CN114605805B - Flame retardant polycarbonate composition and method for preparing the same - Google Patents

Flame retardant polycarbonate composition and method for preparing the same Download PDF

Info

Publication number
CN114605805B
CN114605805B CN202210399952.XA CN202210399952A CN114605805B CN 114605805 B CN114605805 B CN 114605805B CN 202210399952 A CN202210399952 A CN 202210399952A CN 114605805 B CN114605805 B CN 114605805B
Authority
CN
China
Prior art keywords
temperature
parts
area
copolymer
flame retardant
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.)
Active
Application number
CN202210399952.XA
Other languages
Chinese (zh)
Other versions
CN114605805A (en
Inventor
何彬
何继辉
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.)
Guangdong Aldex New Material Co Ltd
Original Assignee
Guangdong Aldex New Material 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 Guangdong Aldex New Material Co Ltd filed Critical Guangdong Aldex New Material Co Ltd
Priority to CN202210399952.XA priority Critical patent/CN114605805B/en
Publication of CN114605805A publication Critical patent/CN114605805A/en
Application granted granted Critical
Publication of CN114605805B publication Critical patent/CN114605805B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • 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
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a flame-retardant polycarbonate composition and a preparation method thereof, wherein the flame-retardant polycarbonate composition is prepared from polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer, bisphenol A bis (diphenyl phosphate), organosilicon flame-retardant synergist, methyl methacrylate-styrene-organosilicon copolymer, styrene-acrylonitrile-glycidyl methacrylate copolymer, hindered phenol antioxidant, phosphite antioxidant, pentaerythritol stearate and modified polytetrafluoroethylene, and the total weight parts of the polycarbonate resin, the polysiloxane-polycarbonate and the acrylonitrile-butadiene-styrene copolymer is 100 parts; the weight ratio of bisphenol A bis (diphenyl phosphate) to the organosilicon flame retardant synergist is 2.5-24:1. The raw material components of the invention are mutually matched, so that the flame-retardant polycarbonate composition has excellent flame retardant property, mechanical property, processing property, chemical resistance and antibacterial property.

Description

Flame retardant polycarbonate composition and method for preparing the same
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a flame-retardant polycarbonate composition and a preparation method thereof.
Background
Along with the development of the medical industry in the world, the development of the wave is more and more rapid, the traditional materials are in a state of fatigue gradually, and the requirements of high strength, high precision and high durability of modern medical instruments are more and more difficult to meet. The polycarbonate PC is used as engineering plastic with wide application, has excellent performances of high strength, high impact resistance, high and low temperature resistance and the like, and can be widely applied to the fields of aerospace, automobile interior and exterior trim, electronic products, household appliances, foods, medical appliances and the like. In addition, PC products can be sterilized in various modes such as light irradiation, high-temperature high-pressure steam and the like, the performance of the PC products cannot be reduced due to the environmental influence of a sterilization process, and the PC products are widely applied to high-pressure syringes, hemodialysis devices, shell surgical masks, disposable medical consumables, laparoscopes and other minimally invasive surgical instruments due to the characteristics of transparency, nontoxicity, tastelessness, difficult pollution, good heat resistance, good drug resistance and the like, and particularly have application in the manufacture of artificial lung tissues and artificial kidney organs.
Although PC materials have excellent material properties that are not comparable to other engineering plastics, PC also has the disadvantage of being prone to stress cracking. The stress cracking is caused by the fact that in the injection molding process, the PC material has high melt viscosity and relatively high molecular chain rigidity, so that high elastic deformation is generated and cannot be released to be remained in a product, and internal stress is formed. When the internal stress is induced by external factors, the energy of elastic deformation needs to be released, and when the energy is larger than the tearing resistance of the PC molecular chain part, the balance inside the product is broken, namely stress cracking is generated. In order to reduce the problems of large internal stress and poor fluidity of PC, an attempt is made to add an ABS material to PC resin to reduce the melt temperature and internal stress of the material.
The flame retardants commonly used for PC materials at present are mainly halogen-based, phosphorus-based and some inorganic flame retardants. Because the material performance and the environmental protection requirements are more and more strict, some halogen-containing flame retardants cannot meet the environmental protection requirements in practical application, the inorganic flame retardants have limited promotion on the upper flame retardation limit of the material, and the phosphorus flame retardants effectively solve the problems of the former two, but have larger consumption of the phosphorus flame retardants under the same flame retardation condition due to the poor flame retardation efficiency, and have larger damage on the mechanical properties of the material. The organic silicon flame retardant synergist is a novel non-halogen charcoal forming flame retardant synergist which is efficient, eco-friendly and has little smoke suppression, and the problem of large consumption of the phosphorus flame retardant can be solved by compounding the rest of phosphorus flame retardants.
In recent years, the stress resistance of polycarbonate is improved at home and abroad, and the methyl methacrylate-styrene-butadiene copolymer and the copolymer of styrene and glycidyl methacrylate are generally selected for synergistic toughening, but the addition of a large amount of toughening agents can lead to the increase of the processing temperature, the reduction of the fluidity and the reduction of the flame retardant property of PC materials. Currently, the poly (trimethylene) polycarbonates in the prior art are poor in flame retardance and processability, and some patents have made some studies on practical application systems of flame retardant polycarbonates for medical use to improve their difficult-to-process properties, such as: the invention discloses a medical flame-retardant and easily-formed polycarbonate material and a preparation method thereof, wherein zinc oxide and boric acid are adopted as reaction raw materials, ammonium persulfate is adopted as an initiator to participate in polymerization reaction with acrylonitrile as a monomer, zinc oxide and zinc borate generated by boric acid have good flame retardance, play a good synergistic effect with hexachlorocyclotriphosphazene, then the obtained polymer is subjected to electrostatic spinning to obtain flame-retardant fiber, and then the flame-retardant fiber is subjected to hydroxylation and amination reaction, finally polyamide is grafted on the surface of the flame-retardant fiber, and then the flame-retardant fiber is mixed with carbonate monomer to participate in polymerization reaction of carbonate to obtain the polycarbonate material with good flame retardance and high mechanical strength; chinese patent CN 107325513a discloses a bacteriostatic polycarbonate material for nano silver deposition medical treatment, which is composed of the following raw materials in parts by weight: 50-75 parts of polycarbonate, 20-25 parts of initiator solution, 10-15 parts of polyvinylpyrrolidone, 10-15 parts of acrylonitrile, 0.5-1 part of chitosan and 0.5-1 part of potassium sorbate; the invention mainly focuses on improving the antibacterial effect of the polycarbonate, and has the defects of unobvious improvement on the flame retardant effect and the chemical resistant agent effect and difficulty in injection molding in the processing process; chinese patent CN 107164824a discloses a sol-type polycarbonate material with high bacteriostasis for medical use, which is composed of the following raw materials in parts by weight: 40-50 parts of poly (trimethylene carbonate), 40-50 parts of a bacteriostat, 8-12 parts of titanyl sulfate, 5-8 parts of acrylonitrile, 0.5-1 part of nylon acid methyl ester and 0.05-0.1 part of 8-hydroxyquinoline; the invention adopts a physical modification method to mainly improve the antibacterial property of the polycarbonate material, but the modified polycarbonate material has high processing temperature and insufficient fluidity and cannot be better applied to large-scale workpieces.
Disclosure of Invention
Based on the above, an object of the present invention is to provide a flame retardant polycarbonate composition which has excellent mechanical properties, fluidity and organic solvent resistance, and can be applied to industries such as medical instruments, etc. while having good flame retardant properties.
The specific technical scheme for realizing the aim of the invention comprises the following steps:
the flame-retardant polycarbonate composition is prepared from the following raw materials in parts by weight:
wherein the sum of the weight parts of the polycarbonate resin, the polysiloxane-polycarbonate and the acrylonitrile-butadiene-styrene copolymer is 100 parts; the weight ratio of the bisphenol A bis (diphenyl phosphate) to the organosilicon flame retardant synergist is 2.5-24:1.
In some embodiments, the flame retardant polycarbonate composition is prepared from the following raw materials in parts by weight:
the weight ratio of the bisphenol A bis (diphenyl phosphate) to the organosilicon flame retardant synergist is 4-10:1.
In some embodiments, the polycarbonate composition is prepared from the following raw materials in parts by weight:
the weight ratio of the bisphenol A bis (diphenyl phosphate) to the organosilicon flame retardant synergist is 4-5:1.
In some of these embodiments, the styrene-acrylonitrile-glycidyl methacrylate copolymer is a reactive compatibilizer in which the mass fraction of glycidyl methacrylate is 2wt% to 4wt%.
In some of these embodiments, the melt index of the polycarbonate resin is 10g/10min to 12g/10min.
In some of these embodiments, the polysiloxane-polycarbonate copolymer has a melt index of 3g/10min to 10g/10min and a siloxane content of 6wt% to 14wt%.
In some of these embodiments, the hindered phenolic antioxidant is stearyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and/or the phosphite antioxidant is bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate.
In some of these embodiments, the silicone flame retardant synergist is FAC-107 and/or STR-100.
In some of these embodiments, the antimicrobial agent is an Ag-based carrier-based inorganic antimicrobial agent.
It is another object of the present invention to provide a method for preparing the above flame retardant polycarbonate composition.
The specific technical scheme for realizing the aim of the invention comprises the following steps:
a method of preparing a flame retardant polycarbonate composition comprising the steps of:
(1) Mixing the dried polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer;
(2) Mixing bisphenol A bis (diphenyl phosphate), organosilicon flame retardant synergist, hindered phenol antioxidant, phosphite antioxidant, pentaerythritol stearate and modified polytetrafluoroethylene and an antibacterial agent;
(3) Mixing the mixed mixture obtained in the step (1) with the mixed mixture obtained in the step (2);
(4) And (3) adding the mixed material obtained in the step (3) into a parallel double-screw extruder through a feeder, and performing melt extrusion granulation in the parallel double-screw extruder to obtain the composite material.
In some of these embodiments, the process parameters of the melt extrusion granulation include: the temperature of the first area is 210-240 ℃, the temperature of the second area is 230-260 ℃, the temperature of the third area is 235-260 ℃, the temperature of the fourth area is 220-260 ℃, the temperature of the fifth area is 220-260 ℃, the temperature of the sixth area is 220-260 ℃, the temperature of the seventh area is 220-260 ℃, the temperature of the eighth area is 220-260 ℃, the temperature of the die head is 240-275 ℃, and the screw rotating speed is 200-600 rpm.
In some of these embodiments, the process parameters of the melt extrusion granulation include: the temperature of the first area is 225-235 ℃, the temperature of the second area is 235-245 ℃, the temperature of the third area is 245-255 ℃, the temperature of the fourth area is 245-255 ℃, the temperature of the fifth area is 245-255 ℃, the temperature of the sixth area is 245-255 ℃, the temperature of the seventh area is 240-250 ℃, the temperature of the eighth area is 240-250 ℃, the temperature of the die head is 255-265 ℃, and the screw rotating speed is 350-500 rpm.
In some of these embodiments, the drying conditions in step (1) include: the temperature is 80-110 ℃ and the time is 4-8 hours.
In some of these embodiments, the drying conditions in step (1) include: the temperature is 100-110 ℃ and the time is 4-6 hours.
In some embodiments, the mixing in step (1) is carried out at a stirring speed of 400 rpm to 600 rpm.
In some embodiments, the mixing in step (2) is carried out at a stirring speed of 400 rpm to 600 rpm.
In some embodiments, the mixing in step (3) is performed at a stirring speed of 400 rpm to 600 rpm for a stirring time of 8min to 12min.
In some of these embodiments, the screw shape of the parallel twin screw extruder is single-flighted.
In some of these embodiments, the parallel twin screw extruder has a ratio L/D of screw length L to diameter D of 35 to 50; more than 1 meshing block areas and more than 1 reverse thread areas are arranged on the screw rod.
In some of these embodiments, the ratio L/D of the screw length L to the diameter D is from 35 to 45; and the screw is provided with 2 meshing block areas and 1 reverse thread area.
The principle of the flame-retardant polycarbonate composition and the preparation method of the invention are as follows:
Unlike traditional bromine-antimony flame retardation, the environment-friendly halogen-free flame retardant bisphenol A bis (diphenyl phosphate) and the organic silicon flame retardation synergist are compounded for use, and the bisphenol A bis (diphenyl phosphate) belongs to a flame retardation plasticizer, and has better capability of improving the flame retardation effect of a polycarbonate composition, but the bisphenol A bis (diphenyl phosphate) can only enable the material to reach V0 under the condition of large use amount, and the fluidity of the material is greatly improved and the toughness is reduced when the bisphenol A bis (diphenyl phosphate) is excessively added; the organic silicon flame retardant synergist belongs to a siloxane grafted flaky solid flame retardant, which hardly has negative influence on other performances while improving the PC flame retardance, and organic silicon molecules can accelerate the surface acceleration of polycarbonate composition to form carbon and reduce the release of smoke. Compared with the traditional methyl methacrylate-styrene-butadiene copolymer, the methyl methacrylate-styrene-organosilicon copolymer replaces butadiene with organosilicon, so that the weather resistance and impact resistance of the material can be effectively improved, the polycarbonate composition has higher toughness and chemical resistance, the material can be applied to a harsher environment for a long time, and the performance retention rate is not reduced. In addition, the Si-O-Si bond on the main chain of the methyl methacrylate-styrene-organic silicon copolymer is more easily grafted with the PC matrix under the action of the styrene-acrylonitrile-glycidyl methacrylate copolymer, so that the flame retardance of the PC matrix is effectively improved, and the problems of difficult compounding and difficult uniform dispersion when the methyl methacrylate-styrene-organic silicon copolymer is added into the PC in a physical mixing mode are solved by adopting the styrene-acrylonitrile-glycidyl methacrylate copolymer (SAG-001) as a compatilizer and an interface improver, so that the compatibility of each component in the formula is improved, the overall fluidity of the material is increased, and each property after melt blending is more excellent.
The invention adopts the antioxidant which is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, has good thermal stability in the process of blending the polycarbonate composition, and the hindered piperidinyl of the antioxidant can provide antioxidant effect and improve the dyeability of the copolymer; the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate having a melting point of 239 ℃ and a thermal decomposition temperature of more than 350 ℃ and good heat resistance and hydrolysis resistance can provide excellent color stability and melt stability to the modified polycarbonate material during high-speed blending, can prevent thermal degradation of polycarbonate, flame retardant and other small molecule auxiliary agents during high temperature, can suppress thermal oxidative discoloration due to long time, and can provide a flame retardant composition for polycarbonate materials (NO x ) Color stability under gaseous environment prevents the chameleon from discolouring. The Ag-based carrier inorganic antibacterial agent is selected, so that the heat-resistant stability is higher, the bacteria can be effectively inhibited from breeding on the surface of a workpiece, and the antibacterial efficiency can reach 99.99%.
The pentaerythritol stearate has the effects of improving the demolding property and increasing the thermal stability of the material, and can effectively weaken the shearing force of the screw on the material and reduce the performance damage of the material due to physical shearing when being independently used as a lubricant.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the bisphenol A bis (diphenyl phosphate) serving as a phosphate flame retardant and an organosilicon flame retardant synergist are compounded, so that the temperature of a processing melt of the polycarbonate composition is effectively reduced, and the processing fluidity is improved; the combination property of the polycarbonate composition is improved by adding polysiloxane-polycarbonate copolymer, methyl methacrylate-styrene-organic silicon copolymer and reactive compatilizer styrene-acrylonitrile-glycidyl methacrylate copolymer, and the internal stress of PC material is reduced by introducing a large amount of siloxane grafts, and meanwhile, notch sensitivity and thick wall brittleness of the PC material are improved. Meanwhile, the addition of a small amount of acrylonitrile-butadiene-styrene copolymer greatly reduces the processing temperature of the whole material on the basis of further reducing the internal stress of PC resin, so that the improved polycarbonate composition has better processability. The raw material components of the invention are matched with each other, so that the obtained flame-retardant polycarbonate composition has excellent flame retardant property, mechanical property, processing property, chemical resistance and antibacterial property, and is suitable for medical products.
2. The preparation method of the flame-retardant polycarbonate composition provided by the invention has the advantages of simple process, easiness in control, low equipment requirement, low investment and contribution to industrial production, and all used equipment is general polymer processing equipment.
Drawings
FIG. 1 is a flow chart of a process for preparing a flame retardant polycarbonate composition of the invention.
Detailed Description
In order that the invention may be understood more fully, the invention will be described with reference to the accompanying drawings. This invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The raw materials used in the examples and comparative examples of the present invention are as follows:
A polycarbonate resin having a weight average molecular weight of 17000-19000 and a melt index of 10g/10min, selected from Japanese Di people Co., ltd;
polysiloxane-polycarbonate copolymer having a weight average molecular weight of 21000-23000, melt index of 3.5g/10min, and silicone content of 14wt%; selected from the korean company of Sanyang limited;
bisphenol a bis (diphenyl phosphate) selected from Shanghai shared gold chemical Co., ltd;
the silicone flame retardant synergist FCA-107 is selected from the company Kang Daoning of America;
methyl methacrylate-styrene-silicone copolymer selected from mitsubishi corporation of japan;
styrene-acrylonitrile-glycidyl methacrylate copolymer, glycidyl Methacrylate (GMA) 3wt%, selected from sigma aldrich (Shanghai) trade company;
stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, selected, for example, from basf, germany;
bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate selected from Shanghai Yao Fine chemical Co., ltd;
pentaerythritol stearate selected from the company Zhaoqing City Sendeli chemical industry Co., ltd;
modified polytetrafluoroethylene, model: SN3300B7, selected from Guangzhou Innovative materials, inc.;
The antibacterial agent BM-102SD is selected from Fu Yu Zhi Co Ltd.
A poly-spiro-phosphate diamide selected from the group consisting of minox chemical engineering, inc;
methyl methacrylate-styrene-butadiene copolymer selected from the group consisting of brillouin corporation;
styrene maleic anhydride copolymer selected from Dongguan star chemical engineering limited company;
the present invention will be described in detail with reference to specific examples.
Example 1A flame retardant polycarbonate composition and method of making the same
The flame-retardant polycarbonate composition of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the flame retardant polycarbonate composition of the embodiment comprises the following steps:
(1) The polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent are added into another stirrer (the rotation speed is 500 rpm) for mixing.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Example 2A flame retardant polycarbonate composition and method of making the same
The flame-retardant polycarbonate composition of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the flame retardant polycarbonate composition of the embodiment comprises the following steps:
(1) The polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent are added into another stirrer (the rotation speed is 500 rpm) for mixing.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Example 3A flame retardant polycarbonate composition and method of making the same
The flame-retardant polycarbonate composition of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the flame retardant polycarbonate composition of the embodiment comprises the following steps:
(1) The polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent are added into another stirrer (the rotation speed is 500 rpm) for mixing.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Example 4A flame retardant polycarbonate composition and method of making the same
The flame-retardant polycarbonate composition of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the flame retardant polycarbonate composition of the embodiment comprises the following steps:
(1) The polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent are added into another stirrer (the rotation speed is 500 rpm) for mixing.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Example 5A flame retardant polycarbonate composition and method of making the same
The flame-retardant polycarbonate composition of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the flame retardant polycarbonate composition of the embodiment comprises the following steps:
(1) The polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent are added into another stirrer (the rotation speed is 500 rpm) for mixing.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Example 6A flame retardant polycarbonate composition and method of making the same
The flame-retardant polycarbonate composition of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the flame retardant polycarbonate composition of the embodiment comprises the following steps:
(1) The polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent are added into another stirrer (the rotation speed is 500 rpm) for mixing.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Example 7A flame retardant polycarbonate composition and method of making the same
The flame-retardant polycarbonate composition of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the flame retardant polycarbonate composition of the embodiment comprises the following steps:
(1) The polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent are added into another stirrer (the rotation speed is 500 rpm) for mixing.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Example 8A flame retardant polycarbonate composition and method of making the same
The flame-retardant polycarbonate composition of the embodiment is prepared from the following raw materials in parts by weight:
the preparation method of the flame retardant polycarbonate composition of the embodiment comprises the following steps:
(1) The polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent are added into another stirrer (the rotation speed is 500 rpm) for mixing.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is double-thread, the ratio L/D of the length L and the diameter D of the screw is 50, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Comparative example 1A flame retardant polycarbonate composition and method of preparing the same
The flame-retardant polycarbonate composition of the comparative example is prepared from the following raw materials in parts by weight:
a method for preparing the flame retardant polycarbonate composition of this comparative example, comprising the steps of:
(1) The polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), stearyl beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent were added to another stirrer (rotation speed 500 rpm) and mixed.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Comparative example 2 flame retardant polycarbonate composition and method for preparing the same
The flame-retardant polycarbonate composition of the comparative example is prepared from the following raw materials in parts by weight:
a method for preparing the flame retardant polycarbonate composition of this comparative example, comprising the steps of:
(1) The polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) The organosilicon flame retardant synergist, the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, the bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, the modified polytetrafluoroethylene and the antibacterial agent are added into another stirrer for mixing at the rotating speed of 500 revolutions per minute.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Comparative example 3A flame retardant polycarbonate composition and method of preparing the same
The flame-retardant polycarbonate composition of the comparative example is prepared from the following raw materials in parts by weight:
a method for preparing the flame retardant polycarbonate composition of this comparative example, comprising the steps of:
(1) The polycarbonate resin and the acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and mixed with the methyl methacrylate-styrene-silicone copolymer and the styrene-acrylonitrile-glycidyl methacrylate copolymer in a stirrer (rotation speed: 500 rpm).
(2) Bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent are added into another stirrer (the rotation speed is 500 rpm) for mixing.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Comparative example 4A flame retardant polycarbonate composition and method of preparing the same
The flame-retardant polycarbonate composition of the comparative example is prepared from the following raw materials in parts by weight:
/>
a method for preparing the flame retardant polycarbonate composition of this comparative example, comprising the steps of:
(1) The polysiloxane-polycarbonate copolymer and the acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and added to a stirrer (rotation speed: 500 rpm) together with the methyl methacrylate-styrene-silicone copolymer and the styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent are added into another stirrer (the rotation speed is 500 rpm) for mixing.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Comparative example 5A flame retardant polycarbonate composition and method of preparing the same
The flame-retardant polycarbonate composition of the comparative example is prepared from the following raw materials in parts by weight:
a method for preparing the polycarbonate composition of this comparative example, comprising the steps of:
(1) The polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent are added into another stirrer (the rotation speed is 500 rpm) for mixing.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Comparative example 6 flame retardant polycarbonate composition and method for preparing the same
The flame-retardant polycarbonate composition of the comparative example is prepared from the following raw materials in parts by weight:
a method for preparing the flame retardant polycarbonate composition of this comparative example, comprising the steps of:
(1) The polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent are added into another stirrer (the rotation speed is 500 rpm) for mixing.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Comparative example 7A flame retardant polycarbonate composition and method of preparing the same
The flame-retardant polycarbonate composition of the comparative example is prepared from the following raw materials in parts by weight:
a method for preparing the flame retardant polycarbonate composition of this comparative example, comprising the steps of:
(1) The polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), poly spiro phosphate diamide, stearyl beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent were added to another stirrer (500 rpm) and mixed.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Comparative example 8A flame retardant polycarbonate composition and method of preparing the same
The flame-retardant polycarbonate composition of the comparative example is prepared from the following raw materials in parts by weight:
a method for preparing the flame retardant polycarbonate composition of this comparative example, comprising the steps of:
(1) The polycarbonate resin, the polysiloxane-polycarbonate copolymer and the acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with the methyl methacrylate-styrene-butadiene copolymer and the styrene-acrylonitrile-glycidyl methacrylate copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent are added into another stirrer (the rotation speed is 500 rpm) for mixing.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Comparative example 9A flame retardant polycarbonate composition and method of preparing the same
The flame-retardant polycarbonate composition of the comparative example is prepared from the following raw materials in parts by weight:
a method for preparing the flame retardant polycarbonate composition of this comparative example, comprising the steps of:
(1) The polycarbonate resin, polysiloxane-polycarbonate copolymer, and acrylonitrile-butadiene-styrene copolymer were dried at a temperature of 100℃for 4 hours, cooled, and then added to a stirrer (rotation speed: 500 rpm) together with the methyl methacrylate-styrene-silicone copolymer and styrene maleic anhydride copolymer to mix.
(2) Bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent are added into another stirrer (the rotation speed is 500 rpm) for mixing.
(3) Pouring the mixed materials obtained in the step (1) and the step (2) into the same high-speed stirrer (the rotating speed is 500 revolutions per minute), and mixing for 10 minutes.
(4) Adding the mixed mixture obtained in the step (3) into a parallel double-screw extruder through a feeder, and carrying out melt extrusion granulation in the parallel double-screw extruder (eight zones in total), wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 245 ℃, the temperature of the die head is 260 ℃, and the rotating speed of the screw is 500rpm; the screw shape of the parallel double-screw extruder is single-thread, the ratio L/D of the length L and the diameter D of the screw is 35, and 2 meshing block areas and 1 reverse thread area are arranged on the screw.
Table 1 list of the raw materials in parts by weight for examples and comparative examples
Note that: a, changing the structure of a screw; PC is a polycarbonate resin; si-PC is a polysiloxane-polycarbonate copolymer; ABS is an acrylonitrile-butadiene-styrene copolymer; BDP is bisphenol A bis (diphenyl phosphate); s-2001 is a methyl methacrylate-styrene-silicone copolymer; SAG-001 is a styrene-acrylonitrile-glycidyl methacrylate copolymer. A is a poly spiro phosphate diamide; b is methyl methacrylate-styrene-butadiene copolymer; c is a styrene maleic anhydride copolymer.
The polycarbonate compositions prepared in the above examples and comparative examples were subjected to the following performance tests:
flame retardant properties: the test was conducted according to UL-94 standard, and the thickness of the bar was 0.7mm.
Melt index: the test is carried out according to GB/T3682-2000 standard, the test temperature is 260 ℃, and the load is 2.16kg.
Solvent resistance test: preparing 0.25-0.33wt% of benzethonium chloride and 15-18wt% of isopropanol, soaking the paper towel, covering the surface of the sample bar under stress, and recording the breaking time (h) of the sample bar, wherein the higher the value is, the better.
Impact properties: the spline thickness was 4mm, measured according to GB/T1843-2008, the higher the value the better.
The results of the performance test are shown in Table 2.
Table 2A list of the properties of the polycarbonate compositions of the examples and comparative examples
Examples 1 to 7 are polycarbonate compositions prepared by adjusting the addition amounts of polycarbonate, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer, bisphenol A bis (diphenyl phosphate), silicone flame retardant synergist, methyl methacrylate-styrene-silicone copolymer, styrene and glycidyl methacrylate copolymer.
In the preparation raw materials of the polycarbonate composition, a flame-retardant system is bisphenol A bis (diphenyl phosphate) and an organosilicon flame-retardant synergist, wherein the weight part of the bisphenol A bis (diphenyl phosphate) is 5-12 parts, and the weight part of the organosilicon flame-retardant synergist is 0.5-2 parts; when the component amounts of the bisphenol a bis (diphenyl phosphate) alone, or the silicone flame retardant synergist alone, are relatively large, i.e., bisphenol a bis (diphenyl phosphate) is close to 12 parts (the silicone flame retardant synergist is not close to 2 parts), or the silicone flame retardant synergist is close to 2 parts (the bisphenol a bis (diphenyl phosphate) is not close to 12 parts), the flame retardant properties of the polycarbonate composition cannot reach 0.7mmv0 (as in examples 1 to 4). When bisphenol A bis (diphenyl phosphate) and the silicone flame retardant synergist are in a proper proportion range, the total addition amount of the bisphenol A bis (diphenyl phosphate) and the silicone flame retardant synergist is reduced to a certain extent, but the flame retardant effect of the bisphenol A bis (diphenyl phosphate) and the silicone flame retardant synergist on the polycarbonate composition is better, and can reach 0.7mmV0, thereby indicating that the bisphenol A bis (diphenyl phosphate) and the silicone flame retardant synergist have a synergistic effect in the polycarbonate composition. When the weight ratio of bisphenol A bis (diphenyl phosphate) to the organosilicon flame retardant synergist is 8:2, the flame retardant effect of the polycarbonate composition is optimal, and the solvent resistance effect and the notch impact strength effect are also better.
The greater the acrylonitrile-butadiene-styrene copolymer and bisphenol A bis (diphenyl phosphate) content in the formulation, the greater the melt index of the polycarbonate composition, and the progressively lower the solvent break duration and notched impact resistance, mainly because the acrylonitrile-butadiene-styrene copolymer progressively decreases in molecular weight, while more bisphenol A bis (diphenyl phosphate) promotes faster plasticization of the polycarbonate, resulting in weaker molecular forces.
The polycarbonate compositions prepared in examples 7 were found to have the best overall properties and the best proportions of the respective raw materials by combining the various factors from the performance data of the polycarbonate compositions prepared in comparative examples 1 to 7.
Example 7 the parallel twin-screw extruder used in example 8 had a double-flighted screw shape, a ratio L/D of screw length L to diameter D of 50, the parallel twin-screw extruder used in example 7 had a single-flighted screw shape, and a ratio L/D of screw length L to diameter D of 35, compared with example 8, and it was found that the polycarbonate composition prepared by using the screw parameters of the parallel twin-screw extruder described in example 7 was better in solvent resistance and processability.
Comparative example 1 compared with example 7, comparative example 1 was added with only one flame retardant bisphenol a bis (diphenyl phosphate) and no silicone flame retardant synergist, and the flame retardant property, solvent resistance and impact strength of the obtained polycarbonate composition were remarkably poor, because the single flame retardant bisphenol a bis (diphenyl phosphate) did not allow the flame retardant property of the polycarbonate composition to reach V0 at the added amount, and the intermolecular forces of the materials were weakened due to a certain plasticizing promoting effect on the polycarbonate, macroscopic appearance was shown by deterioration of the solvent resistance of the materials, and decrease of the impact strength and increase of flowability.
Compared with the comparative example 2, the comparative example 2 only adds one flame retardant, namely the organic silicon flame retardant synergist, but does not add bisphenol A bis (diphenyl phosphate), so that the obtained polycarbonate composition has poor flame retardant property, obviously improved solvent resistance and toughness, and the side surface proves that the bisphenol A bis (diphenyl phosphate) reduces the performance of the polycarbonate composition, and also shows that the special siloxane group of the organic silicon flame retardant synergist can greatly improve the solvent resistance and toughness of the polycarbonate composition.
Comparative example 3 the polycarbonate composition obtained without the addition of the polysiloxane-polycarbonate copolymer in comparative example 3 showed a significant decrease in solvent resistance and impact strength, which indicates that the siloxane-polycarbonate copolymer is essential for improving solvent resistance and impact strength of the polycarbonate composition.
Comparative example 4 in comparison with example 7, in comparative example 4, no polycarbonate was added, but a single polysiloxane-polycarbonate copolymer was used, and the resulting polycarbonate composition had significantly improved solvent resistance and impact strength, but a significantly reduced melt index, resulting in a material that was difficult to process; and because polysiloxane-polycarbonate copolymers are expensive, they are difficult to apply in large quantities to production.
Comparative example 5 in comparison with example 7, 6 parts of methyl methacrylate-styrene-silicone copolymer was added to comparative example 5, and the impact strength of the obtained polycarbonate composition was slightly improved, the solvent resistance of the material was not greatly different, but the melt index was remarkably lowered, and the obtained polycarbonate composition was difficult to process and difficult to advance mass production.
Comparative example 6 in comparison with example 7, the polycarbonate composition obtained by adding 15 parts of the acrylonitrile-butadiene-styrene copolymer in comparative example 6 has a remarkably improved melt index, but the flame retardancy, solvent resistance and impact strength of the material are remarkably reduced due to the increased addition amount of the acrylonitrile-butadiene-styrene copolymer.
Compared with the comparative example 7, the flame retardant in the comparative example 7 is bisphenol A bis (diphenyl phosphate) and poly-spiro phosphate diamide, the flame retardant property of the obtained flame retardant polycarbonate composition is not obviously reduced, the melt index is obviously improved, the solvent resistance and the impact strength of the material are obviously reduced, and the organic silicon flame retardant synergist is obviously better than the poly-spiro phosphate diamide in improving the solvent resistance of the polycarbonate composition, so that the prepared flame retardant polycarbonate composition is more suitable for medical products.
Comparative example 8 in comparison with example 7, the flame retardant polycarbonate composition obtained in comparative example 8 using methyl methacrylate-styrene-butadiene copolymer as a toughening agent has significantly reduced flame retardant properties and solvent resistance as well as impact strength, in addition to an increase in melt index.
Comparative example 9 As compared with example 7, the flame retardant polycarbonate composition obtained in comparative example 9, using a styrene maleic anhydride copolymer as a compatibilizer, has a greatly reduced melt index, although the flame retardant properties, solvent resistance and impact strength are not significantly changed.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (9)

1. The flame-retardant polycarbonate composition is characterized by being prepared from the following raw materials in parts by weight:
40-70 parts of polycarbonate resin,
20-50 parts of polysiloxane-polycarbonate copolymer,
5 to 10 parts of acrylonitrile-butadiene-styrene copolymer,
bisphenol A bis (diphenyl phosphate) 5-12,
0.5 to 2 parts of organic silicon flame retardant synergist,
2-5 parts of methyl methacrylate-styrene-organic silicon copolymer,
0.5 to 2 parts of styrene-acrylonitrile-glycidyl methacrylate copolymer,
0.1 to 0.3 part of hindered phenol antioxidant,
0.1 to 0.5 part of phosphite antioxidant,
0.2 to 0.5 parts of pentaerythritol stearate,
0.3 to 0.5 part of modified polytetrafluoroethylene,
0.2 to 0.4 parts of antibacterial agent,
wherein the sum of the weight parts of the polycarbonate resin, the polysiloxane-polycarbonate and the acrylonitrile-butadiene-styrene copolymer is 100 parts;
the weight ratio of the bisphenol A bis (diphenyl phosphate) to the organic silicon flame retardant synergist is 4-5:1; the organic silicon flame retardant synergist is FAC-107.
2. The flame retardant polycarbonate composition of claim 1, wherein the flame retardant polycarbonate composition is prepared from the following raw materials in parts by weight:
45-70 parts of polycarbonate resin,
25 to 40 parts of polysiloxane-polycarbonate copolymer,
5 to 10 parts of acrylonitrile-butadiene-styrene copolymer,
6-10 parts of bisphenol A bis (diphenyl phosphate),
1 to 2 parts of organic silicon flame retardant synergist,
2-4 parts of methyl methacrylate-styrene-organic silicon copolymer,
0.5 to 2 parts of styrene-acrylonitrile-glycidyl methacrylate copolymer,
0.1 to 0.3 part of hindered phenol antioxidant,
0.1 to 0.5 part of phosphite antioxidant,
0.2 to 0.5 parts of pentaerythritol stearate,
0.3-0.5 parts of modified polytetrafluoroethylene;
0.2-0.4 parts of antibacterial agent.
3. The flame retardant polycarbonate composition of claim 2, wherein the polycarbonate composition is prepared from the following raw materials in parts by weight:
60-65 parts of polycarbonate resin,
25 to 35 parts of polysiloxane-polycarbonate copolymer,
5 to 6 parts of acrylonitrile-butadiene-styrene copolymer,
7-9 parts of bisphenol A bis (diphenyl phosphate),
1 to 2 parts of organic silicon flame retardant synergist,
2-4 parts of methyl methacrylate-styrene-organic silicon copolymer,
0.5 to 1 part of styrene-acrylonitrile-glycidyl methacrylate copolymer,
0.1 to 0.3 part of hindered phenol antioxidant,
0.1 to 0.5 part of phosphite antioxidant,
0.2 to 0.5 parts of pentaerythritol stearate,
0.3-0.5 parts of modified polytetrafluoroethylene;
0.2-0.4 parts of antibacterial agent.
4. The flame retardant polycarbonate composition according to any one of claims 1 to 3, wherein the mass fraction of glycidyl methacrylate in the styrene-acrylonitrile-glycidyl methacrylate copolymer is 2 to 4wt%.
5. The flame retardant polycarbonate composition according to any one of claims 1 to 3, wherein the melt index of the polycarbonate resin is 10g/10min to 12g/10min;
and/or the melt index of the polysiloxane-polycarbonate copolymer is 3g/10 min-10 g/10min, and the siloxane content is 6wt% to 14wt%.
6. The flame retardant polycarbonate composition of any one of claims 1-3, wherein the hindered phenolic antioxidant is octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate;
and/or the phosphite antioxidant is bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate;
and/or the antibacterial agent is an Ag-based carrier inorganic antibacterial agent.
7. The method for preparing a flame retardant polycarbonate composition according to any one of claims 1 to 6, comprising the steps of:
(1) Mixing the dried polycarbonate resin, polysiloxane-polycarbonate copolymer, acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-styrene-silicone copolymer and styrene-acrylonitrile-glycidyl methacrylate copolymer;
(2) Mixing bisphenol A bis (diphenyl phosphate), an organosilicon flame retardant synergist, a hindered phenol antioxidant, a phosphite antioxidant, pentaerythritol stearate, modified polytetrafluoroethylene and an antibacterial agent;
(3) Mixing the mixed mixture obtained in the step (1) with the mixed mixture obtained in the step (2);
(4) And (3) adding the mixed material obtained in the step (3) into a parallel double-screw extruder through a feeder, and performing melt extrusion granulation in the parallel double-screw extruder to obtain the composite material.
8. The method of preparing a flame retardant polycarbonate composition of claim 7, wherein the melt extrusion pelletization process parameters comprise: the temperature of the first area is 210-240 ℃, the temperature of the second area is 230-260 ℃, the temperature of the third area is 235-260 ℃, the temperature of the fourth area is 220-260 ℃, the temperature of the fifth area is 220-260 ℃, the temperature of the sixth area is 220-260 ℃, the temperature of the seventh area is 220-260 ℃, the temperature of the eighth area is 220-260 ℃, the temperature of the die head is 240-275 ℃, and the screw rotating speed is 200-600 rpm;
And/or, the drying conditions in step (1) include: the temperature is 80-110 ℃ and the time is 4-8 hours;
and/or, the stirring speed of the mixing in the step (1) is 400-600 rpm;
and/or, the stirring speed of the mixing in the step (2) is 400-600 rpm;
and/or, in the step (3), the stirring speed of the mixing is 400-600 rpm, and the stirring time is 8-12 min;
and/or the screw shape of the parallel double screw extruder is single-thread;
and/or the ratio L/D of the screw length L to the diameter D of the parallel double-screw extruder is 35-50; more than 1 meshing block areas and more than 1 reverse thread areas are arranged on the screw rod.
9. The method for producing a flame retardant polycarbonate composition according to claim 8, wherein,
the technological parameters of the melt extrusion granulation comprise: the first area temperature is 225-235 ℃, the second area temperature is 235-245 ℃, the third area temperature is 245-255 ℃, the fourth area temperature is 245-255 ℃, the fifth area temperature is 245-255 ℃, the sixth area temperature is 245-255 ℃, the seventh area temperature is 240-250 ℃, the eighth area temperature is 240-250 ℃, the die head temperature is 255-265 ℃ and the screw speed is 350-500 rpm;
And/or, the drying conditions in step (1) include: the temperature is 100-110 ℃ and the time is 4-6 hours;
and/or the ratio L/D of the length L and the diameter D of the screw is 35-45; and the screw is provided with 2 meshing block areas and 1 reverse thread area.
CN202210399952.XA 2022-04-15 2022-04-15 Flame retardant polycarbonate composition and method for preparing the same Active CN114605805B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210399952.XA CN114605805B (en) 2022-04-15 2022-04-15 Flame retardant polycarbonate composition and method for preparing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210399952.XA CN114605805B (en) 2022-04-15 2022-04-15 Flame retardant polycarbonate composition and method for preparing the same

Publications (2)

Publication Number Publication Date
CN114605805A CN114605805A (en) 2022-06-10
CN114605805B true CN114605805B (en) 2023-08-25

Family

ID=81869062

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210399952.XA Active CN114605805B (en) 2022-04-15 2022-04-15 Flame retardant polycarbonate composition and method for preparing the same

Country Status (1)

Country Link
CN (1) CN114605805B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116285283B (en) * 2022-12-26 2024-06-18 中化工程塑料(扬州)有限公司 Halogen-free flame retardant material and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000119502A (en) * 1998-10-15 2000-04-25 Kanegafuchi Chem Ind Co Ltd Flame-retardant thermoplastic resin composition
CN101857717A (en) * 2010-03-10 2010-10-13 上海锦湖日丽塑料有限公司 Flame-retardant polycarbonate alloy with excellent chemical resistance and preparation method thereof
CN105219052A (en) * 2015-10-21 2016-01-06 奉化市旭日鸿宇有限公司 Housing of TV set halogen-free flameproof height flowing PC/ABS material and preparation method thereof
WO2018107969A1 (en) * 2016-12-15 2018-06-21 金发科技股份有限公司 Pc/abs composition, preparation method therefor and use thereof
CN112778741A (en) * 2021-01-11 2021-05-11 广东圆融新材料有限公司 Flame-retardant polycarbonate composition and preparation method thereof
CN112940482A (en) * 2021-04-13 2021-06-11 东莞市东翔塑胶有限公司 Composite material suitable for in-mold injection molding and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000119502A (en) * 1998-10-15 2000-04-25 Kanegafuchi Chem Ind Co Ltd Flame-retardant thermoplastic resin composition
CN101857717A (en) * 2010-03-10 2010-10-13 上海锦湖日丽塑料有限公司 Flame-retardant polycarbonate alloy with excellent chemical resistance and preparation method thereof
CN105219052A (en) * 2015-10-21 2016-01-06 奉化市旭日鸿宇有限公司 Housing of TV set halogen-free flameproof height flowing PC/ABS material and preparation method thereof
WO2018107969A1 (en) * 2016-12-15 2018-06-21 金发科技股份有限公司 Pc/abs composition, preparation method therefor and use thereof
CN112778741A (en) * 2021-01-11 2021-05-11 广东圆融新材料有限公司 Flame-retardant polycarbonate composition and preparation method thereof
CN112940482A (en) * 2021-04-13 2021-06-11 东莞市东翔塑胶有限公司 Composite material suitable for in-mold injection molding and preparation method thereof

Also Published As

Publication number Publication date
CN114605805A (en) 2022-06-10

Similar Documents

Publication Publication Date Title
CN1216101C (en) Preparation method of toughness enhanced and reinforced polybutanediol terephthalate nanometer composition
CN101195707B (en) Glass fiber-reinforced nylon 6-polypropylene alloy material
EP2186846B1 (en) Natural Fiber-Reinforced Polylactic Acid Resin Composition and Molded Product Made Using the Same
CN102108181B (en) Thermoplastic alloy and preparation method thereof
CN103044762A (en) Mineral reinforced halogen-free flame-retardant polypropylene composite material and preparation method thereof
CN102532849B (en) PC/ASA/PBT (poly carbonate/ acrylonitrile-styrene-acrylate/polybutylene terephthalate) alloy material and preparation method thereof
CN112391045B (en) Polycarbonate composition and preparation method and application thereof
CN114605805B (en) Flame retardant polycarbonate composition and method for preparing the same
CN1580126A (en) Preparation of PC/ABS alloy
CN112280273B (en) PMMA/ionomer/PC ternary alloy and preparation method thereof
CN111763383B (en) Good-touch glass fiber reinforced polypropylene composite and preparation method thereof
CN114874616B (en) Anti-yellowing low-scale halogen-free flame-retardant polyamide composite material and preparation method thereof
CN110791049B (en) Flame-retardant reinforced polyphenyl ether/high impact polystyrene composition and preparation method thereof
CN111995843A (en) Low-linear expansion coefficient polybutylene terephthalate composite material and preparation method thereof
US5028649A (en) Polyethylene terephthalate molding compounds with sodium stearate and polyester amides
CN110194893B (en) Silicon-aluminum compound and magnesium hydroxide synergistic flame-retardant nylon composite material and preparation method thereof
CN110551390B (en) High-toughness spraying-free polyamide 6 material and preparation method thereof
EP3130633A1 (en) Polyamides with good mechanics and shrinkage
CN110669334B (en) High-toughness spraying-free polyamide 66 material and preparation method thereof
DE2849593C2 (en) Polyester molding compound
CN1060189C (en) Fire-retardant polyester composite material, and preparation method thereof
CN104710744A (en) Toughened modified PC/PET alloy material with high impact resistant performance and preparation method thereof
CN112940482B (en) Composite material suitable for in-mold injection molding and preparation method thereof
CN115873390A (en) Noise-reducing polycarbonate composition and preparation method thereof
CN103044885A (en) Halogen-free flame-retardant low-temperature resistant polycarbonate and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant