CN109280382A - A kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant and preparation method thereof and application in fiber or film - Google Patents

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

Info

Publication number
CN109280382A
CN109280382A CN201811148676.XA CN201811148676A CN109280382A CN 109280382 A CN109280382 A CN 109280382A CN 201811148676 A CN201811148676 A CN 201811148676A CN 109280382 A CN109280382 A CN 109280382A
Authority
CN
China
Prior art keywords
aromatic heterocyclic
polymer resin
fluorine
dioctyl phthalate
heterocyclic polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201811148676.XA
Other languages
Chinese (zh)
Inventor
王庭辉
刘文熙
潘鑫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201811148676.XA priority Critical patent/CN109280382A/en
Publication of CN109280382A publication Critical patent/CN109280382A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • 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
    • 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
    • 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
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • 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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • 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
    • C08K3/18—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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials

Abstract

The present invention relates to resin technology fields, aromatic heterocyclic polymer resin more particularly to a kind of UV resistant high transparent and fire-retardant and preparation method thereof and application in fiber or film, the aromatic heterocyclic polymer resin of the UV resistant high transparent and fire-retardant the preparation method comprises the following steps: in the absence of being as R, with azobenzene -4, 4 '-dioctyl phthalate and/or azobenzene -3, 3 '-dioctyl phthalate, 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 transparency with higher, limit oxygen index and excellent UV resistant performance of the invention, excellent fireproof performance, heating conduction is excellent, excellent combination property.

Description

A kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant and preparation method thereof With the application in fiber or film
Technical field
The present invention relates to resin technology fields, and in particular to a kind of aromatic heterocyclic polymer tree of UV resistant high transparent and fire-retardant Rouge and preparation method thereof and application in fiber or film.
Background technique
In heterocyclic compound cyclic organic compounds, constitute there are also other atomic time outside the atom carbon atom of ring, it is this kind of Cyclic organic compounds are called heterocyclic compound, and non-carbon is known as hetero atom.The most common hetero atom is oxygen and sulphur, on heterocycle Can have a hetero atom, can also there are two or more hetero atom, hetero atom can be a kind of atom, be also possible to two kinds Different atoms.As cycloalkane, heterocycle can also be divided into alicyclic heterocyclic and heteroaromatic two major classes.In general, heteroaromatic Ring system has a degree of stability and armaticity, and in general chemical reaction, ring is not easily broken.Part heteroaromatic can gather Synthetic macromolecule resin has extensive potential using value due to its unique excellent performance.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, it is high that the purpose of the present invention is to provide a kind of UV resistants The aromatic heterocyclic polymer resin of transparent flame-retarding, the aromatic heterocyclic polymer resin transparency with higher, limit oxygen index and excellent Different UV resistant performance, excellent fireproof performance, heating conduction is excellent, can increase carbon element content, can be used for preparing graphite Change heat sink material, also there is good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special electric conductivity And the performances such as electroluminescent, excellent combination property.
It is another object of the present invention to provide a kind of aromatic heterocyclic polymer resins of UV resistant high transparent and fire-retardant Preparation method, the preparation method step is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, can be big Scale industrial production.
Another purpose of the invention is that a kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant is provided Using.
The purpose of the invention is achieved by the following technical solution: a kind of aromatic heterocyclic polymer of UV resistant high transparent and fire-retardant Resin, the aromatic heterocyclic polymer resin includes with Am-Bn-Cx-DyThe polymer chain of expression, wherein A, B, C and D are 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: 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 is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate；The silicic acid Salt is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate be calcium carbonate, magnesium carbonate and zinc carbonate in extremely Few one kind；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphate is phosphoric acid At least one of calcium, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
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 of UV resistant high transparent and fire-retardant The preparation method of fluoropolymer resin, in the absence of R is, with 3,3 '-diformazan of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene- Sour, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid 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, is obtained The aromatic heterocyclic polymer resin.
It is (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, fluorine-containing to benzene two specifically, polymerized monomer Formic acid and/or fluorine-containing phthalic acid, containing bromo terephthalic acid and/or containing phthalate bromine, 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 (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -), polymerized monomer (contain Fluorine terephthalic acid (TPA) and/or fluorine-containing phthalic acid), polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) Molar ratio with polymerized monomer (4,4 '-biphenyl dicarboxylic acids and/or 3,3 '-biphenyl dicarboxylic acids) is (0.01-0.99): (0.99- 0.01): (0.99-0.01): (0.99-0.01).In order to save cost, it is preferred that polymerized monomer (4,4 '-dioctyl phthalate of azobenzene- And/or azobenzene -3,3 '-dioctyl phthalate), polymerized monomer (fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid), polymerized monomer (containing bromo terephthalic acid and/or containing phthalate bromine) and polymerized monomer (4,4 '-biphenyl dicarboxylic acids and/or 3,3 '-biphenyl two Formic acid) molar ratio be (0.70-0.97): (0.10-0.01): (0.10-0.01): (0.10-0.01).
Further, azobenzene -4, the molar ratio of 3,3 '-dioctyl phthalate of 4 '-dioctyl phthalate and azobenzene-are (0-1): (1-0), The molar ratio of fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid is (0-1): (1-0), containing bromo terephthalic acid and brominated adjacent benzene The molar ratio of dioctyl phthalate is (0-1): (1-0), and the molar ratio of 4,4 '-biphenyl dicarboxylic acids and 3,3 '-biphenyl dicarboxylic acids is (0-1): (1-0)。
A kind of preparation method of the aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant, when R is oxygen, with azo It is benzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid, brominated Terephthalic acid (TPA) and/or containing phthalate bromine, 4,4'- oxydibenzoic acid and/or 3,3'- oxydibenzoic acid, hydrazine sulfate For reaction raw materials, polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.
It is (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, fluorine-containing to benzene two specifically, polymerized monomer Formic acid and/or fluorine-containing phthalic acid contain bromo terephthalic acid and/or contain phthalate bromine, 4,4'- oxydibenzoic acid And/or 3,3'- oxydibenzoic acid), the molar ratio of hydrazine sulfate and oleum be 1:(1.01-5.0): (5-15), wherein sending out Cigarette sulfuric acid molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -), polymerized monomer (contain Fluorine terephthalic acid (TPA) and/or fluorine-containing phthalic acid), polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) Molar ratio with polymerized monomer (4,4 '-oxydibenzoic acids and/or 3,3 '-oxydibenzoic acids) is (0.01-0.99): (0.99-0.01): (0.99-0.01): (0.99-0.01).In order to save cost, it is preferred that polymerized monomer (azobenzene -4,4 ' - Dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate), it is polymerized monomer (fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid), poly- Close monomer (containing bromo terephthalic acid and/or contain phthalate bromine) with polymerized monomer (4,4 '-oxydibenzoic acids and/or 3, 3 '-oxydibenzoic acids) molar ratio be (0.70-0.97): (0.10-0.01): (0.10-0.01): (0.10-0.01).
Further, azobenzene -4, the molar ratio of 3,3 '-dioctyl phthalate of 4 '-dioctyl phthalate and azobenzene-are (0-1): (1-0), The molar ratio of fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid is (0-1): (1-0), containing bromo terephthalic acid and brominated adjacent benzene The molar ratio of dioctyl phthalate is (0-1): (1-0), and 4,4 '-oxydibenzoic acids and 3, the molar ratio of 3 '-oxydibenzoic acids is (0- 1): (1-0).
A kind of preparation method of the aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant, when R is sulphur, with azo It is benzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid, brominated Terephthalic acid (TPA) and/or containing phthalate bromine, 4,4'- diphenyl sulfide dioctyl phthalate and/or 3,3'- diphenyl sulfide dioctyl phthalate, sulphur Sour hydrazine is reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.
It is (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, fluorine-containing to benzene two specifically, polymerized monomer Formic acid and/or fluorine-containing phthalic acid contain bromo terephthalic acid and/or contain 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 (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene -), polymerized monomer (contain Fluorine terephthalic acid (TPA) and/or fluorine-containing phthalic acid), polymerized monomer (containing bromo terephthalic acid and/or contain phthalate bromine) Molar ratio with polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate and/or 3,3 '-diphenyl sulfide dioctyl phthalate) is (0.01-0.99): (0.99-0.01): (0.99-0.01): (0.99-0.01).In order to save cost, it is preferred that polymerized monomer (azobenzene -4,4 ' - Dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate), it is polymerized monomer (fluorine-containing terephthalic acid (TPA) and/or fluorine-containing phthalic acid), poly- Close 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 (0.70-0.97): (0.10-0.01): (0.10-0.01): (0.10- 0.01)。
Further, azobenzene -4, the molar ratio of 3,3 '-dioctyl phthalate of 4 '-dioctyl phthalate and azobenzene-are (0-1): (1-0), The molar ratio of fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid is (0-1): (1-0), containing bromo terephthalic acid and brominated adjacent benzene The molar ratio of dioctyl phthalate is (0-1): (1-0), 4,4 '-diphenyl sulfide dioctyl phthalate and 3, the molar ratio of 3 '-diphenyl sulfide dioctyl phthalate For (0-1): (1-0).
An also purpose of the invention is achieved through the following technical solutions: a kind of heteroaromatic of UV resistant high transparent and fire-retardant The application of fluoropolymer resin, the aromatic heterocyclic polymer resin are applied to fiber or film.
Preferably, the film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, stone Inkization heat dissipation film base material, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand Cover plate.
The beneficial effects of the present invention are: aromatic heterocyclic polymer resin transparency with higher of the invention, limit oxygen Index and excellent UV resistant performance, excellent fireproof performance, heating conduction is excellent, can increase carbon element content, can be used for Preparation graphitization heat sink material also has good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special Electric conductivity and the performances such as electroluminescent, excellent combination property.
Preparation method step of the invention is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, It can large-scale industrial production.
Application of the aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant of the invention in fiber or film.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant, the aromatic heterocyclic polymer resin include with Am-Bn-Cx-DyThe polymer chain of expression, wherein A, B, C and D are the repetitive unit for constituting polymer chain backbone, and are repeated single First A, B, C and D are arranged with random order, and m, n, x and y are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows: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:Wherein, R be oxygen, Sulphur is not present.
The aromatic heterocyclic polymer resin is modified using inorganic filler.
The inorganic filler is in mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide and oxide At least one.
The nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxidation Object is at least one of calcium oxide, zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
The silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
A kind of preparation method of the aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant, in the absence of R is, with idol Pyridine -4,4 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) containing bromo terephthalic acid, 4,4'- biphenyl dicarboxylic acid, hydrazine sulfate are that reaction is former Material, polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (azobenzene -4,4 '-two Formic acid, contains bromo terephthalic acid, 4,4'- biphenyl dicarboxylic acid at fluorine-containing terephthalic acid (TPA)), the molar ratio of hydrazine sulfate and oleum 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 SO in oleum3 Molal quantity meter.
Wherein, polymerized monomer (4,4 '-dioctyl phthalate of azobenzene -), polymerized monomer (fluorine-containing terephthalic acid (TPA)), polymerized monomer The molar ratio of (contain bromo terephthalic acid) with 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 4,4 '-dioctyl phthalate of azobenzene-, fluorine-containing terephthalic acid (TPA), contain bromo terephthalic acid, 4,4'- 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.(azobenzene -4,4 '-dioctyl phthalate, contains bromo terephthalic acid, 4,4'- diphenyl ether diformazan at fluorine-containing terephthalic acid (TPA) to polymerized monomer 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 (4,4 '-dioctyl phthalate of azobenzene -), polymerized monomer (fluorine-containing terephthalic acid (TPA)), polymerized monomer The molar ratio of (contain bromo terephthalic acid) with 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 4,4 '-dioctyl phthalate of azobenzene-, fluorine-containing terephthalic acid (TPA), contain bromo terephthalic acid, 4,4'- bis- Diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer tree Rouge.(azobenzene -4,4 '-dioctyl phthalate, contains bromo terephthalic acid, 4,4'- diphenyl sulfide two at fluorine-containing terephthalic acid (TPA) to polymerized monomer Formic 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), Middle oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (4,4 '-dioctyl phthalate of azobenzene -), polymerized monomer (fluorine-containing terephthalic acid (TPA)), polymerized monomer The molar ratio of (containing bromo terephthalic acid) and polymerized monomer (4,4 '-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): (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 UV resistant high transparent and fire-retardant, the aromatic heterocyclic polymer resin include with Am-Bn-Cx-DyThe polymer chain of expression, wherein A, B, C and D are the repetitive unit for constituting polymer chain backbone, and are repeated single First A, B, C and D are arranged with random order, and m, n, x and y are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows: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:Wherein, R is oxygen, sulphur Or it is not present.
The aromatic heterocyclic polymer resin is modified using inorganic filler.
The inorganic filler is at least one of sulfate, carbonate, silicate, fluosilicate and phosphate.
The sulfate is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate； The silicate is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate is calcium carbonate, magnesium carbonate and carbonic acid At least one of zinc；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphoric acid Salt is at least one of calcium phosphate, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
A kind of preparation method of the aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant, in the absence of R is, with idol Pyridine -3,3 '-dioctyl phthalate, fluorine-containing phthalic acid contain phthalate bromine, 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate for reaction original Material, polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (azobenzene -3,3 '-two Formic acid, contains phthalate bromine, 3,3'- biphenyl dicarboxylic acid at fluorine-containing phthalic acid), the molar ratio of hydrazine sulfate and oleum 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 SO in oleum3 Molal quantity meter.
Wherein, polymerized monomer (3,3 '-dioctyl phthalate of azobenzene -), polymerized monomer (fluorine-containing phthalic acid), polymerized monomer The molar ratio of (contain phthalate bromine) with 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 3,3 '-dioctyl phthalate of azobenzene-, fluorine-containing phthalic acid, contain phthalate bromine, 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.(azobenzene -3,3 '-dioctyl phthalate, contains phthalate bromine, 3,3'- diphenyl ether diformazan at fluorine-containing phthalic acid to polymerized monomer 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 (3,3 '-dioctyl phthalate of azobenzene -), polymerized monomer (fluorine-containing phthalic acid), polymerized monomer The molar ratio of (contain phthalate bromine) with 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 3,3 '-dioctyl phthalate of azobenzene-, fluorine-containing phthalic acid, contain phthalate bromine, 3,3'- bis- Diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer tree Rouge.(azobenzene -3,3 '-dioctyl phthalate, contains phthalate bromine, 3,3'- diphenyl sulfide two at fluorine-containing phthalic acid to polymerized monomer Formic 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), Middle oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (3,3 '-dioctyl phthalate of azobenzene -), polymerized monomer (fluorine-containing phthalic acid), polymerized monomer The molar ratio of (containing phthalate bromine) and polymerized monomer (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): (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 UV resistant high transparent and fire-retardant, the aromatic heterocyclic polymer resin include with Am-Bn-Cx-DyThe polymer chain of expression, wherein A, B, C and D are the repetitive unit for constituting polymer chain backbone, and are repeated single First A, B, C and D are arranged with random order, and m, n, x and y are positive integer；The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows:Its 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:Its 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:
Wherein, R is oxygen, sulphur or is not present.
The aromatic heterocyclic polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber At least one of the short fine, silicone of dimension, glass fibre, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
A kind of preparation method of the aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant, in the absence of R is, with idol It is pyridine -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid, brominated to benzene Dioctyl phthalate and contain phthalate bromine, 4,4'- biphenyl dicarboxylic acid and 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate be reaction raw materials, sending out Polycondensation reaction is carried out in cigarette sulfuric acid, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (azobenzene -4,4 '-dioctyl phthalate and idol Pyridine -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid contain bromo terephthalic acid and brominated O-phthalic Acid, 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 is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene -), polymerized monomer are (fluorine-containing right Phthalic acid and fluorine-containing phthalic acid), polymerized monomer (containing bromo terephthalic acid and containing phthalate bromine) and polymerized monomer The molar ratio of (4,4 '-biphenyl dicarboxylic acids and 3,3 '-biphenyl dicarboxylic acids) is (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 azobenzene -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate is (0.01,0.25,0.50,0.75 Or 0.99): (0.99,0.75,0.50,0.25 or 0.01), the molar ratio of fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid are (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01), containing bromo terephthalic acid and brominated The molar ratio of 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 4,4 '-biphenyl dicarboxylic acids and 3,3 '-biphenyl dicarboxylic acids is (0.01,0.25,0.50,0.75 or 0.99): (0.99, 0.75,0.50,0.25 or 0.01).
When R is oxygen, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene-, fluorine-containing terephthalic acid (TPA) and contain Fluorine phthalic acid contains bromo terephthalic acid and contains phthalate bromine, 4,4'- oxydibenzoic acid and 3,3'- diphenyl ether two Formic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerization (azobenzene -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid contain monomer Bromo terephthalic acid and contain phthalate bromine, 4,4'- oxydibenzoic acid and 3,3'- oxydibenzoic acid), hydrazine sulfate and hair The molar ratio of cigarette sulfuric acid is 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity With SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene -), polymerized monomer are (fluorine-containing right Phthalic acid and fluorine-containing phthalic acid), polymerized monomer (containing bromo terephthalic acid and containing phthalate bromine) and polymerized monomer The molar ratio of (4,4 '-oxydibenzoic acids and 3,3 '-oxydibenzoic acids) is (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01): (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 azobenzene -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate is (0.01,0.25,0.50,0.75 Or 0.99): (0.99,0.75,0.50,0.25 or 0.01), the molar ratio of fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid are (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01), containing bromo terephthalic acid and brominated The molar ratio of 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 4,4 '-oxydibenzoic acids and 3,3 '-oxydibenzoic acids is (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
When R is sulphur, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene-, fluorine-containing terephthalic acid (TPA) and contain Fluorine phthalic acid contains bromo terephthalic acid and contains phthalate bromine, 4,4'- diphenyl sulfide dioctyl phthalate and 3,3'- diphenyl sulfide Ether dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin. Polymerized monomer (azobenzene -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate, fluorine-containing terephthalic acid (TPA) and fluorine-containing O-phthalic Acid contains bromo terephthalic acid and contains phthalate bromine, 4,4'- diphenyl sulfide dioctyl phthalate and 3,3'- diphenyl sulfide dioctyl phthalate), 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 (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene -), polymerized monomer are (fluorine-containing right Phthalic acid and fluorine-containing phthalic acid), polymerized monomer (containing bromo terephthalic acid and containing phthalate bromine) and polymerized monomer The molar ratio of (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): (0.99,0.75, 0.50,0.25 or 0.01).
The molar ratio of azobenzene -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate is (0.01,0.25,0.50,0.75 Or 0.99): (0.99,0.75,0.50,0.25 or 0.01), the molar ratio of fluorine-containing terephthalic acid (TPA) and fluorine-containing phthalic acid are (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01), containing bromo terephthalic acid and brominated The molar ratio of 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 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).
Embodiment 4
A kind of application of the aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant, the aromatic heterocyclic polymer resin are answered For fiber.
Embodiment 5
A kind of application of the aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant, the aromatic heterocyclic polymer resin are answered For film.
The film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, graphitization heat dissipation Film base material, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand-set lid.
After tested, it can achieve using film ultraviolet degradation made from aromatic heterocyclic polymer resin of the invention 1560-1790h, transparency can achieve 85.6-90.5%, and limit oxygen index can achieve 38.8-42.6%, thermal decomposition temperature It can achieve 457-469 DEG C, vertical thermal conductivity can achieve 32.9-53.7W/m-K, and horizontal thermal conductivity factor can achieve 1070-1290W/m-K, transparency, limit oxygen index and excellent UV resistant performance with higher, excellent fireproof performance, Heat-resisting and heating conduction 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 UV resistant high transparent and fire-retardant, it is characterised in that: the aromatic heterocyclic polymer tree Rouge includes with Am-Bn-Cx-DyThe polymer chain of expression, wherein A, B, C and D are the repetitive unit for constituting polymer chain backbone, And repetitive unit A, B, C and D are arranged with random order, m, n, x and y are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B are as follows:Its 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:Its 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:
Wherein, R is oxygen, sulphur or is not present.
2. a kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant according to claim 1, it is characterised in that: The aromatic heterocyclic polymer resin is modified using inorganic filler.
3. a kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant according to claim 2, it is characterised in that: The inorganic filler is mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide, oxide, sulfate, carbonic acid At least one of salt, silicate, fluosilicate and phosphate.
4. a kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant according to claim 3, it is characterised in that: The nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxide is oxidation At least one of calcium, zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
5. a kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant according to claim 4, it is characterised in that: The silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
6. a kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant according to claim 3, it is characterised in that: The sulfate is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate；The silicic acid Salt is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate be calcium carbonate, magnesium carbonate and zinc carbonate in extremely Few one kind；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphate is phosphoric acid At least one of calcium, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
7. a kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant according to claim 1, it is characterised in that: The aromatic heterocyclic polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber, glass At least one of the short fine, silicone of fiber, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
8. such as a kind of described in any item preparations of the aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant of claim 1-7 Method, it is characterised in that: in the absence of R is, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, contain Fluorine terephthalic acid (TPA) and/or fluorine-containing phthalic acid contain bromo terephthalic acid and/or contain phthalate bromine, 4,4'- biphenyl two Formic acid and/or 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the virtue Heterocycle polymer resin；
When R be oxygen when, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, fluorine-containing terephthalic acid (TPA) and/or Fluorine-containing phthalic acid contains bromo terephthalic acid and/or contains 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 be sulphur when, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, fluorine-containing terephthalic acid (TPA) and/or Fluorine-containing phthalic acid contains bromo terephthalic acid and/or contains 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 a kind of answering for the described in any item aromatic heterocyclic polymer resins of UV resistant high transparent and fire-retardant of claim 1-7 With, it is characterised in that: the aromatic heterocyclic polymer resin is applied to fiber or film.
10. a kind of application of the aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant according to claim 9, special Sign is: the film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, graphitization heat dissipation Film base material, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand-set lid.
CN201811148676.XA 2018-09-29 2018-09-29 A kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant and preparation method thereof and application in fiber or film Withdrawn CN109280382A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811148676.XA CN109280382A (en) 2018-09-29 2018-09-29 A kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant and preparation method thereof and application in fiber or film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811148676.XA CN109280382A (en) 2018-09-29 2018-09-29 A kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant and preparation method thereof and application in fiber or film

Publications (1)

Publication Number Publication Date
CN109280382A true CN109280382A (en) 2019-01-29

Family

ID=65182712

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811148676.XA Withdrawn CN109280382A (en) 2018-09-29 2018-09-29 A kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant and preparation method thereof and application in fiber or film

Country Status (1)

Country Link
CN (1) CN109280382A (en)

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

Similar Documents

Publication Publication Date Title
CN106750438B (en) Water/oxygen barrier polymer-based composite material and preparation method and application thereof
CN104530707A (en) Crystal whisker reinforced organic silicon heat conducting material and preparation method thereof
Kumar et al. Properties and applications of polysilanes
CN104530709A (en) Metal reinforced organic silicon heat conducting material and preparation method thereof
CN109280380A (en) 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
CN109306183A (en) Fire-retardant aromatic heterocyclic polymer resin of a kind of high intensity UV resistant and preparation method thereof and application in fiber or film
CN109293897A (en) A kind of aromatic heterocyclic polymer resin of high transparent and fire-retardant and preparation method thereof and application in fiber or film
CN109320703A (en) A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant and preparation method thereof and application in fiber or film
CN109293893A (en) A kind of aromatic heterocyclic polymer resin of UV resistant high transparency and preparation method thereof and application in fiber or film
CN109280382A (en) A kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant and preparation method thereof and application in fiber or film
TW202104449A (en) Thermally conductive polymers
CN109337048A (en) A kind of aromatic heterocyclic polymer resin and preparation method thereof of high intensity UV resistant and application in fiber or film
CN109306180A (en) A kind of aromatic heterocyclic polymer resin of high transparency and preparation method thereof and application in fiber or film
CN109293891A (en) A kind of aromatic heterocyclic polymer resin of high intensity and preparation method thereof and application in fiber or film
CN109401309A (en) A kind of aromatic heterocyclic polymer resin of UV resistant high transparent and fire-retardant and preparation method thereof and application in fiber or film
CN109401306A (en) A kind of aromatic heterocyclic polymer resin and preparation method thereof and application in fiber or film
CN109293898A (en) A kind of aromatic heterocyclic polymer resin of UV resistant high transparency and preparation method thereof and application in fiber or film
CN109337050A (en) A kind of aromatic heterocyclic polymer resin of high intensity UV resistant high transparent and fire-retardant and preparation method thereof and application in fiber or film
KR20150011495A (en) Composite of graphene-polybenzoxazine, and a bipolar plate comprising the composite and a fuel cell including the bipolar plate
CN109401307A (en) A kind of aromatic heterocyclic polymer resin of high transparency and preparation method thereof and application in fiber or film
CN109293894A (en) A kind of aromatic heterocyclic polymer film and its preparation method and application of high intensity UV resistant
CN109306182A (en) 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
CN109293896A (en) A kind of aromatic heterocyclic polymer resin of UV resistant and preparation method thereof and application in fiber or film
CN109401308A (en) A kind of aromatic heterocyclic polymer resin of high transparent and fire-retardant and preparation method thereof and application in fiber or film
CN109280381A (en) A kind of fire-retardant aromatic heterocyclic polymer resin and preparation method thereof and application in fiber or film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20190129