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CN109306181A - A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant and preparation method thereof and application in fiber or film - Google Patents

A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant and preparation method thereof and application in fiber or film Download PDF

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CN109306181A
CN109306181A CN201811146102.9A CN201811146102A CN109306181A CN 109306181 A CN109306181 A CN 109306181A CN 201811146102 A CN201811146102 A CN 201811146102A CN 109306181 A CN109306181 A CN 109306181A
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aromatic heterocyclic
polymer resin
heterocyclic polymer
fire
retardant
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刘文熙
潘鑫
王庭辉
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
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    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
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    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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Abstract

The present invention relates to resin technology fields, more particularly to a kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant and preparation method thereof and in the application of fiber or film, the fire-retardant aromatic heterocyclic polymer resin of the UV resistant the preparation method comprises the following steps: with azobenzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate contain bromo terephthalic acid and/or contain phthalate bromine, hydrazine sulfate for reaction raw materials, polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Aromatic heterocyclic polymer resin of the invention has excellent UV resistant performance and higher limit oxygen index, excellent fireproof performance, also there is the performances such as good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special electric conductivity and electroluminescent, excellent combination property.

Description

A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant and preparation method thereof and in fibre The application of dimension or film
Technical field
The present invention relates to resin technology fields, and in particular to a kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant and its Preparation method and application in fiber or film.
Background technique
In heterocyclic compound cyclic organic compounds, constitute there are also other atomic time outside the atom carbon atom of ring, it is this kind of Cyclic organic compounds are called heterocyclic compound, and non-carbon is known as hetero atom.The most common hetero atom is oxygen and sulphur, on heterocycle Can have a hetero atom, can also there are two or more hetero atom, hetero atom can be a kind of atom, be also possible to two kinds Different atoms.As cycloalkane, heterocycle can also be divided into alicyclic heterocyclic and heteroaromatic two major classes.In general, heteroaromatic Ring system has a degree of stability and armaticity, and in general chemical reaction, ring is not easily broken.Part heteroaromatic can gather Synthetic macromolecule resin has extensive potential using value due to its unique excellent performance.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of resistances of UV resistant There is excellent UV resistant performance and higher limit oxygen to refer to for the aromatic heterocyclic polymer resin of combustion, the aromatic heterocyclic polymer resin Number, excellent fireproof performance also have good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special lead The performances such as electrical property and electroluminescent, excellent combination property.
It is another object of the present invention to provide a kind of preparation sides of aromatic heterocyclic polymer resin that UV resistant is fire-retardant Method, the preparation method step is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, can large-scale Industrial production.
Another purpose of the invention is that providing a kind of application of aromatic heterocyclic polymer resin that UV resistant is fire-retardant.
The purpose of the invention is achieved by the following technical solution: a kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant, The aromatic heterocyclic polymer resin includes with Am-BnThe polymer chain of expression, wherein A and B is to constitute polymer chain backbone Repetitive unit, and repetitive unit A, B are arranged with random order, m and n are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows:Wherein, R1, R2, R3 and R4 are unsubstituted or take The bromine in generation, and at least one in R1, R2, R3 and R4 is the bromine replaced.
Preferably, there is random copolymer configuration, alternate copolymer configuration or block copolymer configuration in the main chain, That is, the polymerization methods of the aromatic heterocyclic polymer resin can be random copolymerization, alternating copolymerization or block copolymerization.
Preferably, the aromatic heterocyclic polymer resin is modified using inorganic filler.
Preferably, the inorganic filler is mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide, oxygen At least one of compound, sulfate, carbonate, silicate, fluosilicate and phosphate.
Preferably, the nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；Institute Stating oxide is at least one of calcium oxide, zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
Preferably, the silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
Preferably, the sulfate be calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, in ferrous sulfate extremely Few one kind；The silicate is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate is calcium carbonate, carbonic acid At least one of magnesium and zinc carbonate；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate； The phosphate is at least one of calcium phosphate, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
Preferably, the aromatic heterocyclic polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, crystalline substance At least one of the short fine, silicone of palpus, carbon fiber, glass fibre, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
Another object of the present invention is achieved through the following technical solutions: a kind of aromatic heterocyclic polymer that UV resistant is fire-retardant The preparation method of resin, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, containing bromo terephthalic acid and/ Or contain phthalate bromine, hydrazine sulfate for reaction raw materials, polycondensation reaction is carried out in oleum, obtains the heteroaromatic polymerization Resin.
It is (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, brominated to benzene two specifically, polymerized monomer Formic acid and/or contain phthalate bromine), the molar ratio of hydrazine sulfate and oleum be 1:(1.01-5.0): (5-15), wherein sending out Cigarette sulfuric acid molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -) (contains with polymerized monomer Bromo terephthalic acid and/or contain phthalate bromine) molar ratio be (0.01-0.99): (0.99-0.01).In order to save into This, it is preferred that polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -) is (brominated with polymerized monomer Terephthalic acid (TPA) and/or contain phthalate bromine) molar ratio be (0.90-0.99): (0.10-0.01).
Further, azobenzene -4, the molar ratio of 3,3 '-dioctyl phthalate of 4 '-dioctyl phthalate and azobenzene-are (0-1): (1-0), Molar ratio containing bromo terephthalic acid and containing phthalate bromine is (0-1): (1-0).
An also purpose of the invention is achieved through the following technical solutions: a kind of aromatic heterocyclic polymer that UV resistant is fire-retardant The application of resin, the aromatic heterocyclic polymer resin are applied to fiber or film.
Preferably, the film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, stone Inkization heat dissipation film base material, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand Cover plate.
The beneficial effects of the present invention are: aromatic heterocyclic polymer resin of the invention have excellent UV resistant performance and Higher limit oxygen index, excellent fireproof performance also have good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, resistance to The performances such as solvent borne, special electric conductivity and electroluminescent, excellent combination property.
Preparation method step of the invention is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, It can large-scale industrial production.
Application of the fire-retardant aromatic heterocyclic polymer resin of UV resistant of the invention in fiber or film.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant, the aromatic heterocyclic polymer resin includes with Am-BnIt indicates Polymer chain, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are arranged with random order Column, m and n are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows:Wherein, R1, R2, R3 and R4 are not take Generation or the bromine replaced, and at least one in R1, R2, R3 and R4 is the bromine replaced.
The aromatic heterocyclic polymer resin is modified using inorganic filler.
The inorganic filler is in mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide and oxide At least one.
The nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxidation Object is at least one of calcium oxide, zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
The silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
A kind of preparation method for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant, with 4,4 '-dioctyl phthalate of azobenzene-and/ Or 3,3 '-dioctyl phthalate of azobenzene-, containing bromo terephthalic acid and/or containing phthalate bromine, hydrazine sulfate be reaction raw materials, sending out Polycondensation reaction is carried out in cigarette sulfuric acid, obtains the aromatic heterocyclic polymer resin.(azobenzene -4,4 '-dioctyl phthalate contains polymerized monomer Bromo terephthalic acid), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 Or 15), wherein oleum molal quantity with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (4,4 '-dioctyl phthalate of azobenzene -) and the molar ratio of polymerized monomer (containing bromo terephthalic acid) are (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
Embodiment 2
A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant, the aromatic heterocyclic polymer resin includes with Am-BnIt indicates Polymer chain, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are arranged with random order Column, m and n are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows:Wherein, R1, R2, R3 and R4 are not take Generation or the bromine replaced, and at least one in R1, R2, R3 and R4 is the bromine replaced.
The aromatic heterocyclic polymer resin is modified using inorganic filler.
The inorganic filler is at least one of sulfate, carbonate, silicate, fluosilicate and phosphate.
The sulfate is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate； The silicate is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate is calcium carbonate, magnesium carbonate and carbonic acid At least one of zinc；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphoric acid Salt is at least one of calcium phosphate, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
A kind of preparation method for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant, with 3,3 '-dioctyl phthalate of azobenzene-, contains Phthalate bromine, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer tree Rouge.The molar ratio of polymerized monomer (azobenzene -3,3 '-dioctyl phthalate contains phthalate bromine), hydrazine sulfate and oleum is 1: (1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity is with SO in oleum3Mole Number meter.
Wherein, polymerized monomer (3,3 '-dioctyl phthalate of azobenzene -) and the molar ratio of polymerized monomer (containing phthalate bromine) are (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
Embodiment 3
A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant, the aromatic heterocyclic polymer resin includes with Am-BnIt indicates Polymer chain, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are arranged with random order Column, m and n are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows:Its In, R1, R2, R3 and R4 are unsubstituted or substituted bromine, and at least one in R1, R2, R3 and R4 is the bromine replaced.
The aromatic heterocyclic polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber At least one of the short fine, silicone of dimension, glass fibre, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
A kind of preparation method for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant, with 4,4 '-dioctyl phthalate of azobenzene-and idol 3,3 '-dioctyl phthalate of pyridine-contains bromo terephthalic acid and contains phthalate bromine, hydrazine sulfate for reaction raw materials, in oleum Polycondensation reaction is carried out, the aromatic heterocyclic polymer resin is obtained.Polymerized monomer (azobenzene -4,4 '-dioctyl phthalate and azobenzene -3, 3 '-dioctyl phthalate, containing bromo terephthalic acid and contain phthalate bromine), the molar ratio of hydrazine sulfate and oleum be 1:(1.01, 2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene -) is (brominated with polymerized monomer Terephthalic acid (TPA) and contain phthalate bromine) molar ratio be (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75, 0.50,0.25 or 0.01).
The molar ratio of azobenzene -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate is (0.01,0.25,0.50,0.75 Or 0.99): (0.99,0.75,0.50,0.25 or 0.01), the molar ratio containing bromo terephthalic acid and containing phthalate bromine are (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
Embodiment 4
A kind of application for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant, the aromatic heterocyclic polymer resin are applied to fibre Dimension.
Embodiment 5
A kind of application for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant, the aromatic heterocyclic polymer resin are applied to thin Film.
The film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, graphitization heat dissipation Film base material, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand-set lid.
After tested, it can achieve using film ultraviolet degradation made from aromatic heterocyclic polymer resin of the invention 1750-1970h, limit oxygen index can achieve 40.2-44.7%, have excellent UV resistant performance and higher limit oxygen Index, excellent fireproof performance.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way, Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.

Claims (10)

1. a kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant, it is characterised in that: the aromatic heterocyclic polymer resin includes With Am-BnThe polymer chain of expression, wherein A and B be constitute polymer chain backbone repetitive unit, and repetitive unit A, B with Random order arrangement, m and n are positive integer；
The structural formula of the repetitive unit A are as follows:And/or
The structural formula of the repetitive unit B are as follows:And/orIts In, R1, R2, R3 and R4 are unsubstituted or substituted bromine, and at least one in R1, R2, R3 and R4 is the bromine replaced.
2. a kind of fire-retardant aromatic heterocyclic polymer resin of UV resistant according to claim 1, it is characterised in that: the virtue Heterocycle polymer resin is modified using inorganic filler.
3. a kind of fire-retardant aromatic heterocyclic polymer resin of UV resistant according to claim 2, it is characterised in that: the nothing Machine filler is mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide, oxide, sulfate, carbonate, silicon At least one of hydrochlorate, fluosilicate and phosphate.
4. a kind of fire-retardant aromatic heterocyclic polymer resin of UV resistant according to claim 3, it is characterised in that: the nitrogen Compound is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxide is calcium oxide, oxidation At least one of zinc, magnesia, iron oxide, silica and titanium dioxide.
5. a kind of fire-retardant aromatic heterocyclic polymer resin of UV resistant according to claim 4, it is characterised in that: described two Silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
6. a kind of fire-retardant aromatic heterocyclic polymer resin of UV resistant according to claim 3, it is characterised in that: the sulphur Hydrochlorate is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate；The silicate is silicon At least one of sour sodium, alumina silicate and magnesium silicate；The carbonate is at least one in calcium carbonate, magnesium carbonate and zinc carbonate Kind；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphate be calcium phosphate, At least one of calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
7. a kind of fire-retardant aromatic heterocyclic polymer resin of UV resistant according to claim 1, it is characterised in that: the virtue Heterocycle polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber, glass fibre, virtue At least one of the short fine, silicone of synthetic fibre pulp, aramid fiber and polytetrafluoroethylene (PTFE).
8. such as a kind of described in any item preparation methods for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant of claim 1-7, It is characterized by: with azobenzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate, containing bromo terephthalic acid and/or containing Phthalate bromine, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer tree Rouge.
9. special such as a kind of described in any item applications for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant of claim 1-7 Sign is: the aromatic heterocyclic polymer resin is applied to fiber or film.
10. a kind of application of the fire-retardant aromatic heterocyclic polymer resin of UV resistant according to claim 9, feature exist In: the film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, graphitization heat dissipation film base Material, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand-set lid.
CN201811146102.9A 2018-09-29 2018-09-29 A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant and preparation method thereof and application in fiber or film Withdrawn CN109306181A (en)

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* Cited by examiner, † Cited by third party
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WO2007133409A2 (en) * 2006-05-01 2007-11-22 E. I. Du Pont De Nemours And Company Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom
CN101437871A (en) * 2006-05-01 2009-05-20 纳幕尔杜邦公司 Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom
CN104093787A (en) * 2012-01-12 2014-10-08 韩华石油化学株式会社 Resin composition for emi shielding, comprising carbon hydride composite
CN104817687A (en) * 2015-05-22 2015-08-05 江苏宝德新材料有限公司 High-purity aromatic polyoxadiazole solution and fiber prepared from high-purity aromatic polyoxadiazole solution
CN104831400A (en) * 2015-05-22 2015-08-12 江苏宝德新材料有限公司 Low-viscosity aromatic polyoxdiazole solution and fiber prepared from same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007133409A2 (en) * 2006-05-01 2007-11-22 E. I. Du Pont De Nemours And Company Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom
CN101437871A (en) * 2006-05-01 2009-05-20 纳幕尔杜邦公司 Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom
CN104093787A (en) * 2012-01-12 2014-10-08 韩华石油化学株式会社 Resin composition for emi shielding, comprising carbon hydride composite
CN104817687A (en) * 2015-05-22 2015-08-05 江苏宝德新材料有限公司 High-purity aromatic polyoxadiazole solution and fiber prepared from high-purity aromatic polyoxadiazole solution
CN104831400A (en) * 2015-05-22 2015-08-12 江苏宝德新材料有限公司 Low-viscosity aromatic polyoxdiazole solution and fiber prepared from same

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