CN113429773B - Flame-retardant reinforced polycarbonate composite material - Google Patents

Flame-retardant reinforced polycarbonate composite material Download PDF

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CN113429773B
CN113429773B CN202110810507.3A CN202110810507A CN113429773B CN 113429773 B CN113429773 B CN 113429773B CN 202110810507 A CN202110810507 A CN 202110810507A CN 113429773 B CN113429773 B CN 113429773B
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flame
parts
composite material
polycarbonate
polycarbonate composite
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CN113429773A (en
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张东宝
于冉
徐良
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Ningxia Qingyan Polymer New Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20General preparatory processes
    • C08G64/30General preparatory processes using carbonates
    • C08G64/307General preparatory processes using carbonates and phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/06Ethers; Acetals; Ketals; Ortho-esters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a flame-retardant reinforced polycarbonate composite material, which comprises the following components in parts by weight: 50-70 parts of fluorenyl polycarbonate; 20-40 parts of glass fiber; 5-10 parts of a flame retardant; 5-10 parts of a dispersing agent; 1-5 parts of an antioxidant; 1-5 parts of a coupling agent; the fluorenyl polycarbonate is prepared by synthesizing bisphenol fluorene and diphenyl carbonate serving as raw materials. The flame-retardant reinforced polycarbonate composite material prepared by the invention has better mechanical property and flame retardant property, and can meet the use requirements of a plurality of occasions with higher flame retardant level requirements.

Description

Flame-retardant reinforced polycarbonate composite material
Technical Field
The invention relates to the field of high polymer materials, in particular to a flame-retardant reinforced polycarbonate composite material.
Background
Polycarbonate (PC) is a representative engineering plastic that is widely used, and PC has excellent physical properties such as heat resistance, high impact strength, good dimensional stability, good transparency, excellent dielectric properties, low water absorption, low toxicity, and the like, and is widely used in the fields of electronic appliances, buildings, automobile industry, packaging containers, office supplies, sports equipment, and the like.
The polycarbonate has certain flame retardance, the flame retardance level reaches UL94 standard V-2 level, the oxygen index LOI is 21-24%, and the polycarbonate cannot be used in occasions with high flame retardance level requirements.
Meanwhile, the glass transition temperature of the polycarbonate is 140 to 150 ℃, and the application of the polycarbonate in the fields of aerospace and the like is limited due to the insufficient heat resistance.
Accordingly, there is still a need for advancement and development of the prior art.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a flame-retardant reinforced polycarbonate composite material, which is improved in flame retardancy and reinforcing effect.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the flame-retardant reinforced polycarbonate composite material comprises the following components in parts by weight:
Figure BDA0003167190770000011
Figure BDA0003167190770000021
the fluorenyl polycarbonate is prepared by synthesizing bisphenol fluorene and diphenyl carbonate serving as raw materials.
The flame-retardant reinforced polycarbonate composite material is characterized in that the flame retardant is a halogen flame retardant.
The flame-retardant reinforced polycarbonate composite material is characterized in that the halogen flame retardant is one or more of decabromodiphenyl ether, decabromodiphenyl ethane, tetrabromobisphenol A or chlorinated paraffin.
The flame-retardant reinforced polycarbonate composite material is characterized in that the dispersing agent is industrial white oil.
The flame-retardant reinforced polycarbonate composite material is characterized in that the antioxidant is an ethylene-octene copolymer.
The flame-retardant reinforced polycarbonate composite material is characterized in that the coupling agent is a titanate coupling agent.
The flame-retardant reinforced polycarbonate composite material is characterized in that the fluorenyl polycarbonate is prepared by the following steps:
mixing bisphenol fluorene and diphenyl carbonate in a nitrogen environment, adding a catalyst, and heating to 150-200 ℃ to obtain a molten reactant;
and heating to 300-350 ℃ to enable the molten reactants to react for 3-4h to obtain the fluorenyl polycarbonate.
The flame-retardant reinforced polycarbonate composite material is characterized in that the catalyst is one of sodium hydroxide, potassium hydroxide, lanthanum acetylacetonate or tetraphenylphosphatidylate.
Has the advantages that: the invention discloses a flame-retardant reinforced polycarbonate composite material, which is characterized in that on one hand, fluorenyl polycarbonate is prepared by synthesizing bisphenol fluorene and diphenyl carbonate as raw materials, the existence of the fluorenyl polycarbonate increases the rigidity of a molecular chain, so that the flexibility of a main chain is reduced, and the movement between molecular chains is difficult, so that the glass transition temperature of the polycarbonate is increased, namely the heat resistance of the polycarbonate is enhanced, on the other hand, the strength of the polycarbonate composite material can be enhanced by adding glass fiber, and in addition, the flame retardant can effectively improve the flame retardant property of the polycarbonate composite material, so that the polycarbonate composite material with both strength and flame retardant property is prepared.
Detailed Description
The invention provides a flame-retardant reinforced polycarbonate composite material, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
At present, the production method of polycarbonate mainly comprises two methods, namely a phosgene interface polycondensation method and a non-phosgene melt transesterification method, wherein the phosgene interface polycondensation method uses toxic phosgene and a dichloromethane solvent, is not beneficial to environmental protection, the non-phosgene melt transesterification method does not use phosgene and a solvent, takes bisphenol compounds and diphenyl carbonate as raw materials, directly generates products under the melting condition, has simple post-treatment and belongs to a green synthesis process.
In the invention, bisphenol fluorene and diphenyl carbonate are used as raw materials to synthesize fluorenyl polycarbonate by adopting a non-phosgene molten ester exchange method, and the method comprises the following specific steps:
s10, mixing bisphenol fluorene and diphenyl carbonate in a nitrogen environment, adding a catalyst, and heating to 150-200 ℃ to obtain a molten reactant;
and S20, heating to 300-350 ℃ to enable the molten reactants to react for 3-4h to obtain the fluorenyl polycarbonate.
Wherein the catalyst is one of sodium hydroxide, potassium hydroxide, lanthanum acetylacetonate or tetraphenylphosphatidylate.
A flame-retardant reinforced polycarbonate composite of the invention is further illustrated by the following specific examples:
example 1
(1) Weighing the following raw materials in parts by weight:
Figure BDA0003167190770000031
Figure BDA0003167190770000041
(2) Mixing the raw materials in a high-speed mixer, putting the mixture into a double-screw extruder, and carrying out melt extrusion, cooling, granulating and packaging on the mixture to obtain the finished product.
Example 2
(1) Weighing the following raw materials in parts by weight:
Figure BDA0003167190770000042
(2) Mixing the raw materials in a high-speed mixer, putting the mixture into a double-screw extruder, and carrying out melt extrusion, cooling, granulating and packaging on the mixture to obtain the finished product.
Example 3
(1) Weighing the following raw materials in parts by weight:
Figure BDA0003167190770000043
(2) Mixing the raw materials in a high-speed mixer, putting the mixture into a double-screw extruder, and carrying out melt extrusion, cooling, granulating and packaging on the mixture to obtain the finished product.
Example 4
(1) Weighing the following raw materials in parts by weight:
Figure BDA0003167190770000051
(2) Mixing the raw materials in a high-speed mixer, putting the mixture into a double-screw extruder, and carrying out melt extrusion, cooling, granulating and packaging on the mixture to obtain the finished product.
Example 5
(1) Weighing the following raw materials in parts by weight:
Figure BDA0003167190770000052
(2) Mixing the raw materials in a high-speed mixer, putting the mixture into a double-screw extruder, and performing melt extrusion, cooling, granulating and packaging to obtain the finished product.
Example 6
(1) Weighing the following raw materials in parts by weight:
Figure BDA0003167190770000053
Figure BDA0003167190770000061
(2) Mixing the raw materials in a high-speed mixer, putting the mixture into a double-screw extruder, and carrying out melt extrusion, cooling, granulating and packaging on the mixture to obtain the finished product.
Further, the samples prepared in examples 1 to 6 were tested for properties in the present invention, and the results are shown in the following table:
Figure BDA0003167190770000062
the results show that the flame-retardant reinforced polycarbonate composite material prepared by the invention has better mechanical property and flame retardant property.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (2)

1. The flame-retardant reinforced polycarbonate composite material is characterized by comprising the following components in parts by weight:
Figure FDA0003882116310000011
the fluorenyl polycarbonate is prepared by synthesizing bisphenol fluorene and diphenyl carbonate serving as raw materials, and the preparation method comprises the following specific steps:
mixing bisphenol fluorene and diphenyl carbonate in a nitrogen environment, adding a catalyst, and heating to 150-200 ℃ to obtain a molten reactant;
heating to 300-350 ℃ to enable the molten reactants to react for 3-4h to obtain fluorenyl polycarbonate;
wherein the catalyst is one of sodium hydroxide, potassium hydroxide, lanthanum acetylacetonate or tetraphenylphosphatidylate.
2. The flame retardant reinforced polycarbonate composite of claim 1, wherein the halogen based flame retardant is one or more of decabromodiphenyl ether, decabromodiphenyl ethane, tetrabromobisphenol a, or chlorinated paraffin.
CN202110810507.3A 2021-07-16 2021-07-16 Flame-retardant reinforced polycarbonate composite material Active CN113429773B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5635239B2 (en) * 2009-03-05 2014-12-03 帝人株式会社 Flame retardant polycarbonate resin composition
JP5431758B2 (en) * 2009-03-24 2014-03-05 帝人株式会社 Polycarbonate resin composition
CN104119665A (en) * 2013-04-24 2014-10-29 沭阳县苏合农产品销售专业合作联社 Flame-retardant glass fiber reinforced polyphenyl ether-polycarbonate composite material and preparation method thereof
CN109836817B (en) * 2019-01-28 2022-02-25 杭州本松新材料技术股份有限公司 Halogen flame retardant and application thereof
CN110157174A (en) * 2019-05-30 2019-08-23 深圳华力兴新材料股份有限公司 A kind of the fire-retardant polycarbonate composite material and preparation method and application of glass fiber reinforcement

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