CN109293891A - A kind of aromatic heterocyclic polymer resin of high intensity and preparation method thereof and application in fiber or film - Google Patents
A kind of aromatic heterocyclic polymer resin of high intensity and preparation method thereof and application in fiber or film Download PDFInfo
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- CN109293891A CN109293891A CN201811145159.7A CN201811145159A CN109293891A CN 109293891 A CN109293891 A CN 109293891A CN 201811145159 A CN201811145159 A CN 201811145159A CN 109293891 A CN109293891 A CN 109293891A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/125—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one oxygen atom in the ring
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/22—Molecular weight
- C08G2261/228—Polymers, i.e. more than 10 repeat units
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3222—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more oxygen atoms as the only heteroatom, e.g. furan
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/35—Macromonomers, i.e. comprising more than 10 repeat units
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- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
Abstract
The present invention relates to resin technology fields, aromatic heterocyclic polymer resin more particularly to a kind of high intensity and preparation method thereof and application in fiber or film, the aromatic heterocyclic polymer resin of the high intensity the preparation method comprises the following steps: when R be oxygen when, with terephthalic acid (TPA) and/or phthalic acid, 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 resin.Aromatic heterocyclic polymer resin intensity with higher of the invention, heating conduction is excellent, also has the performances such as good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, solvent resistance, special electric conductivity and electroluminescent, excellent combination property.
Description
Technical field
The present invention relates to resin technology fields, and in particular to a kind of aromatic heterocyclic polymer resin of high intensity and its preparation side
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 virtues of high intensity
Heterocycle polymer resin, the aromatic heterocyclic polymer resin intensity with higher, heating conduction is excellent, can increase carbon and contain
Amount, can be used for preparing graphitization heat sink material, also have good dimensional stability, heat resistance, resistance to oxidation, electrical isolation, resistance to molten
The performances such as agent, special electric conductivity and electroluminescent, excellent combination property.
It is another object of the present invention to provide a kind of preparation method of the aromatic heterocyclic polymer resin of high intensity, the systems
Preparation Method step is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low, can large-scale industry life
It produces.
Another purpose of the invention is that providing a kind of application of the aromatic heterocyclic polymer resin of high intensity.
The purpose of the invention is achieved by the following technical solution: a kind of aromatic heterocyclic polymer resin of high intensity, the virtue
Heterocycle polymer resin includes with Am-BnThe polymer chain of expression, wherein A and B is the repetition list for constituting polymer chain backbone
Member, and repetitive unit A, B are arranged with random order, m and n are positive integer；
The structural formula of the repetitive unit A are as follows:
The structural formula of the repetitive unit B 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 resin of high intensity
Preparation method, in the absence of R is, with terephthalic acid (TPA) and/or phthalic acid, 4,4'- biphenyl dicarboxylic acid and/or 3,3'-
Biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer tree
Rouge.
Specifically, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid, 4,4 '-biphenyl dicarboxylic acids 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
With SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid) and polymerized monomer (4,4 '-biphenyl dicarboxylic acids and/
Or 3,3 '-biphenyl dicarboxylic acids) molar ratio be (0.01-0.99): (0.99-0.01).In order to save cost, it is preferred that polymerization
Monomer (terephthalic acid (TPA) and/or phthalic acid) and polymerized monomer (4,4 '-biphenyl dicarboxylic acids and/or 3,3 '-biphenyl diformazans
Acid) molar ratio be (0.90-0.99): (0.10-0.01).
Further, the molar ratio of terephthalic acid (TPA) and phthalic acid is (0-1): (1-0), 4,4 '-biphenyl dicarboxylic acids
Molar ratio with 3,3 '-biphenyl dicarboxylic acids is (0-1): (1-0).
A kind of preparation method of the aromatic heterocyclic polymer resin of high intensity, when R is oxygen, with terephthalic acid (TPA) and/or neighbour
Phthalic acid, 4,4'- oxydibenzoic acid and/or 3,3'- oxydibenzoic acid, hydrazine sulfate are reaction raw materials, in oleum
Middle carry out polycondensation reaction, obtains the aromatic heterocyclic polymer resin.
Specifically, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid, 4,4 '-oxydibenzoic acids and/or 3,3 '-
Oxydibenzoic acid), the molar ratio of hydrazine sulfate and oleum be 1:(1.01-5.0): (5-15), wherein oleum mole
Number is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid) and polymerized monomer (4,4 '-oxydibenzoic acids
And/or 3,3 '-oxydibenzoic acids) molar ratio be (0.01-0.99): (0.99-0.01).In order to save cost, preferably
, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid) and polymerized monomer (4,4 '-oxydibenzoic acids and/or 3,3 '-
Oxydibenzoic acid) molar ratio be (0.90-0.99): (0.10-0.01).
Further, the molar ratio of terephthalic acid (TPA) and phthalic acid is (0-1): (1-0), 4,4'- diphenyl ether diformazans
The molar ratio of acid and 3,3'- oxydibenzoic acid is (0-1): (1-0).
A kind of preparation method of the aromatic heterocyclic polymer resin of high intensity, when R is sulphur, with terephthalic acid (TPA) and/or neighbour
Phthalic acid, 4,4'- diphenyl sulfide dioctyl phthalate and/or 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, in smoke
Polycondensation reaction is carried out in sulfuric acid, obtains the aromatic heterocyclic polymer resin.
Specifically, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid, 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
Sour molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid) and polymerized monomer (4,4 '-diphenyl sulfide diformazans
Acid and/or 3,3 '-diphenyl sulfide dioctyl phthalate) molar ratio be (0.01-0.99): (0.99-0.01).It is excellent in order to save cost
Choosing, polymerized monomer (terephthalic acid (TPA) and/or phthalic acid) and polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate and/or 3,
3 '-diphenyl sulfide dioctyl phthalate) molar ratio be (0.90-0.99): (0.10-0.01).
Further, the molar ratio of terephthalic acid (TPA) and phthalic acid is (0-1): (1-0), 4,4'- diphenyl sulfides two
The molar ratio of formic acid and 3,3'- diphenyl sulfide dioctyl phthalate is (0-1): (1-0).
Applicants have found that when using terephthalic acid (TPA) as monomer polymerization, although obtained aromatic heterocyclic polymer resin
Intensity is higher, but shrinking percentage is slightly bigger than normal, and when phthalic acid is added polymerizeing together as monomer, obtained heteroaromatic polymerization
On the basis of keeping higher-strength, shrinking percentage can be improved object tree.
An also purpose of the invention is achieved through the following technical solutions: a kind of aromatic heterocyclic polymer resin of high intensity
Using the aromatic heterocyclic polymer resin is applied to fiber or film.
Preferably, the film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, stone
Inkization heat dissipation film base material, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand
Cover plate.
The beneficial effects of the present invention are: aromatic heterocyclic polymer resin intensity with higher of the invention, heating conduction
It is excellent, carbon element content can be increased, can be used for preparing graphitization heat sink material, also there is good dimensional stability, heat-resisting
The performances such as property, resistance to oxidation, electrical isolation, solvent resistance, special electric conductivity and electroluminescent, excellent combination property.
Preparation method step of the invention is simple, convenient operation and control, and quality is stablized, and high production efficiency, production cost is low,
It can large-scale industrial production.
The application of high-intensitive aromatic heterocyclic polymer resin of the invention in fiber or film.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of aromatic heterocyclic polymer resin of high intensity, the aromatic heterocyclic polymer resin includes with Am-BnThe polymerization of expression
Object chain, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are arranged with random order, m and
N is 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, R be oxygen,
Sulphur is not present.
The aromatic heterocyclic polymer resin is modified using inorganic filler.
The inorganic filler is in mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide and oxide
At least one.
The nitride is silicon nitride and/or boron nitride；The carbide is silicon carbide and/or boron carbide；The oxidation
Object is at least one of calcium oxide, zinc oxide, magnesia, iron oxide, silica and titanium dioxide.
The silica is nano silica, and the titanium dioxide is nano-titanium dioxide.
A kind of preparation method of the aromatic heterocyclic polymer resin of high intensity, in the absence of R is, with terephthalic acid (TPA), 4,
4'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer
Resin.The molar ratio of polymerized monomer (terephthalic acid (TPA), 4,4 '-biphenyl dicarboxylic acids), 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, the molar ratio of polymerized monomer (terephthalic acid (TPA)) and 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).
When R is oxygen, with terephthalic acid (TPA), 4,4'- oxydibenzoic acid, hydrazine sulfate for reaction raw materials, in oleum
Middle carry out polycondensation reaction, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (terephthalic acid (TPA), 4,4 '-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 (terephthalic acid (TPA)) and the molar ratio of polymerized monomer (4,4 '-oxydibenzoic acid) are
(0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
When R is sulphur, with terephthalic acid (TPA) and/or phthalic acid, 4,4'- diphenyl sulfide dioctyl phthalate and/or 3,3'-
Diphenyl sulfide dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer
Resin.The molar ratio of polymerized monomer (terephthalic acid (TPA), 4,4 '-diphenyl sulfide dioctyl phthalate), hydrazine sulfate and oleum is 1:
(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity is with SO in oleum3It rubs
That number meter.
Wherein, polymerized monomer (terephthalic acid (TPA)) and the molar ratio of polymerized monomer (4,4 '-diphenyl sulfide dioctyl phthalate) are
(0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
Embodiment 2
A kind of aromatic heterocyclic polymer resin of high intensity, the aromatic heterocyclic polymer resin includes with Am-BnThe polymerization of expression
Object chain, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are arranged with random order, m and
N is 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, R is oxygen, sulphur
Or it is not present.
The aromatic heterocyclic polymer resin is modified using inorganic filler.
The inorganic filler is at least one of sulfate, carbonate, silicate, fluosilicate and phosphate.
The sulfate is at least one of calcium sulfate, magnesium sulfate, zinc sulfate, barium sulfate, ferric sulfate, ferrous sulfate；
The silicate is at least one of sodium metasilicate, alumina silicate and magnesium silicate；The carbonate is calcium carbonate, magnesium carbonate and carbonic acid
At least one of zinc；The fluosilicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphoric acid
Salt is at least one of calcium phosphate, calcium monohydrogen phosphate, magnesium phosphate and magnesium monohydrogen phosphate.
A kind of preparation method of the aromatic heterocyclic polymer resin of high intensity, in the absence of R is, with phthalic acid, 3,
3'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer
Resin.The molar ratio of polymerized monomer (phthalic acid, 3,3 '-biphenyl dicarboxylic acids), 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, the molar ratio of polymerized monomer (phthalic acid) and 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).
When R is oxygen, with phthalic acid, 3,3'- oxydibenzoic acid, hydrazine sulfate for reaction raw materials, in oleum
Middle carry out polycondensation reaction, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (phthalic acid, 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 (phthalic acid) and the molar ratio of polymerized monomer (3,3 '-oxydibenzoic acid) are
(0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
When R is sulphur, with phthalic acid, 3,3'- diphenyl sulfide dioctyl phthalate, hydrazine sulfate for reaction raw materials, in oleum
Polycondensation reaction is carried out in acid, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (phthalic acid, 3,3 '-diphenyl sulfides two
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 (phthalic acid) and the molar ratio of polymerized monomer (3,3 '-diphenyl sulfide dioctyl phthalate) are
(0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
Embodiment 3
A kind of aromatic heterocyclic polymer resin of high intensity, the aromatic heterocyclic polymer resin includes with Am-BnThe polymerization of expression
Object chain, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are arranged with random order, m and
N is 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, R is oxygen, sulphur or is not present.
The aromatic heterocyclic polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber
At least one of the short fine, silicone of dimension, glass fibre, Fanglun slurry cake, aramid fiber and polytetrafluoroethylene (PTFE).
A kind of preparation method of the aromatic heterocyclic polymer resin of high intensity, in the absence of R is, with terephthalic acid (TPA) and neighbour
Phthalic acid, 4,4'- biphenyl dicarboxylic acid and 3,3'- biphenyl dicarboxylic acid, hydrazine sulfate are reaction raw materials, are contracted in oleum
Poly- reaction, obtains the aromatic heterocyclic polymer resin.Polymerized monomer (terephthalic acid (TPA) and phthalic acid, 4,4 '-biphenyl diformazans
Acid and 3,3 '-biphenyl dicarboxylic acids), the molar ratio of hydrazine sulfate and oleum be 1:(1.01,2.0,3.0,4.0 or 5.0): (5,
8,10,12 or 15), wherein oleum molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and phthalic acid) and polymerized monomer (4,4 '-biphenyl dicarboxylic acids and 3,
3 '-biphenyl dicarboxylic acids) molar ratio be (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or
0.01)。
The molar ratio of terephthalic acid (TPA) and phthalic acid is (0.01,0.25,0.50,0.75 or 0.99): (0.99,
0.75,0.50,0.25 or 0.01), 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 terephthalic acid (TPA) and phthalic acid, 4,4'- oxydibenzoic acid and 3,3'- diphenyl ether diformazan
Acid, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin.Polymerization is single
Body (terephthalic acid (TPA) and phthalic acid, 4,4 '-oxydibenzoic acids and 3,3 '-oxydibenzoic acids), hydrazine sulfate and smoke
The molar ratio of sulfuric acid is 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum molal quantity with
SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and phthalic acid) and polymerized monomer (4,4 '-oxydibenzoic acids and 3,
3 '-oxydibenzoic acids) molar ratio be (0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or
0.01)。
The molar ratio of terephthalic acid (TPA) and phthalic acid is (0.01,0.25,0.50,0.75 or 0.99): (0.99,
0.75,0.50,0.25 or 0.01), 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 terephthalic acid (TPA) and phthalic acid, 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 (terephthalic acid (TPA) and phthalic acid, 4,4 '-diphenyl sulfide dioctyl phthalate and 3,3 '-diphenyl sulfide dioctyl phthalate), sulphur
The molar ratio of sour hydrazine and oleum is 1:(1.01,2.0,3.0,4.0 or 5.0): (5,8,10,12 or 15), wherein oleum
Sour molal quantity is with SO in oleum3Molal quantity meter.
Wherein, polymerized monomer (terephthalic acid (TPA) and phthalic acid) and 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).
The molar ratio of terephthalic acid (TPA) and phthalic acid is (0.01,0.25,0.50,0.75 or 0.99): (0.99,
0.75,0.50,0.25 or 0.01), the molar ratio of 4,4'- diphenyl sulfide dioctyl phthalate and 3,3'- diphenyl sulfide dioctyl phthalate is
(0.01,0.25,0.50,0.75 or 0.99): (0.99,0.75,0.50,0.25 or 0.01).
Embodiment 4
A kind of application of the aromatic heterocyclic polymer resin of high intensity, the aromatic heterocyclic polymer resin are applied to fiber.
Embodiment 5
A kind of application of the aromatic heterocyclic polymer resin of high intensity, the aromatic heterocyclic polymer resin are applied to film.
The film is applied to high temperature gummed tape, FPC substrate, COF substrate, FCCL substrate, carbonization film base material, graphitization heat dissipation
Film base material, high temperature dwell cuticula, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand-set lid.
After tested, it can achieve using film transverse tensile strength made from aromatic heterocyclic polymer resin of the invention
90.6-94.8MPa, longitudinal tensile strength can achieve 148.8-156.7MPa, and thermal decomposition temperature can achieve 467-478 DEG C,
Vertical thermal conductivity can achieve 37.5-57.8W/m-K, and horizontal thermal conductivity factor can achieve 1160-1380W/m-K, have compared with
High intensity, 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 high intensity, it is characterised in that: the aromatic heterocyclic polymer resin includes with Am-Bn
The polymer chain of expression, wherein A and B is the repetitive unit for constituting polymer chain backbone, and repetitive unit A, B are with any suitable
Sequence arrangement, m and n are positive integer；
The structural formula of the repetitive unit A are as follows:And/orIt is described
The structural formula of repetitive unit B are as follows:And/orWherein, R is oxygen, sulphur or is not present.
2. a kind of aromatic heterocyclic polymer resin of high intensity according to claim 1, it is characterised in that: the heteroaromatic is poly-
Polymer resin is modified using inorganic filler.
3. a kind of aromatic heterocyclic polymer resin of high intensity according to claim 2, it is characterised in that: the inorganic filler
For mica, carbon black, white carbon black, talcum powder, wollastonite, nitride, carbide, oxide, sulfate, carbonate, silicate, fluorine
At least one of silicate and phosphate.
4. a kind of aromatic heterocyclic polymer resin of high intensity 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 calcium oxide, zinc oxide, oxygen
Change at least one of magnesium, iron oxide, silica and titanium dioxide.
5. a kind of aromatic heterocyclic polymer resin of high intensity according to claim 4, it is characterised in that: the silica
For nano silica, the titanium dioxide is nano-titanium dioxide.
6. a kind of aromatic heterocyclic polymer resin of high intensity 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 silicate is sodium metasilicate, silicon
At least one of sour aluminium and magnesium silicate；The carbonate is at least one of calcium carbonate, magnesium carbonate and zinc carbonate；The fluorine
Silicate is at least one of prodan, potassium fluosilicate and magnesium fluosilicate；The phosphate be calcium phosphate, calcium monohydrogen phosphate,
At least one of magnesium phosphate and magnesium monohydrogen phosphate.
7. a kind of aromatic heterocyclic polymer resin of high intensity according to claim 1, it is characterised in that: the heteroaromatic is poly-
Polymer resin is modified using modifying agent, and the modifying agent is glass microballoon, whisker, carbon fiber, glass fibre, aramid fiber slurry
At least one of the short fine, silicone of the dregs of rice, aramid fiber and polytetrafluoroethylene (PTFE).
8. such as a kind of described in any item preparation methods of the aromatic heterocyclic polymer resin of high intensity of claim 1-7, feature
It is: in the absence of R is, with terephthalic acid (TPA) and/or phthalic acid, 4,4'- biphenyl dicarboxylic acid and/or 3,3'- biphenyl
Dioctyl phthalate, hydrazine sulfate are reaction raw materials, and polycondensation reaction is carried out in oleum, obtains the aromatic heterocyclic polymer resin；
When R is oxygen, with terephthalic acid (TPA) and/or phthalic acid, 4,4'- oxydibenzoic acid and/or 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；
When R is sulphur, with terephthalic acid (TPA) and/or phthalic acid, 4,4'- diphenyl sulfide dioctyl phthalate and/or 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.
9. such as a kind of described in any item applications of the aromatic heterocyclic polymer resin of high intensity of claim 1-7, 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 high intensity according to claim 9, it is characterised in that: described
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
Protective film, LED light bar, OLED Flexible Displays substrate, conductive film base material, high-temperature insulation film or hand-set lid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110511378A (en) * | 2019-09-04 | 2019-11-29 | 四川大学 | A kind of electrochromic material and the preparation method and application thereof |
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