CN109306183A - Fire-retardant aromatic heterocyclic polymer resin of a kind of high intensity UV resistant and preparation method thereof and application in fiber or film - Google Patents

Fire-retardant aromatic heterocyclic polymer resin of a kind of high intensity UV resistant and preparation method thereof and application in fiber or film Download PDF

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CN109306183A
CN109306183A CN201811147865.5A CN201811147865A CN109306183A CN 109306183 A CN109306183 A CN 109306183A CN 201811147865 A CN201811147865 A CN 201811147865A CN 109306183 A CN109306183 A CN 109306183A
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aromatic heterocyclic
polymer resin
heterocyclic polymer
acid
dioctyl phthalate
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王庭辉
刘文熙
潘鑫
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    • 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
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Abstract

The present invention relates to resin technology fields, more particularly to a kind of aromatic heterocyclic polymer resin that high-intensitive 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 high intensity UV resistant the preparation method comprises the following steps: in the absence of R is, with terephthalic acid (TPA) and/or phthalic acid, azobenzene -4, 4 '-dioctyl phthalate and/or azobenzene -3, 3 '-dioctyl phthalate, containing bromo terephthalic acid and/or contain phthalate bromine, 4, 4'- biphenyl dicarboxylic acid and/or 3, 3'- biphenyl dicarboxylic acid, hydrazine sulfate is reaction raw materials, polycondensation reaction is carried out in oleum, obtain the aromatic heterocyclic polymer resin.Aromatic heterocyclic polymer resin intensity with higher, limit oxygen index and excellent UV resistant performance of the invention, excellent fireproof performance, heating conduction is excellent, excellent combination property.

Description

A kind of aromatic heterocyclic polymer resin and preparation method thereof that high intensity UV resistant is fire-retardant With the application in fiber or film
Technical field
The present invention relates to resin technology fields, and in particular to a kind of aromatic heterocyclic polymer tree that high intensity UV resistant is fire-retardant Rouge 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 fire-retardant aromatic heterocyclic polymer resin of outside line, the aromatic heterocyclic polymer resin intensity with higher, limit oxygen index and excellent UV resistant performance, excellent fireproof performance, heating conduction is excellent, can increase carbon element content, can be used for preparing graphitization Heat sink material, also have good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special electric conductivity with And the performances such as electroluminescent, excellent combination property.
It is another object of the present invention to provide a kind of aromatic heterocyclic polymer resins that high-intensitive UV resistant is fire-retardant Preparation method, the preparation method step is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, can be big Scale industrial production.
Another purpose of the invention is that providing a kind of aromatic heterocyclic polymer resin that high-intensitive UV resistant is fire-retardant Using.
The purpose of the invention is achieved by the following technical solution: a kind of aromatic heterocyclic polymer that high intensity UV resistant is fire-retardant Resin, the aromatic heterocyclic polymer resin includes with Am-Bn-Cx-DyThe polymer chain of expression, wherein A, B, C and D are structure At the repetitive unit of polymer chain backbone, and repetitive unit A, B, C and D are arranged with random order, and m, n, x and y 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 bromine, and at least one in R1, R2, R3 and R4 is the bromine replaced；
The structural formula of the repetitive unit D 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 heteroaromatic that high intensity UV resistant is fire-retardant The preparation method of fluoropolymer resin, in the absence of R is, with terephthalic acid (TPA) and/or phthalic acid, azobenzene -4,4 '-two Formic acid and/or azobenzene -3,3 '-dioctyl phthalate contain bromo terephthalic acid and/or contain phthalate bromine, 4,4'- biphenyl dicarboxylic acid And/or 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the heteroaromatic Fluoropolymer 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 joins containing bromo terephthalic acid and/or containing phthalate bromine, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- Phthalic acid), 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 (terephthalic acid (TPA) and/or phthalic acid), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene- And/or azobenzene -3,3 '-dioctyl phthalate), polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) with polymerize singly The molar ratio of body (4,4 '-biphenyl dicarboxylic acids and/or 3,3 '-biphenyl dicarboxylic acids) is (0.01-0.99): (0.99-0.01): (0.99-0.01): (0.99-0.01).In order to save cost, it is preferred that polymerized monomer (terephthalic acid (TPA) and/or O-phthalic Acid), polymerized monomer (azobenzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate), polymerized monomer it is (brominated to benzene two Formic acid and/or contain phthalate bromine) rub with polymerized monomer (4,4 '-biphenyl dicarboxylic acids and/or 3,3 '-biphenyl dicarboxylic acids) You are than being (0.70-0.97): (0.10-0.01): (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), containing bromo terephthalic acid and contains phthalate bromine Molar ratio be (0-1): (1-0), 4,4 '-biphenyl dicarboxylic acids and 3, the molar ratios of 3 '-biphenyl dicarboxylic acids is (0-1): (1-0).
A kind of preparation method for the aromatic heterocyclic polymer resin that high intensity UV resistant is fire-retardant, when R is oxygen, to benzene two Formic acid and/or phthalic acid, azobenzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate contain bromo terephthalic acid And/or it is former for reaction containing phthalate bromine, 4,4'- oxydibenzoic acid and/or 3,3'- oxydibenzoic acid, hydrazine sulfate Material, polycondensation reaction is carried out in oleum, 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 contains bromo terephthalic acid and/or contains phthalate bromine, 4,4'- oxydibenzoic acid and/or 3,3'- Oxydibenzoic acid), the molar ratio of hydrazine sulfate and oleum be 1:(1.01-5.0): (5-15), wherein oleum mole Number 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), polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) with polymerize singly The molar ratio of body (4,4 '-oxydibenzoic acids and/or 3,3 '-oxydibenzoic acids) is (0.01-0.99): (0.99-0.01): (0.99-0.01): (0.99-0.01).In order to save cost, it is preferred that polymerized monomer (terephthalic acid (TPA) and/or O-phthalic Acid), polymerized monomer (azobenzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate), polymerized monomer (brominated terephthaldehyde Acid and/or contain phthalate bromine) rub with polymerized monomer (4,4 '-oxydibenzoic acids and/or 3,3 '-oxydibenzoic acids) You are than being (0.70-0.97): (0.10-0.01): (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), containing bromo terephthalic acid and contains phthalate bromine Molar ratio be (0-1): (1-0), 4,4 '-oxydibenzoic acids and 3, the molar ratios of 3 '-oxydibenzoic acids is (0-1): (1-0)。
A kind of preparation method for the aromatic heterocyclic polymer resin that high intensity UV resistant is fire-retardant, when R is sulphur, to benzene two Formic acid and/or phthalic acid, azobenzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate contain bromo terephthalic acid And/or containing phthalate bromine, 4,4'- diphenyl sulfide dioctyl phthalate and/or 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate be reaction Raw material carries out polycondensation reaction in oleum, 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 contains bromo terephthalic acid and/or contains phthalate bromine, 4,4'- diphenyl sulfide 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 Sour 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), polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) with polymerize singly The molar ratio of body (4,4 '-diphenyl sulfide dioctyl phthalate and/or 3,3 '-diphenyl sulfide dioctyl phthalate) is (0.01-0.99): (0.99- 0.01): (0.99-0.01): (0.99-0.01).In order to save cost, it is preferred that polymerized monomer (terephthalic acid (TPA) and/or neighbour Phthalic acid), polymerized monomer (azobenzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate), polymerized monomer it is (brominated right Phthalic acid and/or contain phthalate bromine) with polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate and/or 3,3 '-diphenyl sulfides Dioctyl phthalate) molar ratio be (0.70-0.97): (0.10-0.01): (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), containing bromo terephthalic acid and contains phthalate bromine Molar ratio be (0-1): (1-0), 4,4 '-diphenyl sulfide dioctyl phthalate and 3, the molar ratios of 3 '-diphenyl sulfide dioctyl phthalate is (0- 1): (1-0).
Applicants have found that when using terephthalic acid (TPA) as monomer polymerization, although obtained aromatic heterocyclic polymer resin Intensity is higher, but shrinking percentage is slightly bigger than normal, and when phthalic acid is added polymerizeing together as monomer, obtained heteroaromatic polymerization On the basis of keeping higher-strength, shrinking percentage can be improved object tree.
An also purpose of the invention is achieved through the following technical solutions: a kind of heteroaromatic that high intensity UV resistant is fire-retardant The application of fluoropolymer 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, limit oxygen refer to Several and excellent UV resistant performances, excellent fireproof performance, heating conduction is excellent, can increase carbon element content, can be used for making Standby graphitization heat sink material also has good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special The performances such as 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 high-intensitive 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 fire-retardant aromatic heterocyclic polymer resin of high intensity UV resistant, the aromatic heterocyclic polymer resin include with Am-Bn-Cx-DyThe polymer chain of expression, wherein A, B, C and D are the repetitive unit for constituting polymer chain backbone, and are repeated single First A, B, C and D are arranged with random order, and m, n, x and y 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 bromine replaced, and at least one in R1, R2, R3 and R4 is the bromine replaced；
The structural formula of the repetitive unit D 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 for the aromatic heterocyclic polymer resin that high intensity UV resistant is fire-retardant, in the absence of R is, with right Phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-, containing bromo terephthalic acid, 4,4'- biphenyl dicarboxylic acid, hydrazine sulfate be reaction raw materials, Polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (terephthalic acid (TPA), azobenzene- 4,4 '-dioctyl phthalate contain bromo terephthalic acid, 4,4'- biphenyl dicarboxylic 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 oleum3It rubs That number meter.
Wherein, polymerized monomer (terephthalic acid (TPA)), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene -), polymerized monomer are (brominated Terephthalic acid (TPA)) with the molar ratio of polymerized monomer (4,4 '-biphenyl dicarboxylic 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): (0.99,0.75,0.50,0.25 Or 0.01).
When R is oxygen, with terephthalic acid (TPA), 4,4 '-dioctyl phthalate of azobenzene-, contain bromo terephthalic acid, 4,4'- diphenyl ether Dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.It is poly- Close monomer (terephthalic acid (TPA), contains bromo terephthalic acid, 4,4'- oxydibenzoic acid at azobenzene -4,4 '-dioctyl phthalate), hydrazine sulfate Be 1:(1.01,2.0,3.0,4.0 or 5.0) with the molar ratio of oleum: (5,8,10,12 or 15), wherein oleum rubs That number is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA)), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene -), polymerized monomer are (brominated Terephthalic acid (TPA)) with the molar ratio of polymerized monomer (4,4 '-oxydibenzoic 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): (0.99,0.75, 0.50,0.25 or 0.01).
When R is sulphur, with terephthalic acid (TPA), 4,4 '-dioctyl phthalate of azobenzene-, contain bromo terephthalic acid, 4,4'- diphenyl sulfide Ether dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin. Polymerized monomer (terephthalic acid (TPA), contains bromo terephthalic acid, 4,4'- diphenyl sulfide dioctyl phthalate at azobenzene -4,4 '-dioctyl phthalate), sulphur The molar ratio of sour hydrazine and oleum is 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum Sour molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA)), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene -), polymerized monomer are (brominated Terephthalic acid (TPA)) with the molar ratio of polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate) 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): (0.99,0.75, 0.50,0.25 or 0.01).
Embodiment 2
A kind of fire-retardant aromatic heterocyclic polymer resin of high intensity UV resistant, the aromatic heterocyclic polymer resin include with Am-Bn-Cx-DyThe polymer chain of expression, wherein A, B, C and D are the repetitive unit for constituting polymer chain backbone, and are repeated single First A, B, C and D are arranged with random order, and m, n, x and y 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 bromine replaced, and at least one in R1, R2, R3 and R4 is the bromine replaced；
The structural formula of the repetitive unit D 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 for the aromatic heterocyclic polymer resin that high intensity UV resistant is fire-retardant, in the absence of R is, with neighbour Phthalic acid, 3,3 '-dioctyl phthalate of azobenzene-, phthalic acid, 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, are being sent out Polycondensation reaction is carried out in cigarette sulfuric acid, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (phthalic acid, azobenzene -3, 3 '-dioctyl phthalate, phthalic acid, 3,3'- biphenyl dicarboxylic 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 -), polymerized monomer (adjacent benzene Dioctyl phthalate) with the molar ratio of polymerized monomer (3,3 '-biphenyl dicarboxylic 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): (0.99,0.75,0.50,0.25 Or 0.01).
When R is oxygen, with phthalic acid, 3,3 '-dioctyl phthalate of azobenzene-, phthalic acid, 3,3'- diphenyl ether diformazan 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 (phthalic acid, azobenzene -3,3 '-dioctyl phthalate, phthalic acid, 3,3'- oxydibenzoic acid), hydrazine sulfate and oleum The molar ratio of acid 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 to send out SO in cigarette sulfuric acid3Molal quantity meter.
Wherein, polymerized monomer (phthalic acid), polymerized monomer (3,3 '-dioctyl phthalate of azobenzene -), polymerized monomer (adjacent benzene Dioctyl phthalate) with the molar ratio of polymerized monomer (3,3 '-oxydibenzoic 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): (0.99,0.75,0.50,0.25 Or 0.01).
When R is sulphur, with phthalic acid, 3,3 '-dioctyl phthalate of azobenzene-, phthalic acid, 3,3'- diphenyl sulfide two Formic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerization Monomer (phthalic acid, azobenzene -3,3 '-dioctyl phthalate, phthalic acid, 3,3'- diphenyl sulfide dioctyl phthalate), hydrazine sulfate and hair The molar ratio of cigarette sulfuric acid is 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 (phthalic acid), polymerized monomer (3,3 '-dioctyl phthalate of azobenzene -), polymerized monomer (adjacent benzene Dioctyl phthalate) with the molar ratio of polymerized monomer (3,3 '-diphenyl sulfide dioctyl phthalate) 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): (0.99,0.75,0.50,0.25 Or 0.01).
Embodiment 3
A kind of fire-retardant aromatic heterocyclic polymer resin of high intensity UV resistant, the aromatic heterocyclic polymer resin include with Am-Bn-Cx-DyThe polymer chain of expression, wherein A, B, C and D are the repetitive unit for constituting polymer chain backbone, and are repeated single First A, B, C and D are arranged with random order, and m, n, x and y 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: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 structural formula of the repetitive unit D 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 for the aromatic heterocyclic polymer resin that high intensity UV resistant is fire-retardant, in the absence of R is, with right Phthalic acid and phthalic acid, azobenzene -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate, containing bromo terephthalic acid and Containing phthalate bromine, 4,4'- biphenyl dicarboxylic acid and 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, in oleum Polycondensation reaction is carried out, the aromatic heterocyclic polymer resin is obtained.Polymerized monomer (terephthalic acid (TPA) and phthalic acid, azobenzene- 4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate contain bromo terephthalic acid and contain phthalate bromine, 4,4'- biphenyl diformazan Acid and 3,3'- biphenyl dicarboxylic 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), polymerized monomer (containing bromo terephthalic acid and contain phthalate bromine) with 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): (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), containing bromo terephthalic acid and brominated adjacent benzene two The molar ratio of formic acid be (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01), 4,4 '- The molar ratio of biphenyl dicarboxylic acid and 3,3 '-biphenyl dicarboxylic acids be (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 terephthalic acid (TPA) and phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and azobenzene -3,3 ' - Dioctyl phthalate, containing bromo terephthalic acid and containing phthalate bromine, 4,4'- oxydibenzoic acid and 3,3'- oxydibenzoic acid, Hydrazine sulfate is reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (terephthalic acid (TPA) and phthalic acid, azobenzene -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate, brominated terephthaldehyde Acid and contain phthalate bromine, 4,4'- oxydibenzoic acid and 3,3'- oxydibenzoic acid), hydrazine sulfate and oleum rub You are 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 with oleum Middle SO3Molal 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), polymerized monomer (containing bromo terephthalic acid and contain phthalate bromine) with 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): (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), containing bromo terephthalic acid and brominated adjacent benzene two The molar ratio of formic acid be (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01), 4,4 '- The molar ratio of oxydibenzoic acid and 3,3 '-oxydibenzoic acids is (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 terephthalic acid (TPA) and phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and azobenzene -3,3 ' - Dioctyl phthalate contains bromo terephthalic acid and contains phthalate bromine, 4,4'- diphenyl sulfide dioctyl phthalate and 3,3'- diphenyl sulfide diformazan 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, brominated to benzene two Formic acid and contain phthalate bromine, 4,4'- diphenyl sulfide dioctyl phthalate and 3,3'- diphenyl sulfide dioctyl phthalate), hydrazine sulfate and smoke The molar ratio of sulfuric acid is 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 (terephthalic acid (TPA) and phthalic acid), polymerized monomer (4,4 '-dioctyl phthalate of azobenzene-and Azobenzene -3,3 '-dioctyl phthalate), polymerized monomer (containing bromo terephthalic acid and contain phthalate bromine) with 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): (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), containing bromo terephthalic acid and brominated adjacent benzene two The molar ratio of formic acid be (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01), 4,4 '- The molar ratio of diphenyl sulfide dioctyl phthalate and 3,3 '-diphenyl sulfide 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).
Embodiment 4
A kind of application for the aromatic heterocyclic polymer resin that high intensity UV resistant is fire-retardant, the aromatic heterocyclic polymer resin are answered For fiber.
Embodiment 5
A kind of application for the aromatic heterocyclic polymer resin that high intensity UV resistant is fire-retardant, the aromatic heterocyclic polymer resin are answered For 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 86.8-90.6MPa, longitudinal tensile strength can achieve 144.7-152.9MPa, and ultraviolet light and aging test can achieve 1550- 1760h, limit oxygen index can achieve 38.3-42.5%, and thermal decomposition temperature can achieve 456-468 DEG C, vertical thermal conductivity It can achieve 34.5-54.3W/m-K, horizontal thermal conductivity factor can achieve 1090-1270W/m-K, intensity with higher, the limit Oxygen index (OI) and excellent UV resistant performance, excellent fireproof performance, heat-resisting and heating conduction is excellent, can increase carbon and contain Amount, 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 that high intensity UV resistant is fire-retardant, it is characterised in that: the aromatic heterocyclic polymer tree Rouge includes with Am-Bn-Cx-DyThe polymer chain of expression, wherein A, B, C and D are the repetitive unit for constituting polymer chain backbone, And repetitive unit A, B, C and D are arranged with random order, m, n, x and y are positive integer；
The structural formula of the repetitive unit A are as follows:Institute State the structural formula of repetitive unit B are as follows:
The structural formula of the repetitive unit C 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 structural formula of the repetitive unit D are as follows: Wherein, R is oxygen, sulphur or is not present.
2. a kind of fire-retardant aromatic heterocyclic polymer resin of high-intensitive UV resistant according to claim 1, it is characterised in that: The aromatic heterocyclic polymer resin is modified using inorganic filler.
3. a kind of fire-retardant aromatic heterocyclic polymer resin of high-intensitive UV resistant according to claim 2, it is characterised in that: The inorganic filler is mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide, oxide, sulfate, carbonic acid At least one of salt, silicate, fluosilicate and phosphate.
4. a kind of fire-retardant aromatic heterocyclic polymer resin of high-intensitive UV resistant according to claim 3, it is characterised in that: The nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxide is oxidation At least one of calcium, zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
5. a kind of fire-retardant aromatic heterocyclic polymer resin of high-intensitive UV resistant according to claim 4, it is characterised in that: The silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
6. a kind of fire-retardant aromatic heterocyclic polymer resin of high-intensitive UV resistant according to claim 3, it is characterised in that: The sulfate is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate；The silicic acid Salt is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate be calcium carbonate, magnesium carbonate and zinc carbonate in extremely Few one kind；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphate is phosphoric acid At least one of calcium, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
7. a kind of fire-retardant aromatic heterocyclic polymer resin of high-intensitive UV resistant according to claim 1, it is characterised in that: 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 fiber, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
8. such as a kind of described in any item preparations for the aromatic heterocyclic polymer resin that high-intensitive UV resistant is fire-retardant of claim 1-7 Method, it is characterised in that: in the absence of R is, with terephthalic acid (TPA) and/or phthalic acid, 4,4 '-dioctyl phthalate of azobenzene- And/or azobenzene -3,3 '-dioctyl phthalate, containing bromo terephthalic acid and/or containing phthalate bromine, 4,4'- biphenyl dicarboxylic acid and/ Or 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, and it is poly- to obtain the heteroaromatic Polymer resin；
When R is oxygen, with terephthalic acid (TPA) and/or phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -3,3 ' - Dioctyl phthalate contains bromo terephthalic acid and/or contains phthalate bromine, 4,4'- oxydibenzoic acid and/or 3,3'- diphenyl ether two Formic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin；
When R is sulphur, with terephthalic acid (TPA) and/or phthalic acid, 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -3,3 ' - Dioctyl phthalate contains bromo terephthalic acid and/or contains phthalate bromine, 4,4'- diphenyl sulfide dioctyl phthalate and/or 3,3'- diphenyl sulfide Ether dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.
9. such as a kind of answering for the described in any item aromatic heterocyclic polymer resins that high-intensitive UV resistant is fire-retardant 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 fire-retardant aromatic heterocyclic polymer resin of high-intensitive UV resistant according to claim 9, special Sign is: 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.
CN201811147865.5A 2018-09-29 2018-09-29 Fire-retardant aromatic heterocyclic polymer resin of a kind of high intensity UV resistant and preparation method thereof and application in fiber or film Withdrawn CN109306183A (en)

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