CN109280381A - A kind of fire-retardant aromatic heterocyclic polymer resin and preparation method thereof and application in fiber or film - Google Patents

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

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CN109280381A
CN109280381A CN201811146101.4A CN201811146101A CN109280381A CN 109280381 A CN109280381 A CN 109280381A CN 201811146101 A CN201811146101 A CN 201811146101A CN 109280381 A CN109280381 A CN 109280381A
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aromatic heterocyclic
polymer resin
heterocyclic polymer
fire
sulfate
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王庭辉
刘文熙
潘鑫
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    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • 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
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    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
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    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Abstract

The present invention relates to resin technology fields, more particularly to a kind of fire-retardant aromatic heterocyclic polymer resin and preparation method thereof and in the application of fiber or film, the fire-retardant aromatic heterocyclic polymer resin the preparation method comprises the following steps: in the absence of being as R, 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, obtains the aromatic heterocyclic polymer resin.Aromatic heterocyclic polymer resin limit oxygen index with higher of the invention, excellent fireproof performance, heating conduction is excellent, also has 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 fire-retardant aromatic heterocyclic polymer resin and preparation method thereof and in fiber or film Application
Technical field
The present invention relates to resin technology fields, and in particular to a kind of fire-retardant aromatic heterocyclic polymer resin and preparation method thereof With the 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 fire-retardant virtue is miscellaneous Cyclopolymer resin, the aromatic heterocyclic polymer resin limit oxygen index with higher, excellent fireproof performance, heating conduction are excellent It is good, carbon element content can be increased, can be used for preparing graphitization heat sink material, also have good dimensional stability, heat resistance, The performances such as resistance to oxidation, electrical isolation, solvent resistance, special electric conductivity and electroluminescent, excellent combination property.
It is another object of the present invention to provide a kind of preparation method of fire-retardant aromatic heterocyclic polymer resin, the preparations Method and step is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, can large-scale industrial production.
Another purpose of the invention is that providing a kind of application of fire-retardant aromatic heterocyclic polymer resin.
The purpose of the invention is achieved by the following technical solution: a kind of fire-retardant aromatic heterocyclic polymer resin, the virtue are miscellaneous Cyclopolymer 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 arranged with random order, m and n are positive integer；
The structural formula of the repetitive unit A are as follows:And/orIts In, R1, R2, R3 and R4 are unsubstituted or substituted bromine, and at least one in R1, R2, R3 and R4 is the bromine replaced；
The structural formula of the repetitive unit B are as follows:And/or
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 system of fire-retardant aromatic heterocyclic polymer resin Preparation Method, in the absence of R is, with containing bromo terephthalic acid and/or containing phthalate bromine, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- biphenyl dicarboxylic acids, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtain the heteroaromatic polymerization Resin.
Specifically, polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine, 4,4 '-biphenyl dicarboxylic acids 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 (containing bromo terephthalic acid and/or containing phthalate bromine) and polymerized monomer (4,4 '-biphenyl Dioctyl phthalate and/or 3,3 '-biphenyl dicarboxylic acids) molar ratio be (0.01-0.99): (0.99-0.01).It is excellent in order to save cost Choosing, polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) with 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, the molar ratio containing bromo terephthalic acid and containing phthalate bromine is (0-1): (1-0), 4,4 '-connection The molar ratio of phthalic acid and 3,3 '-biphenyl dicarboxylic acids is (0-1): (1-0).
A kind of preparation method of fire-retardant aromatic heterocyclic polymer resin, when R is oxygen, with containing bromo terephthalic acid and/or Containing phthalate bromine, 4,4'- oxydibenzoic acid and/or 3,3'- oxydibenzoic 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.
Specifically, polymerized monomer (containing bromo terephthalic acid and/or contains phthalate bromine, 4,4 '-oxydibenzoic acids And/or 3,3 '-oxydibenzoic acids), the molar ratio of hydrazine sulfate and oleum be 1:(1.01-5.0): (5-15), wherein sending out Cigarette sulfuric acid molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (containing bromo terephthalic acid and/or containing phthalate bromine) and polymerized monomer (4,4 '-hexichol Ether dioctyl phthalate and/or 3,3 '-oxydibenzoic acids) molar ratio be (0.01-0.99): (0.99-0.01).In order to save into This, it is preferred that polymerized monomer (containing bromo terephthalic acid and/or containing phthalate bromine) and polymerized monomer (4,4 '-diphenyl ether two Formic acid and/or 3,3 '-oxydibenzoic acids) molar ratio be (0.90-0.99): (0.10-0.01).
Further, the molar ratio containing bromo terephthalic acid and containing phthalate bromine be (0-1): (1-0), 4,4'- bis- The molar ratio of phenylate dioctyl phthalate and 3,3'- oxydibenzoic acid is (0-1): (1-0).
A kind of preparation method of fire-retardant aromatic heterocyclic polymer resin, when R is sulphur, with containing bromo terephthalic acid and/or Containing phthalate bromine, 4,4'- diphenyl sulfide dioctyl phthalate and/or 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, Polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.
Specifically, polymerized monomer (containing 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 molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (containing bromo terephthalic acid and/or containing phthalate bromine) and polymerized monomer (4,4 '-hexichol Thioether 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 (containing bromo terephthalic acid and/or containing phthalate bromine) and polymerized monomer (4,4 '-diphenyl sulfides Ether dioctyl phthalate and/or 3,3 '-diphenyl sulfide dioctyl phthalate) molar ratio be (0.90-0.99): (0.10-0.01).
Further, the molar ratio containing bromo terephthalic acid and containing phthalate bromine be (0-1): (1-0), 4,4'- bis- The molar ratio of 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 fire-retardant aromatic heterocyclic polymer resin is answered With the aromatic heterocyclic polymer resin is 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 limit oxygen index with higher of the invention, resistance Combustion is had excellent performance, and heating conduction is excellent, can increase carbon element content, can be used for preparing graphitization heat sink material, is also had good The performances such as good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special electric conductivity and electroluminescent, Excellent combination property.
Preparation method step of the invention is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, It can large-scale industrial production.
The application of fire-retardant aromatic heterocyclic polymer resin 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, the aromatic heterocyclic polymer resin includes with Am-BnThe polymer of expression Chain, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are arranged with random order, and m and n are equal For positive integer；
The structural formula of the repetitive unit A 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 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 fire-retardant aromatic heterocyclic polymer resin, in the absence of R is, with containing bromo terephthalic acid, 4,4'- biphenyl dicarboxylic acids, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtain the heteroaromatic polymerization Resin.The molar ratio of polymerized monomer (containing bromo terephthalic acid, 4,4 '-biphenyl dicarboxylic acids), hydrazine sulfate and oleum is 1: (1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity is with SO in oleum3Mole Number meter.
Wherein, polymerized monomer (containing bromo terephthalic acid) and the molar ratio of polymerized monomer (4,4 '-biphenyl dicarboxylic acid) are (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, to contain bromo terephthalic acid, 4,4'- oxydibenzoic acid, hydrazine sulfate for reaction raw materials, in smoke Polycondensation reaction is carried out in sulfuric acid, obtains the aromatic heterocyclic polymer resin.Specifically, polymerized monomer (contain bromo terephthalic acid, 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, polymerized monomer (containing bromo terephthalic acid) and the molar ratio of polymerized monomer (4,4 '-oxydibenzoic acid) are (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, for reaction raw materials, to be sent out containing bromo terephthalic acid, 4,4'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate Polycondensation reaction is carried out in cigarette sulfuric acid, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (contains bromo terephthalic acid, 4,4 '-two 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 with SO in oleum3Molal quantity meter.
Wherein, molar ratio of the polymerized monomer (containing bromo terephthalic acid) with polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate) For (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 fire-retardant aromatic heterocyclic polymer resin, the aromatic heterocyclic polymer resin includes with Am-BnThe polymer of expression Chain, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are arranged with random order, and m and n are equal For positive integer；
The structural formula of the repetitive unit A 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 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 fire-retardant aromatic heterocyclic polymer resin, in the absence of R is, with containing phthalate bromine, 3,3'- biphenyl dicarboxylic acids, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtain the heteroaromatic polymerization Resin.The molar ratio of polymerized monomer (containing phthalate bromine, 3,3 '-biphenyl dicarboxylic acids), hydrazine sulfate and oleum is 1: (1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity is with SO in oleum3Mole Number meter.
Wherein, polymerized monomer (containing phthalate bromine) and the molar ratio of polymerized monomer (3,3 '-biphenyl dicarboxylic acid) are (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, to contain phthalate bromine, 3,3'- oxydibenzoic acid, hydrazine sulfate for reaction raw materials, in smoke Polycondensation reaction is carried out in sulfuric acid, obtains the aromatic heterocyclic polymer resin.Specifically, polymerized monomer (contain phthalate bromine, 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 (containing phthalate bromine) and the molar ratio of polymerized monomer (3,3 '-oxydibenzoic acid) are (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, for reaction raw materials, to be sent out containing phthalate bromine, 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate Polycondensation reaction is carried out in cigarette sulfuric acid, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (contains phthalate bromine, 3,3 '-two 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 with SO in oleum3Molal quantity meter.
Wherein, molar ratio of the polymerized monomer (containing phthalate bromine) with polymerized monomer (3,3 '-diphenyl sulfide dioctyl phthalate) For (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 fire-retardant aromatic heterocyclic polymer resin, the aromatic heterocyclic polymer resin includes with Am-BnThe polymer of expression Chain, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are arranged with random order, and m and n are equal For positive integer；
The structural formula of the repetitive unit A 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 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 fire-retardant aromatic heterocyclic polymer resin, in the absence of R is, with 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 (contains bromo terephthalic acid and brominated O-phthalic Acid, 4,4 '-biphenyl dicarboxylic acids and 3,3 '-biphenyl dicarboxylic 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 (containing bromo terephthalic acid and containing phthalate bromine) and polymerized monomer (4,4 '-biphenyl diformazans 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).
Molar ratio containing bromo terephthalic acid and containing phthalate bromine 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 ratios of 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, containing bromo terephthalic acid and containing phthalate bromine, 4,4'- oxydibenzoic acid and 3,3'- bis- Phenylate dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer tree Rouge.Specifically, polymerized monomer (containing bromo terephthalic acid and contain phthalate bromine, 4,4 '-oxydibenzoic acids and 3,3 '-two Phenylate 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 with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (containing bromo terephthalic acid and containing phthalate bromine) and polymerized monomer (4,4 '-diphenyl ether two Formic 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).
Molar ratio containing bromo terephthalic acid and containing phthalate bromine 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 4,4'- oxydibenzoic acids and 3,3'- oxydibenzoic acid are (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, containing bromo terephthalic acid and containing phthalate bromine, 4,4'- diphenyl sulfide dioctyl phthalate and 3,3'- Diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer Resin.Polymerized monomer (containing bromo terephthalic acid and contains phthalate bromine, 4,4 '-diphenyl sulfide dioctyl phthalate and 3,3 '-diphenyl sulfides Ether 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 with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (containing bromo terephthalic acid and containing phthalate bromine) and polymerized monomer (4,4 '-diphenyl sulfides 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).
Molar ratio containing bromo terephthalic acid and containing phthalate bromine 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, the molar ratio of 3'- diphenyl sulfide dioctyl phthalate For (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 fire-retardant aromatic heterocyclic polymer resin, the aromatic heterocyclic polymer resin are applied to fiber.
Embodiment 5
A kind of application of fire-retardant aromatic heterocyclic polymer resin, 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 40.4- using film limit oxygen index made from aromatic heterocyclic polymer resin of the invention 44.3%, thermal decomposition temperature can achieve 466-477 DEG C, and vertical thermal conductivity can achieve 37.8-58.6W/m-K, and level is led Hot coefficient can achieve 1190-1370W/m-K, limit oxygen index with higher, excellent fireproof performance, heat-resisting and heating conduction It is excellent, carbon element content can be increased, 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 fire-retardant aromatic heterocyclic polymer resin, it is characterised in that: the aromatic heterocyclic polymer resin includes with Am-BnTable The polymer chain shown, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are with random order Arrangement, m and n are positive integer；
The structural formula of the repetitive unit A are as follows:And/orIts In, R1, R2, R3 and R4 are unsubstituted or substituted bromine, and at least one in R1, R2, R3 and R4 is the bromine replaced；
The structural formula of the repetitive unit B are as follows:And/or
Wherein, R is oxygen, sulphur or is not present.
2. the fire-retardant aromatic heterocyclic polymer resin of one kind according to claim 1, it is characterised in that: the heteroaromatic polymerization Resin is modified using inorganic filler.
3. the fire-retardant aromatic heterocyclic polymer resin of one kind 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, carbonate, silicate, fluorine silicon At least one of hydrochlorate and phosphate.
4. the fire-retardant aromatic heterocyclic polymer resin of one kind according to claim 3, it is characterised in that: the nitride is nitrogen SiClx and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxide is calcium oxide, zinc oxide, oxidation At least one of magnesium, iron oxide, silica and titanium dioxide.
5. the fire-retardant aromatic heterocyclic polymer resin of one kind according to claim 4, it is characterised in that: the silica is Nano silica, the titanium dioxide are nano-titanium dioxide.
6. the fire-retardant aromatic heterocyclic polymer resin of one kind according to claim 3, it is characterised in that: the sulfate is sulphur At least one of sour calcium, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate；The silicate is sodium metasilicate, silicic acid At least one of aluminium and magnesium silicate；The carbonate is at least one of calcium carbonate, magnesium carbonate and zinc carbonate；The fluorine silicon Hydrochlorate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphate is calcium phosphate, calcium monohydrogen phosphate, phosphorus At least one of sour magnesium and magnesium monohydrogen phosphate.
7. the fire-retardant aromatic heterocyclic polymer resin of one kind according to claim 1, it is characterised in that: the heteroaromatic polymerization Resin is modified using modifying agent, the modifying agent be glass microballoon, whisker, carbon fiber, glass fibre, Fanglun slurry cake, At least one of the short fine, silicone of aramid fiber and polytetrafluoroethylene (PTFE).
8. such as the preparation method of the fire-retardant aromatic heterocyclic polymer resin of the described in any item one kind of claim 1-7, feature exists In: in the absence of R is, to 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 aromatic heterocyclic polymer Resin；
When R is oxygen, containing bromo terephthalic acid and/or containing phthalate bromine, 4,4'- oxydibenzoic acid and/or 3,3'- Oxydibenzoic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer tree Rouge；
When R is sulphur, to contain bromo terephthalic acid and/or contain phthalate bromine, 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, and it is poly- to obtain the heteroaromatic Polymer resin.
9. such as the application of the fire-retardant aromatic heterocyclic polymer resin of the described in any item one kind of claim 1-7, it is characterised in that: institute Aromatic heterocyclic polymer resin is stated applied to fiber or film.
10. the application of the fire-retardant aromatic heterocyclic polymer resin of one kind according to claim 9, it is characterised in that: described thin 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.
CN201811146101.4A 2018-09-29 2018-09-29 A kind of fire-retardant aromatic heterocyclic polymer resin and preparation method thereof and application in fiber or film Pending CN109280381A (en)

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Citations (5)

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

Patent Citations (5)

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

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