CN109306182A - A kind of aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant and preparation method thereof and application in fiber or film - Google Patents

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

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CN109306182A
CN109306182A CN201811147849.6A CN201811147849A CN109306182A CN 109306182 A CN109306182 A CN 109306182A CN 201811147849 A CN201811147849 A CN 201811147849A CN 109306182 A CN109306182 A CN 109306182A
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aromatic heterocyclic
polymer resin
acid
heterocyclic polymer
fluorine
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刘文熙
潘鑫
王庭辉
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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-strength and high-transparent 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-strength and high-transparent the preparation method comprises the following steps: in the absence of being as R, with terephthalic acid (TPA) and/or phthalic acid, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid, 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, transparency and limit oxygen index of the invention, excellent fireproof performance, heating conduction is excellent, excellent combination property.

Description

A kind of aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant and preparation method thereof and In the application of fiber or film
Technical field
The present invention relates to resin technology fields, and in particular to a kind of aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant And preparation method thereof and fiber or film application.
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 high-intensitive high saturating Bright fire-retardant aromatic heterocyclic polymer resin, aromatic heterocyclic polymer resin intensity with higher, transparency and the limit oxygen index, Excellent fireproof performance, heating conduction is excellent, can increase carbon element content, can be used for preparing graphitization heat sink material, also has The property such as good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special electric conductivity and electroluminescent Can, excellent combination property.
It is another object of the present invention to provide a kind of systems of aromatic heterocyclic polymer resin that high-strength and high-transparent 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 advise greatly Modelling industrial production.
Another purpose of the invention is that providing a kind of answering for aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant With.
The purpose of the invention is achieved by the following technical solution: a kind of aromatic heterocyclic polymer tree that high-strength and high-transparent is fire-retardant Rouge, the aromatic heterocyclic polymer resin includes with Am-Bn-Cx-DyThe polymer chain of expression, wherein A, B, C and D are to constitute The repetitive unit of 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:
The structural formula of the repetitive unit B 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 structural formula of the repetitive unit C are as follows: Wherein, R5, R6, R7 and R8 are unsubstituted or substituted bromine, and at least one in R5, R6, R7 and R8 is the bromine replaced；
The structural formula of the repetitive unit D are as follows: 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-strength and high-transparent is fire-retardant is poly- The preparation method of polymer resin, in the absence of R is, with terephthalic acid (TPA) and/or phthalic acid, fluorine-containing terephthalic acid (TPA) And/or fluorine-containing phthalic acid, containing 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 aromatic heterocyclic polymer Resin.
Specifically, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing adjacent benzene Dioctyl phthalate contains bromo terephthalic acid and/or contains phthalate bromine, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- biphenyl diformazan Acid), the molar ratio of hydrazine sulfate and oleum be 1:(1.01-5.0): (5-15), wherein oleum molal quantity is with oleum SO in acid3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid), polymerized monomer (fluorine-containing terephthalic acid (TPA) and/or Fluorine-containing phthalic acid), polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) with polymerized monomer (4,4 '-connection Phthalic acid and/or 3,3 '-biphenyl dicarboxylic acids) molar ratio be (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 phthalic acid), polymerized monomer (fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid), polymerized monomer (contain bromo terephthalic acid and/or brominated O-phthalic Acid) with the molar ratio of polymerized monomer (4,4 '-biphenyl dicarboxylic acids and/or 3,3 '-biphenyl dicarboxylic acids) 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 be (0-1): (1-0), fluorine-containing terephthalic acid (TPA) and The molar ratio of fluorine-containing phthalic acid is (0-1): (1-0), the molar ratio containing bromo terephthalic acid and containing phthalate bromine are (0-1): (1-0), 4,4 '-biphenyl dicarboxylic acids and 3, the molar ratio of 3 '-biphenyl dicarboxylic acids are (0-1): (1-0).
A kind of preparation method for the aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant, when R is oxygen, with terephthaldehyde Acid and/or phthalic acid, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid contain bromo terephthalic acid and/or brominated neighbour Phthalic acid, 4,4'- oxydibenzoic acid and/or 3,3'- oxydibenzoic acid, hydrazine sulfate are reaction raw materials, in oleum Middle carry out polycondensation reaction, obtains the aromatic heterocyclic polymer resin.
Specifically, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing adjacent benzene Dioctyl phthalate contains bromo terephthalic acid and/or contains phthalate bromine, 4,4'- oxydibenzoic acid and/or 3,3'- diphenyl ether two Formic acid), the molar ratio of hydrazine sulfate and oleum be 1:(1.01-5.0): (5-15), wherein oleum molal quantity is with smoke SO in sulfuric acid3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid), polymerized monomer (fluorine-containing terephthalic acid (TPA) and/or Fluorine-containing phthalic acid), polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) with polymerized monomer (4,4 '-two Phenylate dioctyl phthalate and/or 3,3 '-oxydibenzoic acids) molar ratio be (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 phthalic acid) is gathered Close monomer (fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid), polymerized monomer (contains bromo terephthalic acid and/or brominated neighbour Phthalic acid) with the molar ratio of polymerized monomer (4,4 '-oxydibenzoic acids and/or 3,3 '-oxydibenzoic acids) 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 be (0-1): (1-0), fluorine-containing terephthalic acid (TPA) and The molar ratio of fluorine-containing phthalic acid is (0-1): (1-0), the molar ratio containing bromo terephthalic acid and containing phthalate bromine are (0-1): (1-0), 4,4 '-oxydibenzoic acids and 3, the molar ratio of 3 '-oxydibenzoic acids are (0-1): (1-0).
A kind of preparation method for the aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant, when R is sulphur, with terephthaldehyde Acid and/or phthalic acid, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid contain bromo terephthalic acid and/or brominated neighbour Phthalic acid, 4,4'- diphenyl sulfide dioctyl phthalate and/or 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, in smoke Polycondensation reaction is carried out in sulfuric acid, obtains the aromatic heterocyclic polymer resin.
Specifically, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing adjacent benzene 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), 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 (fluorine-containing terephthalic acid (TPA) and/or Fluorine-containing phthalic acid), polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) with polymerized monomer (4,4 '-two Diphenyl sulfide dioctyl phthalate and/or 3,3 '-diphenyl sulfide dioctyl phthalate) molar ratio be (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 phthalic acid) is gathered Close monomer (fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid), polymerized monomer (contains bromo terephthalic acid and/or brominated neighbour Phthalic acid) with the molar ratio of polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate and/or 3,3 '-diphenyl sulfide dioctyl phthalate) 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 be (0-1): (1-0), fluorine-containing terephthalic acid (TPA) and The molar ratio of fluorine-containing phthalic acid is (0-1): (1-0), the molar ratio containing bromo terephthalic acid and containing phthalate bromine are (0-1): (1-0), 4,4 '-diphenyl sulfide dioctyl phthalate and 3, the molar ratio of 3 '-diphenyl sulfide dioctyl phthalate are (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-strength and high-transparent is fire-retardant is poly- The application of polymer 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 Limit oxygen index, excellent fireproof performance, heating conduction is excellent, can increase carbon element content, can be used for preparing graphitization heat dissipation Material also has good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special electric conductivity and electricity The performances such as photoluminescence, 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-strength and high-transparent of the invention in fiber or film.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant, the aromatic heterocyclic polymer resin 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, 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: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 structural formula of the repetitive unit C are as follows:Wherein, R5, R6, R7 and R8 are not take Generation or the bromine replaced, and at least one in R5, R6, R7 and R8 is the bromine replaced；
The structural formula of the repetitive unit D are as follows:, R is oxygen, sulphur or 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-strength and high-transparent is fire-retardant, in the absence of R is, to benzene Dioctyl phthalate, fluorine-containing terephthalic acid (TPA), containing bromo terephthalic acid, 4,4'- biphenyl dicarboxylic acid, hydrazine sulfate be reaction raw materials, in smoke Polycondensation reaction is carried out in sulfuric acid, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (terephthalic acid (TPA), fluorine-containing terephthaldehyde Acid contains 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 oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA)), polymerized monomer (fluorine-containing terephthalic acid (TPA)), polymerized monomer are (brominated to benzene Dioctyl phthalate) 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), fluorine-containing terephthalic acid (TPA), contain bromo terephthalic acid, 4,4'- 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 (terephthalic acid (TPA), contains bromo terephthalic acid, 4,4'- oxydibenzoic acid at fluorine-containing terephthalic acid (TPA)), 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)), polymerized monomer (fluorine-containing terephthalic acid (TPA)), polymerized monomer are (brominated to benzene Dioctyl phthalate) 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), fluorine-containing terephthalic acid (TPA), contain bromo terephthalic acid, 4,4'- 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 (terephthalic acid (TPA), fluorine-containing terephthalic acid (TPA), contain bromo terephthalic acid, 4,4'- diphenyl sulfide dioctyl phthalate), hydrazine sulfate and The molar ratio of oleum is 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum mole Number is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA)), polymerized monomer (fluorine-containing terephthalic acid (TPA)), polymerized monomer are (brominated to benzene Dioctyl phthalate) 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 aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant, the aromatic heterocyclic polymer resin 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, 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: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 structural formula of the repetitive unit C are as follows:Wherein, R5, R6, R7 and R8 are not take Generation or the bromine replaced, and at least one in R5, R6, R7 and R8 is the bromine replaced；
The structural formula of the repetitive unit D are as follows:R is oxygen, sulphur or not In the presence of.
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-strength and high-transparent is fire-retardant, in the absence of R is, with adjacent benzene Dioctyl phthalate, fluorine-containing phthalic acid contain phthalate bromine, 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate for reaction raw materials, in smoke Polycondensation reaction is carried out in sulfuric acid, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (phthalic acid, fluorine-containing O-phthalic Acid contains phthalate bromine, 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 (fluorine-containing phthalic acid), polymerized monomer (brominated neighbour's 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, fluorine-containing phthalic acid, contain phthalate bromine, 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, contains phthalate bromine, 3,3'- oxydibenzoic acid at fluorine-containing phthalic acid), 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 (phthalic acid), polymerized monomer (fluorine-containing phthalic acid), polymerized monomer (brominated neighbour's 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, fluorine-containing phthalic acid, contain phthalate bromine, 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, fluorine-containing phthalic acid, contain phthalate bromine, 3,3'- diphenyl sulfide dioctyl phthalate), hydrazine sulfate and The molar ratio of oleum is 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum mole Number is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (phthalic acid), polymerized monomer (fluorine-containing phthalic acid), polymerized monomer (brominated neighbour's 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 aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant, the aromatic heterocyclic polymer resin 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, 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: 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 structural formula of the repetitive unit C are as follows: Wherein, R5, R6, R7 and R8 are unsubstituted or substituted bromine, and at least one in R5, R6, R7 and R8 is the bromine replaced；
The structural formula of the repetitive unit D are as follows: 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-strength and high-transparent is fire-retardant, in the absence of R is, to benzene Dioctyl phthalate and phthalic acid, fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid contain bromo terephthalic acid and brominated adjacent benzene two Formic acid, 4,4'- biphenyl dicarboxylic acid and 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, and it is anti-that polycondensation is carried out in oleum It answers, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (terephthalic acid (TPA) and phthalic acid, fluorine-containing terephthalic acid (TPA) and Fluorine-containing phthalic acid contains bromo terephthalic acid and contains phthalate bromine, 4,4'- biphenyl dicarboxylic acid and 3,3'- biphenyl diformazan 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 (fluorine-containing terephthalic acid (TPA) and fluorine-containing neighbour Phthalic acid), polymerized monomer (containing bromo terephthalic acid and contain phthalate bromine) with polymerized monomer (4,4 '-biphenyl dicarboxylic acids With 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 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), containing bromo terephthalic acid and containing phthalate bromine Molar ratio 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 two The molar ratio of formic 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, fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid, contain Bromo terephthalic acid and be anti-containing phthalate bromine, 4,4'- oxydibenzoic acid and 3,3'- oxydibenzoic acid, hydrazine sulfate Raw material is answered, polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (terephthalic acid (TPA) With phthalic acid, fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid, containing bromo terephthalic acid and contain phthalate bromine, 4, 4'- oxydibenzoic acid and 3,3'- oxydibenzoic 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 (fluorine-containing terephthalic acid (TPA) and fluorine-containing neighbour Phthalic acid), polymerized monomer (containing bromo terephthalic acid and contain phthalate bromine) with polymerized monomer (4,4 '-diphenyl ether diformazans 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 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), containing bromo terephthalic acid and containing phthalate bromine Molar ratio 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 ether The molar ratio of dioctyl phthalate and 3,3 '-oxydibenzoic 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 sulphur, with terephthalic acid (TPA) and phthalic acid, fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid, contain Bromo terephthalic acid and containing phthalate bromine, 4,4'- diphenyl sulfide dioctyl phthalate and 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 is (to benzene two Formic acid and phthalic acid, fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid contain bromo terephthalic acid and brominated O-phthalic Acid, 4,4'- diphenyl sulfide 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 oleum3It rubs That number meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and phthalic acid), polymerized monomer (fluorine-containing terephthalic acid (TPA) and fluorine-containing neighbour Phthalic acid), polymerized monomer (containing bromo terephthalic acid and contain phthalate bromine) with polymerized monomer (4,4 '-diphenyl sulfides two Formic acid 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 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), containing bromo terephthalic acid and containing phthalate bromine Molar ratio 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 sulfides The molar ratio of ether 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-strength and high-transparent is fire-retardant, the aromatic heterocyclic polymer resin application In fiber.
Embodiment 5
A kind of application for the aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant, the aromatic heterocyclic polymer resin application In 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 87.5-91.4MPa, longitudinal tensile strength can achieve 145.3-153.2MPa, and transparency can achieve 86.8-89.7%, pole Limited oxygen index can achieve 38.6-42.4%, and thermal decomposition temperature can achieve 455-466 DEG C, and vertical thermal conductivity can achieve 34.8-52.8W/m-K, horizontal thermal conductivity factor can achieve 1050-1260W/m-K, intensity, transparency and the limit with higher Oxygen index (OI), excellent fireproof performance, heat-resisting and heating conduction is excellent, can increase carbon element content, can be used for preparing graphitization and dissipates Hot 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-strength and high-transparent is fire-retardant, it is characterised in that: the aromatic heterocyclic polymer resin Including 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, and m, n, x and y are positive integer；
The structural formula of the repetitive unit A are as follows:And/or
The structural formula of the repetitive unit B are as follows:And/orIts In, R1, R2, R3 and R4 are unsubstituted or substituted fluorine, and at least one in R1, R2, R3 and R4 is the fluorine replaced；
The structural formula of the repetitive unit C are as follows:And/orIts In, R5, R6, R7 and R8 are unsubstituted or substituted bromine, and at least one in R5, R6, R7 and R8 is the bromine replaced；
The structural formula of the repetitive unit D are as follows:And/orR is oxygen, sulphur or is not present.
2. a kind of fire-retardant aromatic heterocyclic polymer resin of high-strength and high-transparent according to claim 1, it is characterised in that: institute Aromatic heterocyclic polymer resin is stated to be modified using inorganic filler.
3. a kind of fire-retardant aromatic heterocyclic polymer resin of high-strength and high-transparent according to claim 2, it is characterised in that: institute Stating 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-strength and high-transparent according to claim 3, it is characterised in that: institute Stating nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxide be calcium oxide, At least one of zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
5. a kind of fire-retardant aromatic heterocyclic polymer resin of high-strength and high-transparent according to claim 4, it is characterised in that: institute Stating silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
6. a kind of fire-retardant aromatic heterocyclic polymer resin of high-strength and high-transparent according to claim 3, it is characterised in that: institute Stating sulfate is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate；The silicate For at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate be calcium carbonate, magnesium carbonate and zinc carbonate at least It is a kind of；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-strength and high-transparent according to claim 1, it is characterised in that: institute It states aromatic heterocyclic polymer resin to be modified using modifying agent, the modifying agent is glass microballoon, whisker, carbon fiber, glass fibers At least one of the short fine, silicone of dimension, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
8. such as a kind of described in any item preparation sides for the aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant claim 1-7 Method, it is characterised in that: in the absence of R is, with terephthalic acid (TPA) and/or phthalic acid, fluorine-containing terephthalic acid (TPA) and/or contain Fluorine phthalic acid contains bromo terephthalic acid and/or contains phthalate bromine, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- biphenyl Dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin；
When R is oxygen, with terephthalic acid (TPA) and/or phthalic acid, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid, Containing bromo terephthalic acid and/or containing phthalate bromine, 4,4'- oxydibenzoic acid and/or 3,3'- oxydibenzoic acid, sulphur Sour hydrazine is 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, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid, Containing bromo terephthalic acid and/or contain phthalate bromine, 4,4'- diphenyl sulfide dioctyl phthalate and/or 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.
9. such as a kind of described in any item applications for the aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant of claim 1-7, It is characterized by: 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-strength and high-transparent according to claim 9, feature Be: the film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, graphitization heat dissipation film Substrate, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand-set lid.
CN201811147849.6A 2018-09-29 2018-09-29 A kind of aromatic heterocyclic polymer resin that high-strength and high-transparent is fire-retardant and preparation method thereof and application in fiber or film Withdrawn CN109306182A (en)

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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007133409A2 (en) * 2006-05-01 2007-11-22 E. I. Du Pont De Nemours And Company Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom
CN101437871A (en) * 2006-05-01 2009-05-20 纳幕尔杜邦公司 Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom
CN104093787A (en) * 2012-01-12 2014-10-08 韩华石油化学株式会社 Resin composition for emi shielding, comprising carbon hydride composite
CN104817687A (en) * 2015-05-22 2015-08-05 江苏宝德新材料有限公司 High-purity aromatic polyoxadiazole solution and fiber prepared from high-purity aromatic polyoxadiazole solution
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Application publication date: 20190205