CN109320703A - A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant and preparation method thereof and application in fiber or film - Google Patents
A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant and preparation method thereof and application in fiber or film Download PDFInfo
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- CN109320703A CN109320703A CN201811147854.7A CN201811147854A CN109320703A CN 109320703 A CN109320703 A CN 109320703A CN 201811147854 A CN201811147854 A CN 201811147854A CN 109320703 A CN109320703 A CN 109320703A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
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- 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
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The present invention relates to resin technology fields, more particularly to a kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant and preparation method thereof and in the application of fiber or film, the fire-retardant aromatic heterocyclic polymer resin of the UV resistant 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, 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 of the invention has excellent UV resistant performance and higher limit oxygen index, excellent fireproof performance, heating conduction is excellent, also there is 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
Technical field
The present invention relates to resin technology fields, and in particular to a kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant and its
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 resistances of UV resistant
There is excellent UV resistant performance and higher limit oxygen to refer to for the aromatic heterocyclic polymer resin of combustion, the aromatic heterocyclic polymer resin
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.
It is another object of the present invention to provide a kind of preparation sides of aromatic heterocyclic polymer resin that UV resistant is fire-retardant
Method, 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
Industrial production.
Another purpose of the invention is that providing a kind of application of aromatic heterocyclic polymer resin that UV resistant is fire-retardant.
The purpose of the invention is achieved by the following technical solution: a kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant,
The aromatic heterocyclic polymer resin includes with Am-Bn-CxThe polymer chain of expression, wherein A, B and C are to constitute polymer chain master
The repetitive unit of chain, and repetitive unit A, B and C are arranged with random order, 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 take
The bromine in generation, 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 that UV resistant is fire-retardant
The preparation method of resin, in the absence of R is, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, brominated
Terephthalic acid (TPA) and/or be anti-containing phthalate bromine, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate
Raw material is answered, 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-, brominated to benzene two specifically, polymerized monomer
Formic acid and/or contain phthalate bromine, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- biphenyl dicarboxylic acid), hydrazine sulfate and oleum
Molar ratio 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
Bromo terephthalic acid and/or contain phthalate bromine) with polymerized monomer (4,4 '-biphenyl dicarboxylic acids and/or 3,3 '-biphenyl diformazans
Acid) molar ratio be (0.01-0.99): (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), polymerized monomer are (containing bromo terephthalic acid and/or brominated
Phthalic acid) it with the molar ratio of polymerized monomer (4,4 '-biphenyl dicarboxylic acids and/or 3,3 '-biphenyl dicarboxylic acids) is (0.80-
0.98): (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),
Molar ratio containing bromo terephthalic acid and containing phthalate bromine is (0-1): (1-0), 4,4 '-biphenyl dicarboxylic acids and 3,3 '-connection
The molar ratio of phthalic acid is (0-1): (1-0).
A kind of preparation method for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant, when R is oxygen, with azobenzene -4,4 ' -
Dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate contain bromo terephthalic acid and/or contain phthalate bromine, 4,4'- diphenyl ether two
Formic acid and/or 3,3'- oxydibenzoic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, are obtained described
Aromatic heterocyclic polymer resin.
It is (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, brominated to benzene two specifically, polymerized monomer
Formic acid and/or contain phthalate bromine, 4,4 '-oxydibenzoic acids and/or 3,3 '-oxydibenzoic acids), hydrazine sulfate and smoke
The molar ratio of sulfuric acid is 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
Bromo terephthalic acid and/or contain phthalate bromine) with polymerized monomer (4,4 '-oxydibenzoic acids and/or 3,3 '-diphenyl ether
Dioctyl phthalate) molar ratio be (0.01-0.99): (0.99-0.01): (0.99-0.01).In order to save cost, it is preferred that polymerization
Monomer (azobenzene -4,4 '-dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate), 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
(0.80-0.98): (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),
Molar ratio containing bromo terephthalic acid and containing phthalate bromine is (0-1): (1-0), 4,4'- oxydibenzoic acids and 3,3'-
The molar ratio of oxydibenzoic acid is (0-1): (1-0).
A kind of preparation method for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant, when R is sulphur, with azobenzene -4,4 ' -
Dioctyl phthalate and/or azobenzene -3,3 '-dioctyl phthalate contain bromo terephthalic acid and/or contain phthalate bromine, 4,4'- diphenyl sulfide
Dioctyl phthalate and/or 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, is obtained
The aromatic heterocyclic polymer resin.
It is (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, brominated to benzene two specifically, polymerized monomer
Formic acid and/or contain phthalate bromine, 4,4 '-diphenyl sulfide dioctyl phthalate and/or 3,3 '-diphenyl sulfide dioctyl phthalate), hydrazine sulfate and
The molar ratio of oleum is 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
Bromo terephthalic acid and/or contain phthalate bromine) with polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate and/or 3,3 '-hexichol
Thioether dioctyl phthalate) molar ratio be (0.01-0.99): (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), polymerized monomer (contain bromo terephthalic acid
And/or contain phthalate bromine) and polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate and/or 3,3 '-diphenyl sulfide dioctyl phthalate)
Molar ratio is (0.80-0.98): (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),
Molar ratio containing bromo terephthalic acid and containing phthalate bromine is (0-1): (1-0), 4,4'- diphenyl sulfide dioctyl phthalate and 3,
The molar ratio of 3'- diphenyl sulfide dioctyl phthalate is (0-1): (1-0).
An also purpose of the invention is achieved through the following technical solutions: a kind of aromatic heterocyclic polymer that UV resistant is fire-retardant
The application of 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 of the invention have excellent UV resistant performance and
Higher limit oxygen index, 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.
Preparation method step of the invention is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low,
It can large-scale industrial production.
Application of the fire-retardant aromatic heterocyclic polymer resin of UV resistant of the invention in fiber or film.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant, the aromatic heterocyclic polymer resin includes with Am-Bn-Cx
The polymer chain of expression, wherein A, B and C are the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B and C are to appoint
Meaning 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 for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant, in the absence of R is, with azobenzene-
4,4 '-dioctyl phthalate, containing bromo terephthalic acid, 4,4'- biphenyl dicarboxylic acid, hydrazine sulfate be reaction raw materials, carried out in oleum
Polycondensation reaction obtains the aromatic heterocyclic polymer resin.Polymerized monomer (azobenzene -4,4 '-dioctyl phthalate, containing bromo terephthalic acid,
4,4'- biphenyl dicarboxylic acid), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,
12 or 15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (4,4 '-dioctyl phthalate of azobenzene -), polymerized monomer (containing bromo terephthalic acid) and polymerized monomer
The molar ratio of (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).
When R is oxygen, with 4,4 '-dioctyl phthalate of azobenzene-, contain bromo terephthalic acid, 4,4'- oxydibenzoic acid, sulfuric acid
Hydrazine is reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (azo
Benzene -4,4 '-dioctyl phthalate contains 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 oleum3Mole
Number meter.
Wherein, polymerized monomer (4,4 '-dioctyl phthalate of azobenzene -), polymerized monomer (containing bromo terephthalic acid) and polymerized monomer
The molar ratio of (4,4 '-oxydibenzoic acid) 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).
When R is sulphur, with 4,4 '-dioctyl phthalate of azobenzene-, contain bromo terephthalic acid, 4,4'- 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.Polymerized monomer is (even
Pyridine -4,4 '-dioctyl phthalate contains bromo terephthalic acid, 4,4 '-diphenyl sulfide dioctyl phthalate), 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 (containing bromo terephthalic acid) and polymerized monomer
The molar ratio of (4,4 '-diphenyl sulfide dioctyl phthalate) be (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,
0.25 or 0.01): (0.99,0.75,0.50,0.25 or 0.01).
Embodiment 2
A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant, the aromatic heterocyclic polymer resin includes with Am-Bn-Cx
The polymer chain of expression, wherein A, B and C are the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B and C are to appoint
Meaning 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 for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant, in the absence of R is, with azobenzene-
3,3 '-dioctyl phthalate contain phthalate bromine, 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate for reaction raw materials, carry out in oleum
Polycondensation reaction obtains the aromatic heterocyclic polymer resin.Polymerized monomer (azobenzene -3,3 '-dioctyl phthalate, containing phthalate bromine,
3,3'- biphenyl dicarboxylic acid), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,
12 or 15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (3,3 '-dioctyl phthalate of azobenzene -), polymerized monomer (containing phthalate bromine) and polymerized monomer
The molar ratio of (4 3,3 '-biphenyl dicarboxylic acid) 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).
When R is oxygen, with 3,3 '-dioctyl phthalate of azobenzene-, contain phthalate bromine, 3,3'- oxydibenzoic acid, sulfuric acid
Hydrazine is reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (azo
Benzene -3,3 '-dioctyl phthalate contains 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 oleum3Mole
Number meter.
Wherein, polymerized monomer (3,3 '-dioctyl phthalate of azobenzene -), polymerized monomer (containing phthalate bromine) and polymerized monomer
The molar ratio of (3,3 '-oxydibenzoic acid) 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).
When R is sulphur, with 3,3 '-dioctyl phthalate of azobenzene-, contain phthalate bromine, 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.Polymerized monomer is (even
Pyridine -3,3 '-dioctyl phthalate contains phthalate bromine, 3,3 '-diphenyl sulfide dioctyl phthalate), 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 (containing phthalate bromine) and polymerized monomer
The molar ratio of (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).
Embodiment 3
A kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant, the aromatic heterocyclic polymer resin includes with Am-Bn-Cx
The polymer chain of expression, wherein A, B and C are the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B and C are to appoint
Meaning 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:Its
In, R1, R2, R3 and R4 are unsubstituted or substituted bromine, and at least one in R1, R2, R3 and R4 is the bromine replaced；
The structural formula of the repetitive unit 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 for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant, in the absence of R is, with azobenzene-
4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate contain bromo terephthalic acid and contain phthalate bromine, 4,4'- biphenyl diformazan
Acid and 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the heteroaromatic
Fluoropolymer resin.(azobenzene -4,4 '-dioctyl phthalate and azobenzene -3,3 '-dioctyl phthalate containing bromo terephthalic acid and contain polymerized monomer
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 is with SO in oleum3Mole
Number meter.
Wherein, polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene -), polymerized monomer are (brominated right
Phthalic acid and contain phthalate bromine) with the molar ratio of polymerized monomer (4,4 '-biphenyl dicarboxylic acids and 3,3 '-biphenyl dicarboxylic acids)
For (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 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 containing bromo terephthalic acid and containing phthalate bromine are
(0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01), 4,4 '-biphenyl dicarboxylic acids and 3,
The molar ratio of 3 '-biphenyl dicarboxylic acids be (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or
0.01)。
When R is oxygen, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene-, containing bromo terephthalic acid and contain
Phthalate bromine, 4,4'- oxydibenzoic acid and 3,3'- oxydibenzoic acid, hydrazine sulfate are reaction raw materials, in oleum
Middle carry out polycondensation reaction, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (azobenzene -4,4 '-dioctyl phthalate and azobenzene -
3,3 '-dioctyl phthalate contain bromo terephthalic acid and contain phthalate bromine, 4,4 '-oxydibenzoic acids and 3,3 '-diphenyl ether diformazans
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 (brominated right
Phthalic acid and contain phthalate bromine) rub with polymerized monomer (4,4 '-oxydibenzoic acids and 3,3 '-oxydibenzoic acids)
You than 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 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 containing bromo terephthalic acid and containing phthalate bromine are
(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,
The molar ratio of 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)。
When R is sulphur, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene-, containing bromo terephthalic acid and contain
Phthalate bromine, 4,4'- diphenyl sulfide dioctyl phthalate and 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, in smoke
Polycondensation reaction is carried out in sulfuric acid, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (azobenzene -4,4 '-dioctyl phthalate and azo
Benzene -3,3 '-dioctyl phthalate contains bromo terephthalic acid and contains phthalate bromine, 4,4 '-diphenyl sulfide dioctyl phthalate and 3,3 '-hexichol
Thioether dioctyl phthalate), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or
15), wherein oleum molal quantity with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and azobenzene -), polymerized monomer are (brominated right
Phthalic acid and contain phthalate bromine) with polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate and 3,3 '-diphenyl sulfide dioctyl phthalate)
Molar ratio be (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01): (0.99,0.75,
0.50,0.25 or 0.01).
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 containing bromo terephthalic acid and containing phthalate bromine are
(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
The molar ratio of 3,3'- diphenyl sulfide dioctyl phthalate is (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25
Or 0.01).
Embodiment 4
A kind of application for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant, the aromatic heterocyclic polymer resin are applied to fibre
Dimension.
Embodiment 5
A kind of application for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant, 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 ultraviolet degradation made from aromatic heterocyclic polymer resin of the invention
1630-1850h, limit oxygen index can achieve 39.4-43.2%, and thermal decomposition temperature can achieve 462-471 DEG C, vertical heat transfer
Coefficient can achieve 36.8-55.7W/m-K, and horizontal thermal conductivity factor can achieve 1110-1340W/m-K, have excellent resistance to purple
Outside line performance and higher limit oxygen index, excellent fireproof performance, heat-resisting and heating conduction is excellent, can increase carbon and contain
Amount, can be used for preparing graphitization heat sink material.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way,
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of aromatic heterocyclic polymer resin that UV resistant is fire-retardant, it is characterised in that: the aromatic heterocyclic polymer resin includes
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 and C are arranged with random order, and m, n and x are positive integer；
The structural formula of the repetitive unit A are as follows:And/or
The structural formula of the repetitive unit B are as follows:And/orIts
In, R1, R2, R3 and R4 are unsubstituted or substituted 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 fire-retardant aromatic heterocyclic polymer resin of UV resistant according to claim 1, it is characterised in that: the virtue
Heterocycle polymer resin is modified using inorganic filler.
3. a kind of fire-retardant aromatic heterocyclic polymer resin of UV resistant according to claim 2, it is characterised in that: the nothing
Machine filler is mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide, oxide, sulfate, carbonate, silicon
At least one of hydrochlorate, fluosilicate and phosphate.
4. a kind of fire-retardant aromatic heterocyclic polymer resin of UV resistant according to claim 3, it is characterised in that: the nitrogen
Compound 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 fire-retardant aromatic heterocyclic polymer resin of UV resistant according to claim 4, it is characterised in that: described two
Silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
6. a kind of fire-retardant aromatic heterocyclic polymer resin of UV resistant according to claim 3, it is characterised in that: the sulphur
Hydrochlorate is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate；The silicate is silicon
At least one of sour sodium, alumina silicate and magnesium silicate；The carbonate is at least one in calcium carbonate, magnesium carbonate and zinc carbonate
Kind；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphate be calcium phosphate,
At least one of calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
7. a kind of fire-retardant aromatic heterocyclic polymer resin of UV resistant according to claim 1, it is characterised in that: the virtue
Heterocycle polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber, glass fibre, virtue
At least one of the short fine, silicone of synthetic fibre pulp, aramid fiber and polytetrafluoroethylene (PTFE).
8. such as a kind of described in any item preparation methods for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant of claim 1-7,
It is characterized by: in the absence of being as R, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, brominated to benzene
Dioctyl phthalate and/or be that reaction is former containing phthalate bromine, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate
Material, polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin；
When R is oxygen, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, containing bromo terephthalic acid and/or
Containing phthalate bromine, 4,4'- oxydibenzoic acid and/or 3,3'- oxydibenzoic acid, hydrazine sulfate are reaction raw materials, are being sent out
Polycondensation reaction is carried out in cigarette sulfuric acid, obtains the aromatic heterocyclic polymer resin；
When R is sulphur, with 3,3 '-dioctyl phthalate of 4,4 '-dioctyl phthalate of azobenzene-and/or azobenzene-, containing bromo terephthalic acid and/or
Containing phthalate bromine, 4,4'- diphenyl sulfide dioctyl phthalate and/or 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials,
Polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.
9. special such as a kind of described in any item applications for the aromatic heterocyclic polymer resin that UV resistant is fire-retardant of claim 1-7
Sign is: the aromatic heterocyclic polymer resin is applied to fiber or film.
10. a kind of application of the fire-retardant aromatic heterocyclic polymer resin of UV resistant according to claim 9, feature exist
In: 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.
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| CN112908542A (en) * | 2021-02-06 | 2021-06-04 | 全通电缆股份有限公司 | Fireproof flame-retardant cable and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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2018
- 2018-09-29 CN CN201811147854.7A patent/CN109320703A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112908542A (en) * | 2021-02-06 | 2021-06-04 | 全通电缆股份有限公司 | Fireproof flame-retardant cable and preparation method thereof |
| CN112908542B (en) * | 2021-02-06 | 2022-02-15 | 全通电缆股份有限公司 | Fireproof flame-retardant cable and preparation method thereof |
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