CN109293896A - A kind of aromatic heterocyclic polymer resin of UV resistant and preparation method thereof and application in fiber or film - Google Patents

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

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CN109293896A
CN109293896A CN201811146084.4A CN201811146084A CN109293896A CN 109293896 A CN109293896 A CN 109293896A CN 201811146084 A CN201811146084 A CN 201811146084A CN 109293896 A CN109293896 A CN 109293896A
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polymer resin
aromatic heterocyclic
dioctyl phthalate
azobenzene
heterocyclic polymer
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王庭辉
刘文熙
潘鑫
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/125—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one oxygen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
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    • C08G2261/122—Copolymers statistical
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/22—Molecular weight
    • C08G2261/228—Polymers, i.e. more than 10 repeat units
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3222—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more oxygen atoms as the only heteroatom, e.g. furan
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/35—Macromonomers, i.e. comprising more than 10 repeat units
    • C08G2261/354—Macromonomers, i.e. comprising more than 10 repeat units containing hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers

Abstract

The present invention relates to resin technology fields, aromatic heterocyclic polymer resin more particularly to a kind of UV resistant and preparation method thereof and application in fiber or film, the aromatic heterocyclic polymer resin of the UV resistant the preparation method comprises the following steps: in the absence of being as R, with azobenzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate are 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, heating conduction is excellent, 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 of UV resistant and preparation method thereof and in fiber or The application of film
Technical field
The present invention relates to resin technology fields, and in particular to a kind of aromatic heterocyclic polymer resin of UV resistant 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 UV resistants Aromatic heterocyclic polymer resin, the aromatic heterocyclic polymer resin have excellent UV resistant performance, and heating conduction is excellent, Ke Yizeng Add carbon element content, can be used for preparing graphitization heat sink material, also there is good dimensional stability, heat resistance, resistance to oxidation, electricity The performances such as insulation, solvent resistance, special electric conductivity and electroluminescent, excellent combination property.
It is another object of the present invention to provide a kind of preparation methods of the aromatic heterocyclic polymer resin of UV resistant, should Preparation method step is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, can large-scale industry life It produces.
Another purpose of the invention is that providing a kind of application of the aromatic heterocyclic polymer resin of UV resistant.
The purpose of the invention is achieved by the following technical solution: a kind of aromatic heterocyclic polymer resin of UV resistant, described Aromatic heterocyclic polymer resin includes with Am-BnThe polymer chain of expression, wherein A and B is the repetition for constituting polymer chain backbone 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, R is oxygen, sulphur or is not present.
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 resin of UV resistant Preparation method, in the absence of R is, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, 4,4'- join Phthalic acid and/or 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains institute State aromatic heterocyclic polymer resin.
Specifically, polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, 4,4 '-biphenyl two Formic acid and/or 3,3 '-biphenyl dicarboxylic acids), 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 (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -) and polymerized monomer (4, 4 '-biphenyl dicarboxylic acids and/or 3,3 '-biphenyl dicarboxylic acids) molar ratio be (0.01-0.99): (0.99-0.01).In order to save Cost, it is preferred that polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -) and polymerized monomer (4, 4 '-biphenyl dicarboxylic acids and/or 3,3 '-biphenyl dicarboxylic acids) 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), The molar ratio of 4,4 '-biphenyl dicarboxylic acids and 3,3 '-biphenyl dicarboxylic acids is (0-1): (1-0).
A kind of preparation method of the aromatic heterocyclic polymer resin of UV resistant, when R is oxygen, with 4,4 '-diformazan of azobenzene- Acid and/or azobenzene -3,3 '-dioctyl phthalate, 4,4'- oxydibenzoic acid and/or 3,3'- oxydibenzoic acid, hydrazine sulfate are anti- Raw material is answered, polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.
Specifically, polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, 4,4 '-diphenyl ether Dioctyl phthalate and/or 3,3 '-oxydibenzoic acids), 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 (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -) and polymerized monomer (4, 4 '-oxydibenzoic acids and/or 3,3 '-oxydibenzoic acids) molar ratio be (0.01-0.99): (0.99-0.01).In order to Save cost, it is preferred that polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -) and polymerized monomer The molar ratio of (4,4 '-oxydibenzoic acids and/or 3,3 '-oxydibenzoic acids) is (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), The molar ratio of 4,4'- oxydibenzoic acid and 3,3'- oxydibenzoic acid is (0-1): (1-0).
A kind of preparation method of the aromatic heterocyclic polymer resin of UV resistant, when R is sulphur, with 4,4 '-diformazan of azobenzene- Acid and/or azobenzene -3,3 '-dioctyl phthalate, 4,4'- diphenyl sulfide dioctyl phthalate and/or 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate For reaction raw materials, polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.
Specifically, polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, 4,4 '-diphenyl sulfides Ether dioctyl phthalate and/or 3,3 '-diphenyl sulfide dioctyl phthalate), the molar ratio of hydrazine sulfate and oleum be 1:(1.01-5.0): (5- 15), wherein oleum molal quantity with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -) and polymerized monomer (4, 4 '-diphenyl sulfide dioctyl phthalate and/or 3,3 '-diphenyl sulfide dioctyl phthalate) molar ratio be (0.01-0.99): (0.99-0.01). In order to save cost, it is preferred that polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -) with polymerize The molar ratio of monomer (4,4 '-diphenyl sulfide dioctyl phthalate and/or 3,3 '-diphenyl sulfide dioctyl phthalate) is (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), The molar ratio of 4,4'- diphenyl sulfide dioctyl phthalate and 3,3'- diphenyl sulfide dioctyl phthalate is (0-1): (1-0).
An also purpose of the invention is achieved through the following technical solutions: a kind of aromatic heterocyclic polymer resin of UV resistant Application, the aromatic heterocyclic polymer resin be 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 has excellent UV resistant performance, Heating conduction is excellent, can increase carbon element content, can be used for preparing graphitization heat sink material, also has good dimensionally stable The performances such as property, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special electric conductivity and electroluminescent, excellent combination property.
Another preparation method step of the invention is simple, convenient operation and control, and quality is stablized, high production efficiency, production cost It is low, it can large-scale industrial production.
Application of the 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 of UV resistant, the aromatic heterocyclic polymer resin includes with Am-BnWhat is indicated is poly- Close object chain, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are arranged with random order, m It is positive integer with n；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows:Wherein, R be oxygen, Sulphur is not present.
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 UV resistant, in the absence of R is, with azobenzene -4,4 ' - Dioctyl phthalate, 4,4'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, it is miscellaneous to obtain the virtue Cyclopolymer resin.Polymerized monomer (azobenzene -4,4 '-dioctyl phthalate, 4,4 '-biphenyl dicarboxylic acids), hydrazine sulfate and oleum Molar ratio is for 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity is with oleum SO in acid3Molal quantity meter.
Wherein, the molar ratio of polymerized monomer (4,4 '-dioctyl phthalate of azobenzene -) and polymerized monomer (4,4 '-biphenyl dicarboxylic acid) For (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
When R is oxygen, with 4,4 '-dioctyl phthalate of azobenzene-, 4,4'- oxydibenzoic acid, hydrazine sulfate for reaction raw materials, Polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (azobenzene -4,4 '-dioctyl phthalate, 4,4 '-oxydibenzoic acids), 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, mole of polymerized monomer (4,4 '-dioctyl phthalate of azobenzene -) and polymerized monomer (4,4 '-oxydibenzoic acid) Than for (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
When R is sulphur, with 4,4 '-dioctyl phthalate of azobenzene-, 4,4'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate for reaction raw materials, Polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (azobenzene -4,4 '-diformazan Acid, 4,4 '-diphenyl sulfide dioctyl phthalate), 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 (4,4 '-dioctyl phthalate of azobenzene -) and polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate) rub You are than being (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 of UV resistant, the aromatic heterocyclic polymer resin includes with Am-BnWhat is indicated is poly- Close object chain, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are arranged with random order, m It is positive integer with n；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows:Wherein, R is oxygen, sulphur Or it is not present.
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 UV resistant, in the absence of R is, with azobenzene -3,3 ' - Dioctyl phthalate, 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, it is miscellaneous to obtain the virtue Cyclopolymer resin.Polymerized monomer (azobenzene -3,3 '-dioctyl phthalate, 3,3 '-biphenyl dicarboxylic acids), hydrazine sulfate and oleum Molar ratio is for 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity is with oleum SO in acid3Molal quantity meter.
Wherein, the molar ratio of polymerized monomer (3,3 '-dioctyl phthalate of azobenzene -) and polymerized monomer (3,3 '-biphenyl dicarboxylic acid) For (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
When R is oxygen, with 3,3 '-dioctyl phthalate of azobenzene-, 3,3'- oxydibenzoic acid, hydrazine sulfate for reaction raw materials, Polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (azobenzene -3,3 '-dioctyl phthalate, 3,3 '-oxydibenzoic acids), 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, mole of polymerized monomer (3,3 '-dioctyl phthalate of azobenzene -) and polymerized monomer (3,3 '-oxydibenzoic acid) Than for (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
When R is sulphur, with 3,3 '-dioctyl phthalate of azobenzene-, 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate for reaction raw materials, Polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (azobenzene -3,3 '-diformazan Acid, 3,3 '-diphenyl sulfide dioctyl phthalate), 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 azobenzene -) and polymerized monomer (3,3 '-diphenyl sulfide dioctyl phthalate) rub You are than being (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 of UV resistant, the aromatic heterocyclic polymer resin includes with Am-BnWhat is indicated is poly- Close object chain, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are arranged with random order, m It is positive integer with n；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows: Wherein, R is oxygen, sulphur or is not present.
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 UV resistant, in the absence of R is, with azobenzene -4,4 ' - 3,3 '-dioctyl phthalate of dioctyl phthalate and azobenzene-, 4,4'- biphenyl dicarboxylic acid and 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, Polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (azobenzene -4,4 '-dioctyl phthalate With azobenzene -3,3 '-dioctyl phthalate, 4,4 '-biphenyl dicarboxylic acids and 3,3 '-biphenyl dicarboxylic acids), mole of hydrazine sulfate and oleum Than for 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity is in oleum SO3Molal quantity meter.
Wherein, polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene -) and polymerized monomer (4,4 '- Biphenyl dicarboxylic acid and 3,3 '-biphenyl dicarboxylic acids) 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), 4,4 '-biphenyl dicarboxylic acids and 3, the molar ratio of 3 '-biphenyl dicarboxylic acids For (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
When R is oxygen, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene-, 4,4'- oxydibenzoic acid It is reaction raw materials with 3,3'- oxydibenzoic acid, hydrazine sulfate, polycondensation reaction is carried out in oleum, obtains the heteroaromatic Fluoropolymer resin.Polymerized monomer (azobenzene -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate, 4,4 '-oxydibenzoic acids With 3,3 '-oxydibenzoic acids), 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 -) and polymerized monomer (4,4 '- Oxydibenzoic acid and 3,3 '-oxydibenzoic acids) 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), 4,4'- oxydibenzoic acids and 3,3'- oxydibenzoic acid rubs You are than being (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
When R is sulphur, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene-, 4,4'- diphenyl sulfide diformazan Acid and 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the virtue Heterocycle polymer resin.Polymerized monomer (azobenzene -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate, 4,4 '-diphenyl sulfides Dioctyl phthalate and 3,3 '-diphenyl sulfide dioctyl phthalate), 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 -) and polymerized monomer (4,4 '- Diphenyl sulfide dioctyl phthalate and 3,3 '-diphenyl sulfide dioctyl phthalate) 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), 4,4'- diphenyl sulfide dioctyl phthalate and 3,3'- diphenyl sulfide dioctyl phthalate 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).
Embodiment 4
A kind of application of the aromatic heterocyclic polymer resin of UV resistant, the aromatic heterocyclic polymer resin are applied to fiber.
Embodiment 5
A kind of application of the aromatic heterocyclic polymer resin of UV resistant, the aromatic heterocyclic polymer resin are 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 ultraviolet degradation made from aromatic heterocyclic polymer resin of the invention 1780-1960h, thermal decomposition temperature can achieve 465-476 DEG C, and vertical thermal conductivity can achieve 38.3-58.4W/m-K, water Flat thermal coefficient can achieve 1180-1350W/m-K, have excellent UV resistant performance, and heat-resisting and heating conduction is excellent, can To increase carbon element content, it can be used for preparing graphitization heat sink material.
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 UV resistant, it is characterised in that: the aromatic heterocyclic polymer resin includes with Am- BnThe polymer chain of expression, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are with any Sequence arranges, and 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, R is oxygen, sulphur or is not present.
2. a kind of aromatic heterocyclic polymer resin of UV resistant according to claim 1, it is characterised in that: the heteroaromatic Fluoropolymer resin is modified using inorganic filler.
3. a kind of aromatic heterocyclic polymer resin of UV resistant according to claim 2, it is characterised in that: described inorganic to fill out Material be mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide, oxide, sulfate, carbonate, silicate, At least one of fluosilicate and phosphate.
4. a kind of aromatic heterocyclic polymer resin of UV resistant according to claim 3, it is characterised in that: the nitride For silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxide be calcium oxide, zinc oxide, At least one of magnesia, iron oxide, silica and titanium dioxide.
5. a kind of aromatic heterocyclic polymer resin of UV resistant according to claim 4, it is characterised in that: the titanium dioxide Silicon is nano silica, and the titanium dioxide is nano-titanium dioxide.
6. a kind of aromatic heterocyclic polymer resin of UV resistant according to claim 3, it is characterised in that: the sulfate For at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate；The silicate be sodium metasilicate, At least one of alumina silicate and magnesium silicate；The carbonate is at least one of calcium carbonate, magnesium carbonate and zinc carbonate；It is described Fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphate is calcium phosphate, phosphoric acid hydrogen At least one of calcium, magnesium phosphate and magnesium monohydrogen phosphate.
7. a kind of aromatic heterocyclic polymer resin of UV resistant according to claim 1, it is characterised in that: the heteroaromatic Fluoropolymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber, glass fibre, aramid fiber slurry At least one of the short fine, silicone of the dregs of rice, aramid fiber and polytetrafluoroethylene (PTFE).
8. special such as a kind of described in any item preparation methods of the aromatic heterocyclic polymer resin of UV resistant of claim 1-7 Sign is: in the absence of R is, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, 4,4'- biphenyl two Formic acid and/or 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the virtue Heterocycle polymer resin；
When R is oxygen, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, 4,4'- oxydibenzoic acid And/or 3,3'- oxydibenzoic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, it is miscellaneous to obtain the virtue Cyclopolymer resin；
When R is sulphur, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, 4,4'- diphenyl sulfide dioctyl phthalate And/or 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the virtue Heterocycle polymer resin.
9. such as a kind of described in any item applications of the aromatic heterocyclic polymer resin of UV resistant of claim 1-7, feature exists In: the aromatic heterocyclic polymer resin is applied to fiber or film.
10. a kind of application of the aromatic heterocyclic polymer resin of UV resistant according to claim 9, it is characterised in that: institute Film is stated applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, graphitization heat dissipation film base material, height Warm protective film, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand-set lid.
CN201811146084.4A 2018-09-29 2018-09-29 A kind of aromatic heterocyclic polymer resin of UV resistant and preparation method thereof and application in fiber or film Pending CN109293896A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08199048A (en) * 1995-01-23 1996-08-06 Mitsubishi Chem Corp Polyethylene terephthalate resin composition
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
JPH08199048A (en) * 1995-01-23 1996-08-06 Mitsubishi Chem Corp Polyethylene terephthalate resin composition
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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