CN106700065A - Method for preparing heterocyclic aramid solution - Google Patents
Method for preparing heterocyclic aramid solution Download PDFInfo
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- CN106700065A CN106700065A CN201710065110.XA CN201710065110A CN106700065A CN 106700065 A CN106700065 A CN 106700065A CN 201710065110 A CN201710065110 A CN 201710065110A CN 106700065 A CN106700065 A CN 106700065A
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- aramid fiber
- heterocycle aramid
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- diamines
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- GNOIPBMMFNIUFM-UHFFFAOYSA-N CN(C)P(N(C)C)(N(C)C)=O Chemical compound CN(C)P(N(C)C)(N(C)C)=O GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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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
- D01F13/00—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like
- D01F13/04—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like of synthetic polymers
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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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
- D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
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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
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
- D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
Abstract
The invention belongs to the technical fields of heterocyclic aramid solution and preparation thereof, and specifically, relates to a method for preparing a heterocyclic aramid solution, wherein the method comprises the steps: a diamine substance and an aromatic dicarbonyl chloride are subjected to a polymerization reaction in an inert gas atmosphere and in a hexamethylphosphoric triamide solution containing no cosolvent, wherein the diamine substance comprises 2-(4-aminophenyl)-5-aminobenzimidazole.
Description
Technical field
The invention belongs to heterocycle aramid fiber solution and its preparing technical field, in particular to a kind of heterocycle aramid fiber solution
Preparation method.
Background technology
Heterocyclic Aramid Fibre belongs to the organic fiber of high strength and modulus, its mechanical property and its composite performance with resin
All it is higher than traditional aramid fiber II fibers (the Kevlar fibers of Du Pont).It has been widely used in ballistic-resistant article, special protecting clothing
The field such as dress and electronic equipment, the composite that it is made with resin has also applied the fields such as Aero-Space, defence and military.Tradition
Heterocycle aramid fiber be by paraphthaloyl chloride, p-phenylenediamine and its Third monomer【2- (4- aminophenyls) -5- amino benzo miaows
Azoles】Heterocycle aramid fiber solution is obtained using solution polycondensation, then height directly can be obtained by heat treatment/hot-stretch after wet spinning
The heterocycle aramid fiber finished silk of intensity high-modulus；Or heterocycle aramid fiber solution is separated out in water form resin, then dense
Liquid crystal is configured in sulfuric acid, using with Kevlar fibers same process carrying out spinning and be thermally treated resulting in heterocycle aramid fiber finished silk.
No matter however, which kind of technique to prepare Heterocyclic Aramid Fibre using, being required for molten in synthesizing heterocyclic aramid fiber solution
The cosolvent (such as calcium chloride, lithium chloride) of inorganic salts is added in agent.It is used to have for example in the A of patent CN 103764720
Machine solvent is N- dimethylacetylamides or METHYLPYRROLIDONE, uses cosolvent to be then respectively calcium chloride and chlorination
Lithium；In patent US20100029159, organic solvent used by synthesizing heterocyclic aramid fiber is N- dimethylacetylamides, N- dimethyl methyls
Acid amides, METHYLPYRROLIDONE or dimethyl-imidazolinone, inorganic salts cosolvent used be calcium chloride and lithium chloride, and
The consumption of inorganic salts is the 3%~10% of organic solvent mass fraction.The addition of inorganic salts can bring several shortcomings, and first is to increase
Addition sheet, including inorganic salts cost, the increased process cost of the power consumption of final wash inorganic salts and recovery inorganic salts institute in itself
Deng；Second is that inorganic salts can cause certain corrosion to equipment.3rd, inorganic salts in process of setting and water-washing process, from fibre
When dimension macromolecular chain diffusion inside is to outside, some holes will necessarily be left, this can cause the decline of fibrous mechanical property；Such as nothing
Machine salt has been remained, and during Post isothermal treatment, then can equally drop low-fiber mechanical property.Thus, can directly adopt
With a kind of organic solvent come synthesizing heterocyclic aramid fiber stosteSo as to reduces cost, the mechanical property of raising fiber.
In view of this, it is special to propose the present invention.
The content of the invention
The purpose of the present invention is directed to the deficiencies in the prior art, there is provided a kind of heterocycle aramid fiber without cosolvent inorganic salts is molten
Liquid and preparation method thereof.
In order to realize above-mentioned purpose of the invention, spy uses following technical scheme：
A kind of preparation method of heterocycle aramid fiber solution, including：Diamines material is with aromatic dimethyl chloride in inert gas
Under atmosphere, there is polymerisation in the HMPA solution for not containing cosolvent；
The Diamines material includes 2- (4- aminophenyls) -5- aminobenzimidazoles.
A kind of heterocycle aramid fiber solution without cosolvent inorganic salts that the present invention is provided and preparation method thereof, used by the method
The chemical constitution of solvent HMPA (HMPA) is as follows：
3 N and 1 oxygen can form hydrogen bond with heterocycle aramid fiber macromolecular chain (amido link, imidazole ring) in one HMPA
Interact, thus with 4 hydrogen bond receptor points, far above traditional N- dimethylacetylamides, dinethylformamide, N- first
Base -2-Pyrrolidone polar aprotic solvent.Thus effectively heterocycle aramid fiber macromolecular chain " separation " can be opened so that heterocycle
Aramid fiber is dissolved in HMPA.And N- dimethylacetylamides, dinethylformamide, METHYLPYRROLIDONE etc. tradition are molten
Agent does not possess the ability then, it is necessary to add inorganic salts to aid in dissolving.
Moisture is 50~500ppm in wherein HMPA, and moisture is preferably 150~300ppm.Resulting heterocycle virtue
Synthetic fibre glue mass fraction is 5%~8%, and the mass fraction of solvent HMPA is 92%~95%.
The intrinsic viscosity of the heterocycle aramid fiber solution prepared by this method is 8~11dL/g.The present invention is using conventional wet method
Spinning directly prepares heterocycle aramid fiber precursor, then carries out static heat treatment at 350~380 DEG C or carries out heat at 360~400 DEG C
Stretching obtains heterocycle aramid fiber finished silk.Or by heterocycle aramid fiber solution with water precipitating process, after be configured to concentrated sulfuric acid dissolution it is molten
Liquid spinning, is that can obtain heterocycle aramid fiber precursor using conventional dry-jet wet spinning (consistent with Kevlar spinning techniques), then
360~400 DEG C carry out hot-stretch and obtain heterocycle aramid fiber finished silk.Prepared heterocycle aramid fiber finished silk tensile strength 26~
33cN/dt, initial modulus is in 700~1100cN/dt.
Diamine monomer is 2-'s (4- aminophenyls) -5- aminobenzimidazoles (PABZ) wherein used in synthesizing heterocyclic aramid fiber
Chemical constitution is as follows：
Preferably, the preparation method of heterocycle aramid fiber solution as described above, the inert gas is nitrogen, helium, argon gas
In one kind.
Preferably, the preparation method of heterocycle aramid fiber solution as described above, the aromatic dimethyl chloride is phenyl-diformyl
Chlorine and/or biphenyl dimethyl chloride (BPC).
" virtue " or " aryl " refers to aromatic hydrocarbon ring system in the present invention.Aryl is single loop system or bicyclic system.It is single
Cyclophane basic ring refers to phenyl.Bicyclic aryl ring refer to two phenyl ring be joined directly together (biphenyl) or two phenyl ring by one its
Its group or atom bridging.Also include in addition to containing a phenyl ring or two heteroaryls of phenyl ring, containing 1~5, suitably 1~
4th, more suitably 1 or 2 hetero atom as the member atoms in ring aromatic rings.Can containing more than one heteroatomic heteroaryl
To contain different hetero atoms.Heteroaryl can alternatively be replaced by one or more substitution base as defined herein.Heteroaryl
It is single loop system or fused ring bicyclic system.Bicyclic heteroaryl ring has 5-6 member atoms.Bicyclic heteroaryl ring has 8-10
Member atoms.Bicyclic heteroaryl ring includes wherein main hetero-aromatic ring and secondary monocyclic cycloalkyl, cycloalkenyl, Heterocyclylalkyl, aryl
Or heteroaryl ring is attached those rings to form fused ring bicyclic system.Wherein, heteroaryl includes pyrrole radicals, pyrazolyl, imidazole radicals, Evil
Oxazolyl, isoxazolyl, oxadiazolyls, thiazolyl, isothiazolyl, thiadiazolyl group, furyl, furazanyl, thienyl, triazolyl,
Pyridine radicals, pyrimidine radicals, pyridazinyl, pyrazinyl, triazine radical, tetrazine base, tetrazole radical, indyl, isoindolyl, indolizine base, Yin
Diindyl oxazolyl, purine radicals, quinolyl, isoquinolyl, quinoxalinyl, quinazolyl, pteridyl, cinnolines base, benzimidazolyl, benzo
Pyranose, benzoxazolyl, benzo isoxazolyl, benzofuranyl, isobenzofuran-base, benzothiazolyl, benzisothia oxazolyl,
Benzothienyl, furopyridyl, naphthyridines base, Pyrazolopyridine base, pyrazolopyrimidine base, 3H- [1,2,3] triazol [4,
5-d] pyrimidine radicals and 3H- [1,2,3] triazol [4,5-b] pyridine radicals.
" hetero atom " refers to nitrogen, sulphur or oxygen atom.
Preferably, the preparation method of heterocycle aramid fiber solution as described above, the phthalyl chloride includes paraphenylene terephthalamide
Chlorine (TPC) and/or adjacent chlorine paraphthaloyl chloride (Cl-TPC).
Preferably, the preparation method of heterocycle aramid fiber solution as described above, also includes fragrance two in the Diamines material
Amine.
Preferably, the preparation method of heterocycle aramid fiber solution as described above, the phenyl ring number of the aromatic diamines is 1 or 2
It is individual.
Preferably, the preparation method of heterocycle aramid fiber solution as described above, 2- (4- the aminophenyls) -5- amino benzos
Mole percent of the imidazoles in the Diamines material is 30%~100%.
Preferably, the preparation method of heterocycle aramid fiber solution as described above, the aromatic diamines include p-phenylenediamine
(PDA), 2- (4- aminophenyls) -5- An bases benzoxazole (BOA), 4,4 ',-diaminobenzene anilid (DABA), adjacent chlorine pair
Phenylenediamine (PDA-Cl), benzidine (BZ), 3,3 '-dihydroxybiphenyl amine (DHB), 3,3 '-dimethoxy benzidine (DHO),
2,5- bis- chloro- Isosorbide-5-Nitrae phenylenediamines (DCl-PDA), 2,5- dihydroxy-Isosorbide-5-Nitrae phenylenediamine (DAR) and 2- chloro- 4,4 ' ,-diaminourea benzoyl
For one or more in aniline (DABA-Cl).
Preferably, the preparation method of heterocycle aramid fiber solution as described above, described six are dissolved into by the Diamines material
By solution temperature control at -10~10 DEG C after in methyl phosphoric triamide solution, then aromatic dimethyl chloride addition is gone forward side by side
Row reaction.
Preferably, the preparation method of heterocycle aramid fiber solution as described above, the aromatic dimethyl chloride is added at twice
Or disposable addition.
Preferably, the preparation method of heterocycle aramid fiber solution as described above, when the aromatic dimethyl chloride is added：
Addition and the 70%~90% of the Diamines material equivalent for the first time, again by temperature after reaction 10min~1h
20~50 DEG C are risen to, adds remaining aromatic dimethyl chloride to continue to react 0.5~3h；
Or；
The disposable acyl chlorides added with the Diamines material equivalent, again rises to temperature after reaction 10min~30min
20~50 DEG C, continue to react 0.5~3h.
Compared with prior art, beneficial effects of the present invention are：
3 N and 1 O can form interaction of hydrogen bond with heterocycle aramid fiber macromolecular chain in (1) HMPA, thus
With 4 hydrogen bond receptor points.Dissolving heterocycle aramid fiber ability is strong, it is not necessary to add inorganic salts as cosolvent.Obtained by simultaneously
Solid content is higher, up to 5~8%.
(2) do not use inorganic salts as cosolvent, reduce washing, reclaim the operation of inorganic salts, reduce the corrosion to equipment,
So as to cost is greatly lowered.
(3) it is to be capable of achieving HMPA recyclings using conventional extraction-rectification recovery process.And routinely containing inorganic
In the dicyandiamide solution of salt, because inorganic salts and solvent (DMAC, NMP) can form strong interaction, inorganic salts when causing to reclaim
Partial solvent can be taken away, is unfavorable for the raising of solvent recovering rate.And directly using HMPA as solvent, the rate of recovery can be higher, can
Reach 95~98%.Recovered solvent can be directly used for next polymerization, not influence polymerisation, the characteristic of resulting heterocycle aramid fiber
Viscosity number is held essentially constant.
(4) using the HMPA solvents of co-solvent, resulting heterocycle aramid fiber intrinsic viscosity is higher, can reach 8~11dL/g,
Prepared fibrous inside hole and impurity are less, cause mechanical property higher.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, are
The conventional products for obtaining can be bought by city.
1) intrinsic viscosity of heterocycle aramid fiber is tested using Ubbelohde viscometer
Test condition：Temperature is 30 ± 0.5 DEG C；With the concentrated sulfuric acid as solvent；Heterocycle aramid fiber concentration is 0.5g/dL.Ubbelohde glues
Spend a diameter of 1.1~1.2mm of meter.
Experimentation：Heterocycle aramid fiber precursor is carried out into drying and removes moisture, weigh 1.25g Fibrinolysis in the dense sulphur of 25ml
In acid, the constant temperature in Water Tank with Temp.-controlled (30 DEG C), concentrated sulfuric acid neat solvent is determined with Ubbelohde viscometer respectively and heterocycle aramid fiber/sulfuric acid is molten
Liquid flows through capillary required time t0And t.Then intrinsic viscosity is determined using " one point method "：ηr=t/t0ηsp=ηr-1[η]=[2
(ηsp-lnηr)]1/2/C
2) tensile strength and initial modulus of following examples and the heterocycle aramid fiber finished fiber obtained by comparative example are to use
Britain Instron4302 type strength testers, according to the method for ASTM D 885-2007, according to fixture spacing 215mm, fixture movement
Speed 25mm/min, simple tension test.
Embodiment 1
160 grams of PABZ are added in the HMPA solvents of 7.0L, moisture is 300ppm wherein in solvent.It is subsequently adding
77.14 grams of PDA, under nitrogen protection stirring reduces the temperature to 0 DEG C after after two amine solvents.(TPC is total to be subsequently adding 232 grams of TPC
80%) reaction temperature is risen to 30 DEG C again after the reaction 20min of amount, be subsequently added into remaining TPC stirring 1h can obtain it is sticky
Heterocycle aramid fiber solution, wherein the ratio between molar fraction TPC: PABZ: PDA=10: 5: 5, heterocycle aramid fiber solid content is 5.0%.
Gained heterocycle aramid fiber solution is prepared into precursor using conventional wet spinning, and is obtained in 360 DEG C of static heat treatments
Heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 97%.Test miscellaneous using Ubbelohde viscometer
The intrinsic viscosity of cyclophane synthetic fibre, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table an institute
Show.
Embodiment 2
The HMPA solvents reclaimed in embodiment 1 are carried out into polymerisation again.155.2 grams of PABZ are added into 6.79L to return
In the HMPA solvents of receipts, wherein it is 300ppm to control moisture in solvent.74.82 grams of PDA are subsequently adding, under nitrogen protection
Stirring reduces the temperature to 0 DEG C after after two amine solvents.After being subsequently adding 225.04 grams of TPC (80% of TPC total amounts) reactions 20min
Reaction temperature is risen to 30 DEG C again, remaining TPC stirrings 1h is added followed by and be can obtain sticky heterocycle aramid fiber solution, wherein
The ratio between molar fraction TPC: PABZ: PDA=10: 5: 5, heterocycle aramid fiber solid content is 5.0%.
Gained heterocycle aramid fiber solution is prepared into precursor using conventional wet spinning, and is obtained in 360 DEG C of static heat treatments
Heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 96%.Test miscellaneous using Ubbelohde viscometer
The intrinsic viscosity of cyclophane synthetic fibre, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table an institute
Show.
Embodiment 3
Method according to embodiment 1 carries out polymerisation, wherein TPC: PABZ: PDA=10: 7: 3, heterocycle aramid fiber solid content
It is 5.5%, moisture is 200ppm in solvent HMPA.Two kinds of diamines of PABZ and PDA to solvent are first added under argon gas protection
In HMDA, after after two amine solvents, -10 DEG C are cooled the temperature to.It is subsequently adding reaction temperature liter after 90% TPC reacts 30 minutes
To 20 DEG C, it is subsequently added into remaining TPC stirrings 0.5h and can obtain sticky heterocycle aramid fiber solution
Gained heterocycle aramid fiber solution is prepared into precursor using conventional wet spinning, and is obtained in 380 DEG C of static heat treatments
Heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 98%.Test miscellaneous using Ubbelohde viscometer
The intrinsic viscosity of cyclophane synthetic fibre, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table an institute
Show.
Embodiment 4
Method according to embodiment 1 carries out polymerisation, and wherein TPC: PABZ: PDA=10: 10: 0, heterocycle aramid fiber contains admittedly
It is 6% to measure, and moisture is 250ppm in solvent HMPA.In first adding PABZ to solvent HMDA under helium protection, diamines is treated
After dissolving, -5 DEG C are cooled the temperature to.It is subsequently adding after 70% TPC reacts 10 minutes and reaction temperature is risen to 40 DEG C, then adds
Enter remaining TPC stirrings 2h and can obtain sticky heterocycle aramid fiber solution.
Gained heterocycle aramid fiber solution is prepared into precursor using conventional wet spinning, and is obtained in 370 DEG C of static heat treatments
Heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 98%.Test miscellaneous using Ubbelohde viscometer
The intrinsic viscosity of cyclophane synthetic fibre, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table an institute
Show.
Embodiment 5
Method according to embodiment 1 carries out polymerisation, and wherein Cl-TPC: PABZ: PDA=10: 5: 5, heterocycle aramid fiber is solid
Content is 5.5%, and moisture is 150ppm in solvent HMPA.Diamines PABZ and PDA to solvent is first added under nitrogen protection
In HMDA, after after two amine solvents, 0 DEG C is cooled the temperature to.It is subsequently adding reaction temperature after 80% Cl-TPC reacts 30 minutes
50 DEG C are risen to, remaining TPC stirrings 1h is subsequently added into and be can obtain sticky heterocycle aramid fiber solution.
Gained heterocycle aramid fiber solution is prepared into precursor using conventional wet spinning, and is obtained in 370 DEG C of static heat treatments
Heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 95%.Test miscellaneous using Ubbelohde viscometer
The intrinsic viscosity of cyclophane synthetic fibre, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table an institute
Show.
Embodiment 6
Method according to embodiment 1 carries out polymerisation, and wherein TPC: PABZ: Cl-PDA=10: 5: 5, heterocycle aramid fiber is solid
Content is 5.8%, and moisture is 220ppm in solvent HMPA.Diamines PABZ and Cl-PDA is first added to molten under argon gas protection
In agent HMDA, after after two amine solvents, 5 DEG C are cooled the temperature to.Then disposable addition is reacted 10 minutes with the TPC of diamines equivalent
Reaction temperature is risen into 40 DEG C of stirring 3h afterwards and can obtain sticky heterocycle aramid fiber solution.
Gained heterocycle aramid fiber solution is prepared into precursor using conventional wet spinning, and is obtained in 380 DEG C of static heat treatments
Heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 96%.Test miscellaneous using Ubbelohde viscometer
The intrinsic viscosity of cyclophane synthetic fibre, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table an institute
Show.
Embodiment 7
Method according to embodiment 1 carries out polymerisation, wherein BPC: PABZ: PDA=10: 3: 7, heterocycle aramid fiber solid content
It is 6.5%, moisture is 100ppm in solvent HMPA.Diamines PABZ and PDA to solvent HMDA is first added under nitrogen protection
In, after after two amine solvents, cool the temperature to 4 DEG C.Then the TPC with diamines equivalent is disposably added, will after reacting 20 minutes
Temperature rises to 30 DEG C, and stirring 1h is that can obtain sticky heterocycle aramid fiber solution.
Gained heterocycle aramid fiber solution is prepared into precursor using conventional wet spinning, and is obtained in 380 DEG C of static heat treatments
Heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 96%.Test miscellaneous using Ubbelohde viscometer
The intrinsic viscosity of cyclophane synthetic fibre, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table an institute
Show.
Embodiment 8
Method according to embodiment 1 carries out polymerisation, wherein TPC: PABZ: DHB=10: 5: 5, heterocycle aramid fiber solid content
It is 6.0%, moisture is 500ppm in solvent HMPA.Diamines PABZ and DHB to solvent HMDA is first added under helium protection
In, after after two amine solvents, cool the temperature to 8 DEG C.It is subsequently adding after 70% TPC reacts 40 minutes and reaction temperature is risen to 30
DEG C, it is subsequently added into remaining TPC stirrings 2h and can obtain sticky heterocycle aramid fiber solution.
Gained heterocycle aramid fiber solution is prepared into precursor using conventional wet spinning, and is obtained in 360 DEG C of dynamic hot-stretch
Heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 95%.Test miscellaneous using Ubbelohde viscometer
The intrinsic viscosity of cyclophane synthetic fibre, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table an institute
Show.
Embodiment 9
Method according to embodiment 1 carries out polymerisation, wherein TPC: PABZ: DHO=10: 6: 4, heterocycle aramid fiber solid content
It is 8.0%, moisture is 300ppm in solvent HMPA.Diamines PABZ and DHO to solvent HMDA is first added under nitrogen protection
In, after after two amine solvents, cool the temperature to 5 DEG C.It is subsequently adding after 75% TPC reacts 40 minutes and reaction temperature is risen to 30
DEG C, it is subsequently added into remaining TPC stirrings 2h and can obtain sticky heterocycle aramid fiber solution.
Gained heterocycle aramid fiber solution is prepared into precursor using conventional wet spinning, and is obtained in 380 DEG C of dynamic hot-stretch
Heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 95%.Test miscellaneous using Ubbelohde viscometer
The intrinsic viscosity of cyclophane synthetic fibre, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table an institute
Show.
Embodiment 10
Method according to embodiment 1 carries out polymerisation, wherein TPC: PABZ: DAR=10: 7: 3, heterocycle aramid fiber solid content
It is 5.0%, moisture is 50ppm in solvent HMPA.Diamines PABZ and DAR to solvent HMDA is first added under nitrogen protection
In, after after two amine solvents, cool the temperature to 5 DEG C.It is subsequently adding after 90% TPC reacts 30 minutes and reaction temperature is risen to 30
DEG C, it is subsequently added into remaining TPC stirrings 1h and can obtain sticky heterocycle aramid fiber solution.
Gained heterocycle aramid fiber solution is prepared into precursor using conventional wet spinning, and is obtained in 400 DEG C of dynamic hot-stretch
Heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 97%.Test miscellaneous using Ubbelohde viscometer
The intrinsic viscosity of cyclophane synthetic fibre, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table an institute
Show.
Embodiment 11
Method according to embodiment 1 carries out polymerisation, wherein TPC: PABZ: PDA: DCl-PDA=10: 5: 3: 2, heterocycle
Aramid fiber solid content is 5.0%, and moisture is 300ppm in solvent HMPA.Under nitrogen protection first add diamines PABZ, PDA and
In DCl-PDA to solvent HMDA, after after two amine solvents, 0 DEG C is cooled the temperature to.After being subsequently adding 90% TPC reactions 30 minutes
Reaction temperature is risen to 30 DEG C, remaining TPC stirrings 0.5h is subsequently added into and be can obtain sticky heterocycle aramid fiber solution.
Gained heterocycle aramid fiber solution is washed, separates out to obtain heterocycle aramid fiber resin.The resin is dissolved in again dense
Polymer solution is configured in sulfuric acid, using it is conventional it is dry squirt method and carry out spinning prepare precursor, and in 400 DEG C of dynamic hot-stretch
Obtain heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 96%.Surveyed using Ubbelohde viscometer
The intrinsic viscosity of heterocycle aramid fiber is tried, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table
Shown in one.
Embodiment 12
Method according to embodiment 1 carries out polymerisation, and wherein TPC: PABZ: DABA: DABA-Cl=10: 5: 2: 3, it is miscellaneous
Cyclophane synthetic fibre solid content is 5.5%, and moisture is 250ppm in solvent HMPA.Argon gas protection under first add diamines PABZ,
In DABA and DABA-Cl to solvent HMDA, after after two amine solvents, 0 DEG C is cooled the temperature to.Then disposable addition and diamines etc. is worked as
Reaction temperature is risen to 30 DEG C by the TPC of amount after reacting 30 minutes, is followed by stirring for 0.5h and be can obtain sticky heterocycle aramid fiber solution.
Gained heterocycle aramid fiber solution is washed, separates out to obtain heterocycle aramid fiber resin.The resin is dissolved in again dense
Polymer solution is configured in sulfuric acid, using it is conventional it is dry squirt method and carry out spinning prepare precursor, and in 400 DEG C of dynamic hot-stretch
Obtain heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 96%.Surveyed using Ubbelohde viscometer
The intrinsic viscosity of heterocycle aramid fiber is tried, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table
Shown in one.
Embodiment 13
Method according to embodiment 1 carries out polymerisation, and wherein TPC: BPC: PABZ: BZ=8: 2: 5: 5, heterocycle aramid fiber is solid
Content is 7%, and moisture is 450ppm in solvent HMPA.Diamines PABZ, BZ to solvent HMDA are first added under nitrogen protection
In, after after two amine solvents, cool the temperature to 0 DEG C.It is subsequently adding reaction temperature liter after 88% TPC and BPC reacts 30 minutes
To 30 DEG C, it is subsequently added into remaining TPC and BPC stirrings 0.5h and can obtain sticky heterocycle aramid fiber solution.
Gained heterocycle aramid fiber solution is washed, separates out to obtain heterocycle aramid fiber resin.The resin is dissolved in again dense
Polymer solution is configured in sulfuric acid, using it is conventional it is dry squirt method and carry out spinning prepare precursor, and in 390 DEG C of dynamic hot-stretch
Obtain heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 97%.Surveyed using Ubbelohde viscometer
The intrinsic viscosity of heterocycle aramid fiber is tried, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table
Shown in one.
Comparative example 1
160 grams of PABZ are added in the DMAC/LiCl solvents of 8.84L, wherein the mass fraction of LiCl is 3.5%, molten
Moisture is 300ppm in agent.77.14 grams of PDA are subsequently adding, stirring under nitrogen protection drops temperature after after two amine solvents
To 0 DEG C.Reaction temperature is risen to 30 DEG C again after being subsequently adding 232 grams of TPC (80% of TPC total amounts) reactions 20min, is subsequently added into
Remaining TPC stirrings 1h is that can obtain sticky heterocycle aramid fiber solution, wherein the ratio between molar fraction TPC: PABZ: PDA=10: 5:
5, heterocycle aramid fiber solid content is 4.1%.
Gained heterocycle aramid fiber solution is prepared into precursor using conventional wet spinning, and is obtained in 360 DEG C of static heat treatments
Heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 93%.Test miscellaneous using Ubbelohde viscometer
The intrinsic viscosity of cyclophane synthetic fibre, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table an institute
Show.
Comparative example 2
Method according to embodiment 3 carries out polymerisation, first adds two kinds of diamines of PABZ and PDA to solvent NMP/CaCl2
(CaCl in solvent2Mass fraction be 4%) in, under nitrogen protection after after two amine solvents, cool the temperature to -10 DEG C.Then plus
Enter 90% TPC react 30 minutes after reaction temperature is risen to 20 DEG C, being subsequently added into remaining TPC stirring 0.5h can be glued
Thick heterocycle aramid fiber solution.Wherein TPC: PABZ: PDA=10: 7: 3, heterocycle aramid fiber solid content is 4.5%, solvent NMP/CaCl2
Middle moisture is 200ppm.
Gained heterocycle aramid fiber solution is prepared into precursor using conventional wet spinning, and is obtained in 380 DEG C of static heat treatments
Heterocycle aramid fiber finished silk.And solvent recovery is carried out to whole process, solvent recovering rate is 94%.Test miscellaneous using Ubbelohde viscometer
The intrinsic viscosity of cyclophane synthetic fibre, its result is as shown in Table 1；The tensile strength and initial modulus of heterocycle aramid fiber finished silk are shown in Table an institute
Show.
Table one
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from of the invention
Many other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of preparation method of heterocycle aramid fiber solution, it is characterised in that including：Diamines material exists with aromatic dimethyl chloride
Under atmosphere of inert gases, there is polymerisation in the HMPA solution for not containing cosolvent；
The Diamines material includes 2- (4- aminophenyls) -5- aminobenzimidazoles.
2. the preparation method of heterocycle aramid fiber solution according to claim 1, it is characterised in that the inert gas is nitrogen
One kind in gas, helium, argon gas.
3. the preparation method of heterocycle aramid fiber solution according to claim 1, it is characterised in that the aromatic dimethyl chloride
It is phthalyl chloride and/or biphenyl dimethyl chloride.
Preferably, the phthalyl chloride includes paraphthaloyl chloride and/or adjacent chlorine paraphthaloyl chloride.
4. the preparation method of heterocycle aramid fiber solution according to claim 1, it is characterised in that in the Diamines material also
Including aromatic diamines.
5. the preparation method of heterocycle aramid fiber solution according to claim 4, it is characterised in that the phenyl ring of the aromatic diamines
Number is 1 or 2.
6. the preparation method of heterocycle aramid fiber solution according to claim 4, it is characterised in that 2- (the 4- aminobenzenes
Base) the mole percent of -5- aminobenzimidazoles in the Diamines material be 30%~100%.
7. the preparation method of the heterocycle aramid fiber solution according to any one of claim 5~6, it is characterised in that the fragrance
Diamines includes p-phenylenediamine, 2- (4- aminophenyls) -5- An bases benzoxazole, 4,4 ',-diaminobenzene anilid, adjacent chlorine pair
Phenylenediamine, benzidine, 3,3 '-dihydroxybiphenyl amine, 3, the chloro- Isosorbide-5-Nitrae phenylenediamine of 3 '-dimethoxy benzidine, 2,5- bis-, 2,5-
Dihydroxy-Isosorbide-5-Nitrae phenylenediamine and 2- chloro- 4,4 ', one or more in-diaminobenzene anilid.
8. the preparation method of heterocycle aramid fiber solution according to claim 1, it is characterised in that the Diamines material is molten
Solution to after in the HMPA solution by solution temperature control at -10~10 DEG C, then by the formyl of the aromatic series two
Chlorine is added and reacted.
9. the preparation method of heterocycle aramid fiber solution according to claim 8, it is characterised in that the aromatic dimethyl chloride
Add at twice or disposable addition.
10. the preparation method of heterocycle aramid fiber solution according to claim 9, it is characterised in that adding the aromatic series
During dimethyl chloride：
Addition and the 70%~90% of the Diamines material equivalent for the first time, again rises to temperature after reaction 10min~1h
20~50 DEG C, remaining aromatic dimethyl chloride is added to continue to react 0.5~3h；
Or；
The disposable acyl chlorides added with the Diamines material equivalent, temperature is risen to 20 again after reaction 10min~30min~
50 DEG C, continue to react 0.5~3h.
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| CN108503827A (en) * | 2018-03-15 | 2018-09-07 | 四川大学 | A kind of heterocycle aramid fiber and preparation method thereof, fibrous material and bulletproof armour |
| CN108559077A (en) * | 2018-05-14 | 2018-09-21 | 四川大学 | The preparation method and heterocycle aramid fiber product of heterocycle aramid fiber solution and preparation method thereof and heterocycle aramid fiber finished silk |
| CN109518459A (en) * | 2018-11-28 | 2019-03-26 | 四川大学 | A kind of method of modifying and modified high performance organic fiber of high-performance organic fibre |
| CN109942810A (en) * | 2019-04-18 | 2019-06-28 | 四川大学 | A kind of heteroaromatic polyamide laminated film and preparation method with high breakdown strength |
| CN110565197A (en) * | 2019-09-20 | 2019-12-13 | 株洲时代新材料科技股份有限公司 | Preparation method of heterocyclic aramid 1313 fiber |
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| CN115678004A (en) * | 2021-07-30 | 2023-02-03 | 中蓝晨光化工研究设计院有限公司 | High-strength high-modulus heterocyclic aramid fiber and preparation method thereof |
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| CN115678004A (en) * | 2021-07-30 | 2023-02-03 | 中蓝晨光化工研究设计院有限公司 | High-strength high-modulus heterocyclic aramid fiber and preparation method thereof |
| CN115678004B (en) * | 2021-07-30 | 2024-02-23 | 中蓝晨光化工研究设计院有限公司 | High-strength high-modulus heterocyclic aramid fiber and preparation method thereof |
| CN114464952A (en) * | 2022-01-30 | 2022-05-10 | 中材锂膜有限公司 | High-heat-resistance heterocyclic aramid fiber coated diaphragm and preparation method thereof |
| CN117966294A (en) * | 2024-03-29 | 2024-05-03 | 江苏新视界先进功能纤维创新中心有限公司 | Fiber and preparation method thereof |
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