CN109337049A - A kind of aromatic heterocyclic polymer resin of high intensity UV resistant high transparency and preparation method thereof and application in fiber or film - Google Patents
A kind of aromatic heterocyclic polymer resin of high intensity UV resistant high transparency and preparation method thereof and application in fiber or film Download PDFInfo
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- CN109337049A CN109337049A CN201811146053.9A CN201811146053A CN109337049A CN 109337049 A CN109337049 A CN 109337049A CN 201811146053 A CN201811146053 A CN 201811146053A CN 109337049 A CN109337049 A CN 109337049A
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
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Abstract
The present invention relates to resin technology fields, aromatic heterocyclic polymer resin more particularly to a kind of high-intensitive UV resistant high transparency and preparation method thereof and application in fiber or film, the aromatic heterocyclic polymer resin of the high intensity UV resistant high transparency the preparation method comprises the following steps: with terephthalic acid (TPA) and/or phthalic acid, azobenzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid, hydrazine sulfate are reaction raw materials, polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Aromatic heterocyclic polymer resin intensity with higher, transparency and excellent UV resistant performance of the invention, 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
Technical field
The present invention relates to resin technology fields, and in particular to a kind of aromatic heterocyclic polymer of high intensity UV resistant high transparency
Resin and preparation method thereof 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 resistance to purples of high intensity
The aromatic heterocyclic polymer resin of outside line high transparency, the aromatic heterocyclic polymer resin intensity with higher, transparency and excellent
UV resistant performance also has good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special conduction
The performances such as property and electroluminescent, excellent combination property.
It is another object of the present invention to provide a kind of aromatic heterocyclic polymer resins of high-intensitive UV resistant high transparency
Preparation method, the preparation method step is simple, convenient operation and control, quality stablize, high production efficiency, production cost is low, can
Large-scale industrial production.
Another purpose of the invention is that providing a kind of aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparency
Application.
The purpose of the invention is achieved by the following technical solution: a kind of heteroaromatic polymerization of high intensity UV resistant high transparency
Resin, the aromatic heterocyclic polymer resin includes with Am-Bn-CxThe polymer chain of expression, wherein A, B and C are to constitute to gather
The repetitive unit of object chain main chain is closed, and repetitive unit A, B and C are arranged with random order, m, n and x 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:
The structural formula of the repetitive unit C are as follows:Wherein, R1, R2, R3 and R4 are unsubstituted or take
The fluorine in generation, and at least one in R1, R2, R3 and R4 is the fluorine 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 virtue of high intensity UV resistant high transparency is miscellaneous
The preparation method of cyclopolymer resin, with terephthalic acid (TPA) and/or phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and/or idol
3,3 '-dioctyl phthalate of pyridine-, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid, hydrazine sulfate are reaction raw materials, in oleum
Polycondensation reaction is carried out in acid, obtains the aromatic heterocyclic polymer resin.
Specifically, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and/or azo
Benzene -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid), the molar ratio of hydrazine sulfate and oleum be
1:(1.01-5.0): (5-15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene-
And/or azobenzene -3,3 '-dioctyl phthalate) with the molar ratio of polymerized monomer (fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid)
For (0.01-0.99): (0.99-0.01): (0.99-0.01).In order to save cost, it is preferred that polymerized monomer (terephthalic acid (TPA)
And/or phthalic acid), polymerized monomer (azobenzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate) with polymerize it is single
The molar ratio of body (fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid) is (0.80-0.98): (0.10-0.01):
(0.10-0.01)。
Further, the molar ratio of terephthalic acid (TPA) and phthalic acid is (0-1): (1-0), azobenzene -4,4 '-two
The molar ratio of 3,3 '-dioctyl phthalate of formic acid and azobenzene-is (0-1): (1-0), fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid
Molar ratio be (0-1): (1-0).Applicants have found that when using terephthalic acid (TPA) as monomer polymerization, obtained heteroaromatic
Although fluoropolymer resin intensity is higher, shrinking percentage is slightly bigger than normal, and when phthalic acid is added polymerizeing together as monomer, it obtains
On the basis of keeping higher-strength, shrinking percentage can be improved the aromatic heterocyclic polymer tree arrived.
An also purpose of the invention is achieved through the following technical solutions: a kind of virtue of high intensity UV resistant high transparency is miscellaneous
The application of cyclopolymer 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 intensity with higher of the invention, transparency and
Excellent UV resistant performance also has good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special
Electric conductivity and the performances such as 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 aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparency 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 of high intensity UV resistant high transparency, the aromatic heterocyclic polymer resin include with
Am-Bn-CxThe polymer chain of expression, wherein A, B and C are the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B
It is arranged with C with random order, m, n and x 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:
The structural formula of the repetitive unit C are as follows:Wherein, R1, R2, R3 and R4 are not take
Generation or the fluorine replaced, and at least one in R1, R2, R3 and R4 is the fluorine 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 of the aromatic heterocyclic polymer resin of high intensity UV resistant high transparency, with terephthalic acid (TPA), idol
4,4 '-dioctyl phthalate of pyridine-, fluorine-containing terephthalic acid (TPA), hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, is obtained
To the aromatic heterocyclic polymer resin.Polymerized monomer (terephthalic acid (TPA), azobenzene -4,4 '-dioctyl phthalate, fluorine-containing terephthaldehyde
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 is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA)), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene -) are (fluorine-containing with polymerized monomer
Terephthalic acid (TPA)) 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): (0.99,0.75,0.50,0.25 or 0.01).
Embodiment 2
A kind of aromatic heterocyclic polymer resin of high intensity UV resistant high transparency, the aromatic heterocyclic polymer resin include with
Am-Bn-CxThe polymer chain of expression, wherein A, B and C are the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B
It is arranged with C with random order, m, n and x 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:
The structural formula of the repetitive unit C are as follows:Wherein, R1, R2, R3 and R4 are not take
Generation or the fluorine replaced, and at least one in R1, R2, R3 and R4 is the fluorine 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 of the aromatic heterocyclic polymer resin of high intensity UV resistant high transparency, with phthalic acid, idol
3,3 '-dioctyl phthalate of pyridine-, fluorine-containing phthalic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, is obtained
To the aromatic heterocyclic polymer resin.Polymerized monomer (phthalic acid, azobenzene -3,3 '-dioctyl phthalate, fluorine-containing O-phthalic
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 is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (phthalic acid), polymerized monomer (3,3 '-dioctyl phthalate of azobenzene -) are (fluorine-containing with polymerized monomer
Phthalic acid) 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): (0.99,0.75,0.50,0.25 or 0.01).
Embodiment 3
A kind of aromatic heterocyclic polymer resin of high intensity UV resistant high transparency, the aromatic heterocyclic polymer resin include with
Am-Bn-CxThe polymer chain of expression, wherein A, B and C are the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B
It is arranged with C with random order, m, n and x 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:
The structural formula of the repetitive unit C are as follows:
Wherein, R1, R2, R3 and R4 are unsubstituted or substituted fluorine, and at least one in R1, R2, R3 and R4 is the fluorine 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 of the aromatic heterocyclic polymer resin of high intensity UV resistant high transparency, with terephthalic acid (TPA) and neighbour
Phthalic acid, azobenzene -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and fluorine-containing O-phthalic
Acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerization is single
Body is (terephthalic acid (TPA) and phthalic acid, azobenzene -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate, fluorine-containing to benzene two
Formic acid and/or fluorine-containing phthalic 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 is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and phthalic acid), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene-and
Azobenzene -3,3 '-dioctyl phthalate) with the molar ratio of polymerized monomer (fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid) be (0.01,
0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25 or
0.01)。
The molar ratio of terephthalic acid (TPA) and phthalic acid 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 of 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene-be (0.01,
0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01), fluorine-containing terephthalic acid (TPA) and fluorine-containing adjacent benzene two
The molar ratio of formic acid is (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 of the aromatic heterocyclic polymer resin of high intensity UV resistant high transparency, the aromatic heterocyclic polymer resin
Applied to fiber.
Embodiment 5
A kind of application of the aromatic heterocyclic polymer resin of high intensity UV resistant high transparency, the aromatic heterocyclic polymer resin
Applied to 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 transverse tensile strength made from aromatic heterocyclic polymer resin of the invention
88.5-92.3MPa, longitudinal tensile strength can achieve 146.9-154.5MPa, and ultraviolet light and aging test can achieve 1620-
1810h, transparency can achieve 88.6-91.5%, intensity, transparency and excellent UV resistant performance with higher.
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 of high intensity UV resistant high transparency, it is characterised in that: the aromatic heterocyclic polymer
Resin includes with Am-Bn-CxThe polymer chain of expression, wherein A, B and C are the repetitive unit for constituting polymer chain backbone, and
Repetitive unit A, B and C are arranged with random order, and m, n and x 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:
The structural formula of the repetitive unit C are as follows:
Wherein, R1, R2, R3 and R4 are unsubstituted or substituted fluorine, and at least one in R1, R2, R3 and R4 is the fluorine replaced.
2. a kind of aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparency according to claim 1, feature exist
In: the aromatic heterocyclic polymer resin is modified using inorganic filler.
3. a kind of aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparency according to claim 2, feature exist
In: the inorganic filler be mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide, oxide, sulfate,
At least one of carbonate, silicate, fluosilicate and phosphate.
4. a kind of aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparency according to claim 3, feature exist
In: the nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxide is oxygen
Change at least one of calcium, zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
5. a kind of aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparency according to claim 4, feature exist
In: the silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
6. a kind of aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparency according to claim 3, feature exist
In: the sulfate is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate；The silicon
Hydrochlorate is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate is in calcium carbonate, magnesium carbonate and zinc carbonate
It is at least one；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphate is phosphorus
At least one of sour calcium, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
7. a kind of aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparency according to claim 1, feature exist
In: the aromatic heterocyclic polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber, glass
At least one of the short fine, silicone of glass fiber, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
8. such as a kind of described in any item systems of the aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparency of claim 1-7
Preparation Method, it is characterised in that: with terephthalic acid (TPA) and/or phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-
3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid, hydrazine sulfate be reaction raw materials, in oleum into
Row polycondensation reaction obtains the aromatic heterocyclic polymer resin.
9. such as a kind of answering for the described in any item aromatic heterocyclic polymer resins of high-intensitive UV resistant high transparency of claim 1-7
With, it is characterised in that: the aromatic heterocyclic polymer resin is applied to fiber or film.
10. a kind of application of the aromatic heterocyclic polymer resin of high-intensitive UV resistant high transparency according to claim 9,
Be characterized in that: the film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, graphitization and dissipates
Hotting mask substrate, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand-set lid.
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| CN201811146053.9A CN109337049A (en) | 2018-09-29 | 2018-09-29 | A kind of aromatic heterocyclic polymer resin of high intensity UV resistant high transparency and preparation method thereof and application in fiber or film |
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| CN201811146053.9A CN109337049A (en) | 2018-09-29 | 2018-09-29 | A kind of aromatic heterocyclic polymer resin of high intensity UV resistant high transparency and preparation method thereof and application in fiber or film |
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| CN109337049A true CN109337049A (en) | 2019-02-15 |
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Citations (5)
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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 |
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2018
- 2018-09-29 CN CN201811146053.9A patent/CN109337049A/en not_active Withdrawn
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| 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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