7.
5. the manufacturing process of described a kind of flame retardant microcapsule ABS/PC alloy according to claim 1 is characterized in that described char-forming agent is tetramethylolmethane (PER), dipentaerythritol (DPER) or starch.
6. the manufacturing process of described a kind of flame retardant microcapsule ABS/PC alloy according to claim 5 is characterized in that described char-forming agent is dipentaerythritol.
7. the manufacturing process of described a kind of flame retardant microcapsule ABS/PC alloy according to claim 1, it is characterized in that described synergetic effect additive is Nano-class zinc oxide (ZnO), silicon-dioxide (SiO2) or the titanium dioxide (TiO2) of particle diameter below 100nm.
8. the manufacturing process of described a kind of flame retardant microcapsule ABS/PC alloy according to claim 7 is characterized in that described synergetic effect additive is Nano-class zinc oxide.
9. the manufacturing process of described a kind of flame retardant microcapsule ABS/PC alloy according to claim 1, it is characterized in that, described organopolysiloxane is polydimethylsiloxane, poly-aminosiloxane or silicone resin, its viscosity (25 ℃) is 2000-3500 (mPa.s), flash-point 〉=310 ℃, the organopolysiloxane addition accounts for the 6%-8% of microcapsule flame retardant total amount, is dissolved in and forms the silicone oil diluent in acetone or the dehydrated alcohol.
10. the manufacturing process of described a kind of flame retardant microcapsule ABS/PC alloy according to claim 1, it is characterized in that, ABS after the step c oven dry and PC pellet are added in the twin screw extruder 200 ℃ of-240 ℃ of lower blend granulations, with the flame-proof ABS that obtains/PC alloy particle 80 ℃-100 ℃ lower dry 6-8 hour.
CN201210558539XA 2012-12-14 2012-12-14 Process for manufacturing flame-retardant microencapsulation acrylonitrile butadiene styrene (ABS)/ polycarbonate (PC) alloy Pending CN102993677A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210558539XA CN102993677A (en) 2012-12-14 2012-12-14 Process for manufacturing flame-retardant microencapsulation acrylonitrile butadiene styrene (ABS)/ polycarbonate (PC) alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210558539XA CN102993677A (en) 2012-12-14 2012-12-14 Process for manufacturing flame-retardant microencapsulation acrylonitrile butadiene styrene (ABS)/ polycarbonate (PC) alloy

Publications (1)

Publication Number Publication Date
CN102993677A true CN102993677A (en) 2013-03-27

Family

ID=47922820

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210558539XA Pending CN102993677A (en) 2012-12-14 2012-12-14 Process for manufacturing flame-retardant microencapsulation acrylonitrile butadiene styrene (ABS)/ polycarbonate (PC) alloy

Country Status (1)

Country Link
CN (1) CN102993677A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104592405A (en) * 2014-12-18 2015-05-06 新疆德美隆合成材料科技有限公司 Amylose carbon forming agent and production method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
刘正英: "《工程塑料改性技术》", 31 December 2008, 化学工业出版社 *
杨有财: "磷-氮型无卤膨胀阻燃ABS树脂性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑(月刊)》 *
石建江: "无卤阻燃PC/ABS合金的研制及应用", 《工程塑料应用》 *
贾修伟: "《纳米阻燃材料》", 31 December 2005, 化学工业出版社 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104592405A (en) * 2014-12-18 2015-05-06 新疆德美隆合成材料科技有限公司 Amylose carbon forming agent and production method thereof

Similar Documents

Publication Publication Date Title
CN102936405A (en) Preparation method of microencapsulated flame-retardant ABS (Acrylonitrile Butadiene Styrene)/PC (Poly Carbonate) alloy
CN103205099A (en) Microencapsulated flame retardant alloy making method
CN103214809A (en) Method for preparing flame retardant micro encapsulation alloy
CN104744763A (en) Antistatic fire retardant master batch for modification of polyethylene
CN102993677A (en) Process for manufacturing flame-retardant microencapsulation acrylonitrile butadiene styrene (ABS)/ polycarbonate (PC) alloy
CN102993678A (en) Process for preparing flame-retardant microencapsulation alloy
CN102993675A (en) Preparation process of flame-retardant microencapsulated alloy
CN102977577A (en) Method for preparing microencapsulated flame-retardant alloy
CN102936404A (en) Preparation process of microencapsulated flame-retardant ABS (Acrylonitrile Butadiene Styrene)/PC (Poly Carbonate) alloy
CN103044875A (en) Method for preparing micro encapsulation flame retardation alloy
CN102942777A (en) Preparation method of microencapsulated flame-retardant alloy
CN103205098A (en) Microencapsulated flame retardant ABS/PC alloy making method
CN103214811A (en) Method for preparing flame retardant micro encapsulation ABS/PC alloy
CN102993679A (en) Method for preparing flame-retardant microencapsulation alloy
CN102993674A (en) Process for preparing flame-retardant microencapsulation alloy
CN103013082A (en) Manufacturing technique of flame-retardant microcapsule ABS/PC alloy
CN103013084A (en) Method for producing flame-retardant microencapsulation ABS (acrylonitrile butadiene styrene)/PC (polycarbonate) alloy
CN103013083A (en) Manufacturing method of flame-retardant microcapsule ABS/PC alloy
CN103044881A (en) Manufacturing process of microencapsulation flame-retardant alloy
CN102993676A (en) Preparation method of flame-retardant microencapsulated alloy
CN103013085A (en) Method for producing flame-retardant microencapsulation alloy
CN102977578A (en) Method for preparing microencapsulated flame-retardant alloy
CN103059538A (en) Method for manufacturing flame-retardant acrylonitrile butadiene styrene/ polycarbonate (ABS/ PC) alloy
CN103044880A (en) Method for preparing flame retardant micro encapsulation alloy
CN103044882A (en) Preparation process of microencapsulation flame-retardant alloy

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20130327