CN109293899A - A kind of aromatic heterocyclic polymer resin of high-strength anti-flaming and preparation method thereof and application in fiber or film - Google Patents

A kind of aromatic heterocyclic polymer resin of high-strength anti-flaming and preparation method thereof and application in fiber or film Download PDF

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CN109293899A
CN109293899A CN201811148705.2A CN201811148705A CN109293899A CN 109293899 A CN109293899 A CN 109293899A CN 201811148705 A CN201811148705 A CN 201811148705A CN 109293899 A CN109293899 A CN 109293899A
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aromatic heterocyclic
polymer resin
heterocyclic polymer
acid
terephthalic acid
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潘鑫
刘文熙
王庭辉
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3228—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing nitrogen and oxygen as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers

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Abstract

The present invention relates to resin technology fields, aromatic heterocyclic polymer resin more particularly to a kind of high-strength anti-flaming and preparation method thereof and application in fiber or film, the aromatic heterocyclic polymer resin of the high-strength anti-flaming the preparation method comprises the following steps: in the absence of being as R, with terephthalic acid (TPA) and/or phthalic acid, 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, polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Aromatic heterocyclic polymer film intensity with higher of the invention and limit oxygen index, 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 aromatic heterocyclic polymer resin of high-strength anti-flaming and preparation method thereof and in fiber Or the application of film
Technical field
The present invention relates to resin technology fields, and in particular to a kind of the aromatic heterocyclic polymer resin and its system of high-strength anti-flaming Preparation Method and application in fiber or film.
Background technique
In heterocyclic compound cyclic organic compounds, constitute there are also other atomic time outside the atom carbon atom of ring, it is this kind of Cyclic organic compounds are called heterocyclic compound, and non-carbon is known as hetero atom.The most common hetero atom is oxygen and sulphur, on heterocycle Can have a hetero atom, can also there are two or more hetero atom, hetero atom can be a kind of atom, be also possible to two kinds Different atoms.As cycloalkane, heterocycle can also be divided into alicyclic heterocyclic and heteroaromatic two major classes.In general, heteroaromatic Ring system has a degree of stability and armaticity, and in general chemical reaction, ring is not easily broken.Part heteroaromatic can gather Synthetic macromolecule resin has extensive potential using value due to its unique excellent performance.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, the purpose of the present invention is to provide a kind of high-strength anti-flamings Aromatic heterocyclic polymer resin, the aromatic heterocyclic polymer film intensity with higher and 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 good dimensionally stable The performances such as property, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special electric conductivity and electroluminescent, excellent combination property.
It is another object of the present invention to provide a kind of preparation method of the aromatic heterocyclic polymer resin of high-strength anti-flaming, The preparation method step is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, can large-scale industry Production.
Another purpose of the invention is that providing a kind of application of the aromatic heterocyclic polymer resin of high-strength anti-flaming.
The purpose of the invention is achieved by the following technical solution: a kind of aromatic heterocyclic polymer resin of high-strength anti-flaming, institute Stating aromatic heterocyclic polymer resin includes with Am-Bn-CxThe polymer chain of expression, wherein A, B and C are equal
For the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B and C are arranged with random order, and m, n and x are equal For 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 bromine, and at least one in R1, R2, R3 and R4 is the bromine replaced；
The structural formula of the repetitive unit C are as follows: Wherein, R is oxygen, sulphur or is not present.
Preferably, there is random copolymer configuration, alternate copolymer configuration or block copolymer configuration in the main chain, That is, the polymerization methods of the aromatic heterocyclic polymer resin can be random copolymerization, alternating copolymerization or block copolymerization.
Preferably, the aromatic heterocyclic polymer resin is modified using inorganic filler.
Preferably, the inorganic filler is mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide, oxygen At least one of compound, sulfate, carbonate, silicate, fluosilicate and phosphate.
Preferably, the nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；Institute Stating oxide is at least one of calcium oxide, zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
Preferably, the silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
Preferably, the sulfate be calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, in ferrous sulfate extremely Few one kind；The silicate is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate is calcium carbonate, carbonic acid At least one of magnesium and zinc carbonate；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate； The phosphate is at least one of calcium phosphate, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
Preferably, the aromatic heterocyclic polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, crystalline substance At least one of the short fine, silicone of palpus, carbon fiber, glass fibre, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
Another object of the present invention is achieved through the following technical solutions: a kind of aromatic heterocyclic polymer tree of high-strength anti-flaming The preparation method of rouge with terephthalic acid (TPA) and/or phthalic acid, containing bromo terephthalic acid and/or contains in the absence of R is Phthalate bromine, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, in oleum Middle carry out polycondensation reaction, obtains the aromatic heterocyclic polymer resin.
Specifically, (terephthalic acid (TPA) and/or phthalic acid contain bromo terephthalic acid and/or brominated adjacent benzene to polymerized monomer Dioctyl phthalate, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- biphenyl dicarboxylic acid), the molar ratio of hydrazine sulfate and oleum be 1: (1.01-5.0): (5-15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid), polymerized monomer (containing bromo terephthalic acid and/or Containing phthalate bromine) with the molar ratio of polymerized monomer (4,4 '-biphenyl dicarboxylic acids and/or 3,3 '-biphenyl dicarboxylic acids) be (0.01-0.99): (0.99-0.01): (0.99-0.01).In order to save cost, it is preferred that polymerized monomer (terephthalic acid (TPA) And/or phthalic acid), polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) with polymerized monomer (4,4 '- Biphenyl dicarboxylic acid and/or 3,3 '-biphenyl dicarboxylic acids) molar ratio be (0.80-0.98): (0.10-0.01): (0.10-0.01).
Further, the molar ratio of terephthalic acid (TPA) and phthalic acid is (0-1): (1-0), containing bromo terephthalic acid and Molar ratio containing phthalate bromine is (0-1): (1-0), 4,4 '-biphenyl dicarboxylic acids and 3, the molar ratio of 3 '-biphenyl dicarboxylic acids For (0-1): (1-0).
A kind of preparation method of the aromatic heterocyclic polymer resin of high-strength anti-flaming, when R be oxygen when, with terephthalic acid (TPA) and/ Or phthalic acid, containing bromo terephthalic acid and/or contain phthalate bromine, 4,4'- oxydibenzoic acid and/or 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, (terephthalic acid (TPA) and/or phthalic acid contain bromo terephthalic acid and/or brominated adjacent benzene to polymerized monomer Dioctyl phthalate, 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 oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid), polymerized monomer (containing bromo terephthalic acid and/or Containing phthalate bromine) with the molar ratio of polymerized monomer (4,4 '-oxydibenzoic acids and/or 3,3 '-oxydibenzoic acids) be (0.01-0.99): (0.99-0.01): (0.99-0.01).In order to save cost, it is preferred that polymerized monomer (terephthalic acid (TPA) And/or phthalic acid), polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) with polymerized monomer (4,4 '- Oxydibenzoic acid and/or 3,3 '-oxydibenzoic acids) molar ratio be (0.80-0.98): (0.10-0.01): (0.10- 0.01)。
Further, the molar ratio of terephthalic acid (TPA) and phthalic acid is (0-1): (1-0), containing bromo terephthalic acid and Molar ratio containing phthalate bromine is (0-1): (1-0), 4,4'- oxydibenzoic acids and 3,3'- oxydibenzoic acid rub You are than being (0-1): (1-0).
A kind of preparation method of the aromatic heterocyclic polymer resin of high-strength anti-flaming, when R be sulphur when, with terephthalic acid (TPA) and/ Or phthalic acid, containing 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, obtains the aromatic heterocyclic polymer Resin.
Specifically, (terephthalic acid (TPA) and/or phthalic acid contain bromo terephthalic acid and/or brominated adjacent benzene to polymerized monomer Dioctyl phthalate, 4,4 '-diphenyl sulfide dioctyl phthalate and/or 3,3 '-diphenyl sulfide dioctyl phthalate), the molar ratio of hydrazine sulfate and oleum For 1:(1.01-5.0): (5-15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid), polymerized monomer (containing bromo terephthalic acid and/or Containing phthalate bromine) with mole of polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate and/or 3,3 '-diphenyl sulfide dioctyl phthalate) Than for (0.01-0.99): (0.99-0.01): (0.99-0.01).In order to save cost, it is preferred that polymerized monomer (terephthaldehyde Acid and/or phthalic acid), polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) with polymerized monomer (4, 4 '-diphenyl sulfide dioctyl phthalate and/or 3,3 '-diphenyl sulfide dioctyl phthalate) molar ratio be (0.80-0.98): (0.10-0.01): (0.10-0.01)。
Further, the molar ratio of terephthalic acid (TPA) and phthalic acid is (0-1): (1-0), containing bromo terephthalic acid and Molar ratio containing phthalate bromine is (0-1): (1-0), 4,4'- diphenyl sulfide dioctyl phthalate and 3,3'- diphenyl sulfide dioctyl phthalate Molar ratio be (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 aromatic heterocyclic polymer tree of high-strength anti-flaming The application of rouge, 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 film intensity with higher of the invention and limit oxygen refer to Number, excellent fireproof performance, heating conduction is excellent, can increase carbon element content, can be used for preparing graphitization heat sink material, also has There are 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.
Preparation method step of the invention is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, It can large-scale industrial production.
Application of the aromatic heterocyclic polymer resin of high-strength anti-flaming of the invention in fiber or film.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of aromatic heterocyclic polymer resin of high-strength anti-flaming, the aromatic heterocyclic polymer resin includes with Am-Bn-CxTable The polymer chain shown, wherein A, B and C are the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B and C are with any Sequence arranges, and m, n and x are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows: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 C are as follows:Wherein, R be oxygen, Sulphur is not present.
The aromatic heterocyclic polymer resin is modified using inorganic filler.
The inorganic filler is in mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide and oxide At least one.
The nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxidation Object is at least one of calcium oxide, zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
The silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
A kind of preparation method of the aromatic heterocyclic polymer resin of high-strength anti-flaming, in the absence of R is, with terephthaldehyde Acid, containing bromo terephthalic acid, 4,4'- biphenyl dicarboxylic acid, hydrazine sulfate be reaction raw materials, polycondensation reaction is carried out in oleum, Obtain the aromatic heterocyclic polymer resin.Polymerized monomer (terephthalic acid (TPA) contains bromo terephthalic acid, 4,4'- biphenyl dicarboxylic acid), The molar ratio of hydrazine sulfate and oleum is for 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein smoke Sulfuric acid molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA)), polymerized monomer (containing bromo terephthalic acid) and polymerized monomer (4,4 '-connection Phthalic acid) molar ratio be (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25 or 0.01).
It is reaction with terephthalic acid (TPA), containing bromo terephthalic acid, 4,4'- oxydibenzoic acid, hydrazine sulfate when R is oxygen Raw material carries out polycondensation reaction in oleum, obtains the aromatic heterocyclic polymer resin.(terephthalic acid (TPA) contains polymerized monomer 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 (terephthalic acid (TPA)), polymerized monomer (containing bromo terephthalic acid) and polymerized monomer (4,4 '-two Phenylate 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).
When R is sulphur, with terephthalic acid (TPA), be anti-containing bromo terephthalic acid, 4,4'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate Raw material is answered, polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (terephthalic acid (TPA), Containing bromo terephthalic acid, 4,4 '-diphenyl sulfide dioctyl phthalate), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0, 3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA)), polymerized monomer (containing bromo terephthalic acid) and polymerized monomer (4,4 '-two 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).
Embodiment 2
A kind of aromatic heterocyclic polymer resin of high-strength anti-flaming, the aromatic heterocyclic polymer resin includes with Am-Bn-CxTable The polymer chain shown, wherein A, B and C are the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B and C are with any Sequence arranges, and m, n and x are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows: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 C are as follows:Wherein, R is oxygen, sulphur Or it is not present.
The aromatic heterocyclic polymer resin is modified using inorganic filler.
The inorganic filler is at least one of sulfate, carbonate, silicate, fluosilicate and phosphate.
The sulfate is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate； The silicate is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate is calcium carbonate, magnesium carbonate and carbonic acid At least one of zinc；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphoric acid Salt is at least one of calcium phosphate, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
A kind of preparation method of the aromatic heterocyclic polymer resin of high-strength anti-flaming, in the absence of R is, with O-phthalic Acid contains phthalate bromine, 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate for reaction raw materials, and polycondensation reaction is carried out in oleum, Obtain the aromatic heterocyclic polymer resin.Polymerized monomer (phthalic acid contains phthalate bromine, 3,3'- biphenyl dicarboxylic acid), The molar ratio of hydrazine sulfate and oleum is for 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein smoke Sulfuric acid molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (phthalic acid), polymerized monomer (containing phthalate bromine) and polymerized monomer (3,3 '-connection Phthalic acid) molar ratio be (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,0.50,0.25 or 0.01).
It is reaction with phthalic acid, containing phthalate bromine, 3,3'- oxydibenzoic acid, hydrazine sulfate when R is oxygen Raw material carries out polycondensation reaction in oleum, obtains the aromatic heterocyclic polymer resin.(phthalic acid contains polymerized monomer 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 (phthalic acid), polymerized monomer (containing phthalate bromine) and polymerized monomer (3,3 '-two Phenylate 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).
When R is sulphur, with phthalic acid, be anti-containing phthalate bromine, 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate Raw material is answered, polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (phthalic acid, Containing phthalate bromine, 3,3 '-diphenyl sulfide dioctyl phthalate), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0, 3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (phthalic acid), polymerized monomer (containing phthalate bromine) and polymerized monomer (3,3 '-two 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).
Embodiment 3
A kind of aromatic heterocyclic polymer resin of high-strength anti-flaming, the aromatic heterocyclic polymer resin includes with Am-Bn-CxTable The polymer chain shown, wherein A, B and C are the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B and C are with any Sequence arranges, and m, n and x are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows: 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 C are as follows: Wherein, R is oxygen, sulphur or is not present.
The aromatic heterocyclic polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber At least one of the short fine, silicone of dimension, glass fibre, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
A kind of preparation method of the aromatic heterocyclic polymer resin of high-strength anti-flaming, in the absence of R is, with terephthalic acid (TPA) With phthalic acid, containing bromo terephthalic acid and containing phthalate bromine, 4,4'- biphenyl dicarboxylic acid and 3,3'- biphenyl dicarboxylic 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 contain bromo terephthalic acid and contain phthalate bromine, 4,4'- biphenyl dicarboxylic 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 with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and phthalic acid), polymerized monomer (contain bromo terephthalic acid and brominated neighbour Phthalic acid) with the molar ratio of polymerized monomer (4,4 '-biphenyl dicarboxylic acids 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): (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 containing bromo terephthalic acid and containing phthalate bromine 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 '-biphenyl dicarboxylic acids 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).
When R is oxygen, with terephthalic acid (TPA) and phthalic acid, contains bromo terephthalic acid and contains phthalate bromine, 4, 4'- oxydibenzoic acid and 3,3'- oxydibenzoic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, Obtain the aromatic heterocyclic polymer resin.Polymerized monomer (terephthalic acid (TPA) and phthalic acid, containing bromo terephthalic acid and brominated Phthalic acid, 4,4 '-oxydibenzoic acids and 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 oleum3Mole Number meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and phthalic acid), polymerized monomer (contain bromo terephthalic acid and brominated neighbour Phthalic acid) with the molar ratio of polymerized monomer (4,4 '-oxydibenzoic acids 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): (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 containing bromo terephthalic acid and containing phthalate bromine 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'- oxydibenzoic acids and 3,3'- diphenyl ether two The molar ratio of formic acid is (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
When R is sulphur, with terephthalic acid (TPA) and phthalic acid, contains bromo terephthalic acid and contains phthalate bromine, 4, 4'- diphenyl sulfide dioctyl phthalate and 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation is carried out in oleum Reaction, obtains the aromatic heterocyclic polymer resin.(terephthalic acid (TPA) and phthalic acid contain bromo terephthalic acid to polymerized monomer With contain phthalate bromine, 4,4 '-diphenyl sulfide dioctyl phthalate and 3,3 '-diphenyl sulfide dioctyl phthalate), hydrazine sulfate and oleum Molar ratio is for 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity is with oleum SO in acid3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and phthalic acid), polymerized monomer (contain bromo terephthalic acid and brominated neighbour Phthalic acid) with the molar ratio of polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate and 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)。
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 containing bromo terephthalic acid and containing phthalate bromine 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'- diphenyl sulfide dioctyl phthalate and 3,3'- diphenyl sulfide The molar ratio of ether 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 of the aromatic heterocyclic polymer resin of high-strength anti-flaming, the aromatic heterocyclic polymer resin are applied to fibre Dimension.
Embodiment 5
A kind of application of the aromatic heterocyclic polymer resin of high-strength anti-flaming, the aromatic heterocyclic polymer resin are applied to thin 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 89.5-92.1MPa, longitudinal tensile strength can achieve 147.4-155.4MPa, and limit oxygen index can achieve 39.8- 43.6%, thermal decomposition temperature can achieve 460-472 DEG C, and vertical thermal conductivity can achieve 37.1-57.2W/m-K, and level is led Hot coefficient can achieve 1150-1330W/m-K, intensity with higher and limit oxygen index, excellent fireproof performance, heat-resisting and lead Hot property is excellent, can increase carbon element content, can be used for preparing graphitization heat sink material.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way, Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.

Claims (10)

1. a kind of aromatic heterocyclic polymer resin of high-strength anti-flaming, it is characterised in that: the aromatic heterocyclic polymer resin include with Am-Bn-CxThe polymer chain of expression, wherein A, B and C are the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B It is arranged with C with random order, m, n and x are positive integer；
The structural formula of the repetitive unit A are as follows:And/orIt is described The structural formula of repetitive unit B are as follows:And/orWherein, R1, R2, R3 and R4 is 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 C are as follows:And/orWherein, R is oxygen, sulphur or is not present.
2. a kind of aromatic heterocyclic polymer resin of high-strength anti-flaming according to claim 1, it is characterised in that: the virtue is miscellaneous Cyclopolymer resin is modified using inorganic filler.
3. a kind of aromatic heterocyclic polymer resin of high-strength anti-flaming according to claim 2, it is characterised in that: described inorganic Filler is mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide, oxide, sulfate, carbonate, silicic acid At least one of salt, fluosilicate and phosphate.
4. a kind of aromatic heterocyclic polymer resin of high-strength anti-flaming according to claim 3, it is characterised in that: the nitridation Object is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxide is calcium oxide, oxidation At least one of zinc, magnesia, iron oxide, silica and titanium dioxide.
5. a kind of aromatic heterocyclic polymer resin of high-strength anti-flaming according to claim 4, it is characterised in that: the dioxy SiClx is nano silica, and the titanium dioxide is nano-titanium dioxide.
6. a kind of aromatic heterocyclic polymer resin of high-strength anti-flaming according to claim 3, it is characterised in that: the sulfuric acid Salt is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate；The silicate is silicic acid At least one of sodium, alumina silicate and magnesium silicate；The carbonate is at least one of calcium carbonate, magnesium carbonate and zinc carbonate； The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphate is calcium phosphate, phosphoric acid At least one of hydrogen calcium, magnesium phosphate and magnesium monohydrogen phosphate.
7. a kind of aromatic heterocyclic polymer resin of high-strength anti-flaming according to claim 1, it is characterised in that: the virtue is miscellaneous Cyclopolymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber, glass fibre, aramid fiber At least one of the short fine, silicone of pulp, aramid fiber and polytetrafluoroethylene (PTFE).
8. such as a kind of described in any item preparation methods of the aromatic heterocyclic polymer resin of high-strength anti-flaming of claim 1-7, It is characterized in that: in the absence of R is, with terephthalic acid (TPA) and/or phthalic acid, containing bromo terephthalic acid and/or brominated neighbour Phthalic acid, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate be reaction raw materials, in oleum into Row polycondensation reaction obtains the aromatic heterocyclic polymer resin；
When R is oxygen, with terephthalic acid (TPA) and/or phthalic acid, containing bromo terephthalic acid and/or containing phthalate bromine, 4,4'- oxydibenzoic acids and/or 3,3'- oxydibenzoic acid, hydrazine sulfate are reaction raw materials, and polycondensation is carried out in oleum Reaction, obtains the aromatic heterocyclic polymer resin；
When R is sulphur, with terephthalic acid (TPA) and/or phthalic acid, 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, are carried out in oleum Polycondensation reaction obtains the aromatic heterocyclic polymer resin.
9. such as a kind of described in any item applications of the aromatic heterocyclic polymer resin of high-strength anti-flaming of claim 1-7, feature Be: the aromatic heterocyclic polymer resin is applied to fiber or film.
10. a kind of application of the aromatic heterocyclic polymer resin of high-strength anti-flaming according to claim 9, it is characterised in that: The film be 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.
CN201811148705.2A 2018-09-29 2018-09-29 A kind of aromatic heterocyclic polymer resin of high-strength anti-flaming and preparation method thereof and application in fiber or film Withdrawn CN109293899A (en)

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WO2007133409A2 (en) * 2006-05-01 2007-11-22 E. I. Du Pont De Nemours And Company Two step preparation of random polyoxadiazole copolymer and articles resulting therefrom
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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: 20190201