CN116813902B - Poly (m-phenylene isophthalamide) solution, meta-aramid spinning solution and preparation method thereof - Google Patents
Poly (m-phenylene isophthalamide) solution, meta-aramid spinning solution and preparation method thereof Download PDFInfo
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- 238000009987 spinning Methods 0.000 title claims abstract description 90
- 239000004760 aramid Substances 0.000 title claims abstract description 30
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 title claims description 34
- 239000002904 solvent Substances 0.000 claims abstract description 62
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 98
- 238000006116 polymerization reaction Methods 0.000 claims description 93
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 54
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 45
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000000835 fiber Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 13
- 230000003472 neutralizing effect Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- -1 polyisophthaloyl Polymers 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 238000005345 coagulation Methods 0.000 claims description 9
- 230000015271 coagulation Effects 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 230000003381 solubilizing effect Effects 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 239000011550 stock solution Substances 0.000 claims 1
- SHTJVLLCHPKPDD-UHFFFAOYSA-N 3-(7-azabicyclo[3.3.1]nona-1(9),2,4-triene-7-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2CC=3C=CC=C(C=3)C2)=C1 SHTJVLLCHPKPDD-UHFFFAOYSA-N 0.000 abstract 2
- 238000006386 neutralization reaction Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 239000012295 chemical reaction liquid Substances 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 13
- 238000004090 dissolution Methods 0.000 description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 238000002166 wet spinning Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 229960001701 chloroform Drugs 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 230000001112 coagulating effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- WBNUVPGJLHTDTD-UHFFFAOYSA-N 4-ethyl-5-methylimidazolidin-2-one Chemical compound CCC1NC(=O)NC1C WBNUVPGJLHTDTD-UHFFFAOYSA-N 0.000 description 2
- IWNWLPUNKAYUAW-UHFFFAOYSA-N Ethylendiamine dihydroiodide Chemical compound I.I.NCCN IWNWLPUNKAYUAW-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 241000364051 Pima Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012681 fiber drawing Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyamides (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a poly m-phenylene isophthalamide solution, a meta-aramid spinning solution and a preparation method thereof. The m-xylylene isophthalamide solution of the present invention comprises m-xylylene isophthalamide and a solvent comprising a compound represented by the formula (1), which solution can achieve low viscosity even if it contains hydrogen chloride, thus allowing production in a continuous manner, and can be used as a meta-aramid spinning dope for producing meta-aramid fibers efficiently and stably.
Description
Technical Field
The invention relates to a poly m-phenylene isophthalamide solution, a meta-aramid spinning solution and a preparation method thereof, belonging to the field of high-performance fibers.
Background
The meta-aramid fiber is a special fiber made of poly-m-phenylene isophthalamide (also referred to as PMIA in this text), has the characteristics of heat resistance, flame retardance, excellent insulativity and the like, and has important application value in the fields of heat protection, insulation, honeycomb, high-temperature filtration and the like.
Industrial production of meta-aramid fiber generally includes three parts: polymerization, solvent recovery and spinning. The meta-aramid fiber industrial production technology has been developed for decades, and a relatively mature process is formed at present: the polymerization generally adopts low-temperature solution polycondensation, namely, monomers of m-phenylenediamine (MPD) and isophthaloyl dichloride (IPC) are spontaneously polymerized in a solvent of N, N-dimethylacetamide (DMAc) to generate PMIA polymer; the polymerization solution is directly subjected to wet spinning to form fibers after neutralization and elimination of byproduct hydrogen chloride; the waste liquid with solvent generated by spinning washing is recycled through separation and purification of solvent recovery.
DMAc is a good solvent for PMIA and two monomers (MPD and IPC), and the solution formed after polymerization is stable, which is favorable for the subsequent spinning process, so that the DMAc is a solvent for producing PIMA and meta-aramid fiber which is commonly used in industry at present.
Patent document 1 discloses a method for polymerizing PMIA, in which MPD and IPC are prepolymerized in a solvent DMAc, then neutralized with ammonia gas, then subjected to cyclic filtration, then subjected to final polymerization, and then subjected to secondary neutralization with an organic amine.
Patent document 2 discloses a method for continuously preparing PMIA, wherein a polar solvent, an MPD melt and an IPC melt are respectively metered and conveyed, enter a twin-screw mixer for mixing and preliminary reaction to generate an oligomer, enter from the bottommost end of a polymerization reactor, continue to react for a certain time, and the formed PMIA resin solution flows out from the upper side part of the polymerization reactor, thereby continuously preparing the PMIA resin solution.
Citation document
Patent document 1: CN109400873A
Patent document 2: CN106046364A
Disclosure of Invention
Problems to be solved by the invention
The production process of meta-aramid fiber using DMAc as a solvent also has a number of problems, such as:
(1) Side reaction problem: DMAc has unstable molecular structure and is easy to generate irreversible side reaction with polymerization reaction byproduct hydrogen chloride and monomer acyl chloride at high temperature, so that the polymerization reaction is required to be strictly controlled to be carried out in a low-temperature environment, otherwise PMIA molecular weight is extremely easy to be low or molecular weight distribution is extremely wide, the mechanical properties of the obtained fiber are seriously affected, however, the heat release amount of the polymerization reaction is large, and the problem of difficulty in considering the required low-temperature condition is solved;
(2) Neutralization problem: DMAc has insufficient dissolving capacity for polymer PMIA, and the polymerization system viscosity is high due to the hydrogen bonding action of the superimposed byproduct hydrogen chloride, DMAc and PMIA, so that the polymerization solution taking DMAc as a solvent is necessary to neutralize the byproduct hydrogen chloride, and the two schemes for neutralizing the hydrogen chloride have obvious defects: although the neutralization with ammonia gas can ensure moderate viscosity of the polymerization solution and is beneficial to subsequent spinning, the process of removing the neutralization product ammonium chloride after the neutralization makes the polymerization difficult to continuously proceed, but the discontinuous polymerization inevitably affects the stability of the polymerization process, thereby affecting the stability of the subsequent fiber performance; although neutralization with calcium hydroxide (or calcium oxide) may not affect the continuity of the polymerization process, the complexing effect of calcium ions results in a high viscosity of the polymer solution, which has a significant impact on the quality of subsequent spinning.
Therefore, although the meta-aramid fiber has been industrially produced for decades abroad, and the industrial mass production of China has been realized for decades, there is still a need to develop a more optimal meta-aramid fiber preparation process.
Accordingly, an object of the present invention is to provide a poly (m-phenylene isophthalamide) solution, a meta-aramid spinning dope, and a method for preparing the same, which can achieve low viscosity of the solution even without neutralizing hydrogen chloride, a byproduct of polymerization reaction, thereby allowing easy production in a continuous manner, and which can be used as a meta-aramid spinning dope to obtain high quality meta-aramid fibers.
Solution for solving the problem
The present inventors have conducted intensive studies to solve the above problems, and have found that the above problems can be solved by using a compound represented by the formula (1) as a solvent.
Specifically, the present invention solves the problems of the present invention by the following means.
[1] A polyisophthaloyl metaphenylene diamine solution comprising polyisophthaloyl metaphenylene diamine and a solvent comprising a compound represented by the following formula (1):
wherein R is 1 And R is 2 Independently of each other, methyl, ethyl or propyl, n being an integer from 1 to 5.
[2]According to [1]]The solution, wherein, in the formula (1), R 1 And R is 2 Independently of one another, methyl or ethyl, n being 1, 2 or 3; preferably, R 1 And R is 2 All represent methyl groups, and n is 1 or 2.
[3] The solution according to [1] or [2], characterized by further comprising a solubilizing salt which is one or more selected from the group consisting of halides of alkali metals or alkaline earth metals, preferably one or more selected from the group consisting of chlorides of alkali metals or alkaline earth metals; more preferably one or more selected from calcium chloride and lithium chloride; the content of the auxiliary soluble salt is 0 to 5wt% relative to the solvent.
[4] The solution according to [1] or [2], wherein hydrogen chloride is further contained, and the content of the hydrogen chloride is 3 to 7wt%.
[5] The solution according to [1] or [2], wherein the content of the polymetaphenylene isophthalamide is 14 to 22wt%; the viscosity of the solution is 10-80 Pa.s.
[6] A meta-aramid spinning dope comprising the polyisophthaloyl metaphenylene diamine solution as described in any one of [1] to [5 ].
[7] A preparation method of a poly m-phenylene isophthalamide solution or meta-aramid spinning solution comprises the following steps:
polymerizing m-phenylenediamine and m-phthaloyl chloride in a solvent to obtain a polymerization solution, and optionally defoaming and filtering the polymerization solution;
wherein the solvent comprises a compound represented by the following formula (1):
wherein R is 1 And R is 2 Independently of each other, methyl, ethyl or propyl, n being an integer from 1 to 5.
[8] The production method according to [7], wherein the step of neutralizing hydrogen chloride in the polymerization liquid is not included.
[9] A method for preparing meta-aramid fiber, comprising the steps of:
spinning the meta-aramid spinning solution of [6] to obtain a primary spun fiber, and then washing the primary spun fiber with water, and optionally drying, oiling and winding to obtain a meta-aramid fiber;
wherein the spinning process uses an aqueous alkali as a coagulation bath, the alkali being preferably at least one selected from the group consisting of sodium hydroxide and potassium hydroxide.
[10] The method for producing a meta-aramid fiber according to [9], further comprising a step of recovering a solvent from a spinning waste liquid produced by coagulation bath and water washing, the solvent recovering step comprising:
neutralizing the spinning waste liquid by using alkali, extracting by using an extracting agent, performing reduced pressure distillation on an organic phase, and rectifying heavy components obtained by the reduced pressure distillation.
ADVANTAGEOUS EFFECTS OF INVENTION
Compared with the prior art, the invention has the following beneficial effects:
(1) The solvent used in the invention is not easy to generate side reaction, and the low-temperature polymerization condition is not required to be strictly controlled, thereby greatly improving the production efficiency and reducing the production cost; the spinning (temperature) operation elasticity is allowed, so that the fiber structure and performance are more convenient to regulate and control;
(2) The polyisophthaloyl metaphenylene diamine solution of the present invention can achieve low viscosity even if it contains hydrogen chloride, thus allowing production to be performed in a continuous manner, particularly allowing polymerization and spinning processes to be continuously performed, and greatly improving production stability and efficiency;
(3) On the basis of the existing process production line, the poly (m-phenylene isophthalamide) solution can be produced by only changing the solvent and fine-tuning the production process, and the production device does not need to be greatly changed, so that the cost of process improvement is greatly reduced;
(4) The meta-aramid spinning solution can be used for obtaining high-quality meta-aramid fibers.
Detailed Description
Various exemplary embodiments, features and aspects of the invention are described in detail below. The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better illustration of the invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, well known methods, procedures, means, equipment and steps have not been described in detail so as not to obscure the present invention.
Unless otherwise indicated, all units used in this specification are units of international standard, and numerical values, ranges of values, etc. appearing in the present invention are understood to include systematic errors unavoidable in industrial production.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
Reference throughout this specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, when "normal temperature" or "room temperature" is used, the temperature may be 10 to 40 ℃.
An object of the present invention is to provide a polyisophthaloyl metaphenylene diamine solution comprising polyisophthaloyl metaphenylene diamine and a solvent comprising a compound represented by the following formula (1):
wherein R is 1 And R is 2 Independently of each other, methyl, ethyl or propyl, n being an integer from 1 to 5.
The solvent used in the invention has the characteristics of stable structure and better solubility to PMIA. In addition, when a solubilizing salt (e.g., lithium chloride) is used, the solubilizing salt may form a coordination complex with the PMIA, further enhancing the dissolution of the PMIA by the solvent system.
The invention can solve the problem that DMAc is easy to generate side reaction by using the compound of formula (1) in a solvent system, and can improve the solubility of the solvent to the polymer at the same time, thereby reducing the viscosity of the polymer solution obtained by polymerization. The research result proves that the solvent system can ensure continuous and stable follow-up spinning even without neutralizing byproduct hydrogen chloride, thereby realizing continuous polymerization and high-quality spinning of meta-aramid fiber.
Preferably, R in formula (1) 1 And R is 2 Independently of one another, methyl or ethyl, n being 1, 2 or 3.
More preferably, R 1 And R is 2 All represent methyl groups, and n is 1 or 2. In this preferred embodiment, the solvent used in the present invention comprises one or both selected from 1, 3-Dimethylpropyleneurea (DMPU) and 1, 3-dimethyl-2-imidazolidinone (DMI).
Wherein the structures of the 1, 3-dimethylpropyleneurea and the 1, 3-dimethyl-2-imidazolidinone are respectively as follows:
the solvent may contain, in addition to the compound of formula (1), solvents commonly used for producing PMIA, such as N, N-dimethylacetamide, N-methylpyrrolidone, etc.
In one embodiment, the solvent contains 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, even more preferably 90% by mass or more of the compound of formula (1).
In a more preferred embodiment, the solvent consists of a compound of formula (1).
Preferably, the water content of the solvent is 100ppm or less.
In one embodiment, the PMIA solution of the invention further comprises a solubilizing salt, which is one or more selected from the halides of alkali metals or alkaline earth metals, preferably one or more selected from the chlorides of alkali metals or alkaline earth metals; more preferably one or more selected from calcium chloride and lithium chloride.
In one embodiment, the content of the auxiliary salt is 0 to 5wt% with respect to the solvent.
In one embodiment, the PMIA solution of the present invention further comprises hydrogen chloride, the content of which is 3 to 7wt%. The monomers MPD and IPC are polymerized to generate PMIA and generate hydrogen chloride as a byproduct, and the hydrogen chloride exists in a solution obtained by polymerization under the condition that neutralization treatment is not carried out.
In one embodiment, the PMIA solution of the present invention has a PMIA content of 14 to 22wt%; the viscosity of the solution is 10-80 Pa.s.
The PMIA solution can be directly used as meta-aramid spinning solution, and can also be used as meta-aramid spinning solution after being subjected to treatments such as defoaming, filtering and the like.
It is another object of the present invention to provide a meta-aramid spinning dope comprising the PMIA solution of the present invention. Preferably, the meta-aramid spinning dope of the present invention consists of the PMIA solution of the present invention.
Another object of the present invention is to provide a method for preparing a PMIA solution or meta-aramid spinning dope, which comprises the steps of:
polymerizing m-phenylenediamine and m-phthaloyl chloride in a solvent to obtain a polymerization solution, and optionally defoaming and filtering the polymerization solution;
wherein the solvent comprises a compound represented by the above formula (1).
In a specific embodiment, the preparation method of the PMIA solution or meta-aramid spinning dope of the present invention is a continuous process, which comprises the following steps:
prepolymerization: continuously feeding m-phenylenediamine solution and m-phthaloyl chloride melt into a prepolymerization reactor for prepolymerization reaction to obtain a prepolymerization reaction solution; wherein the m-phenylenediamine solution comprises m-phenylenediamine and a solvent comprising a compound represented by the above formula (1); the molar feed ratio of the isophthaloyl dichloride to the m-phenylenediamine is 0.90-0.95: 1, a step of;
and (3) final polymerization: continuously feeding the prepolymerization reaction liquid and m-phthaloyl chloride melt into a final polymerization reactor for final polymerization reaction to obtain a final polymerization reaction liquid, wherein the molar feed ratio of the m-phthaloyl chloride to m-phenylenediamine in the prepolymerization stage is (0.04-0.11): 1, a step of;
and optionally passing the final polymerization reaction solution through a defoaming and/or filtering device.
In one embodiment, the preparation method of the PMIA solution or meta-aramid spinning dope of the present invention does not include a step of neutralizing hydrogen chloride in the polymerization solution (the prepolymerization solution and the final polymerization solution).
As described above, the neutralization of hydrogen chloride is a cause of difficulty in achieving both low viscosity and continuous production of the PMIA solution, and the present invention can obtain a PMIA solution having a low viscosity that can be used as a spinning dope without neutralizing hydrogen chloride by using a specific solvent.
In one embodiment, the temperature of the m-phenylenediamine solution is from-10 to 0 ℃; the concentration of the m-phenylenediamine is 0.8-1.2 mol/l.
In one embodiment, the isophthaloyl dichloride melt temperature is 50 to 70 ℃.
In one embodiment, the temperature of the prepolymerization reaction is 0 to 50 ℃; the reaction time is 5-30 min.
In one embodiment, the temperature of the final polymerization reaction is from 20 to 50 ℃; the reaction time is 5-60 min.
In one embodiment, the prepolymerization is carried out in a continuous tubular reactor; the final polymerization is carried out in a twin-screw reactor.
In one embodiment, the m-phenylenediamine solution further comprises a solubilizing salt as described above.
In one embodiment, the polymerization solution (final polymerization reaction solution) is subjected to a defoaming treatment to remove bubbles therein. The deaeration may be carried out in a manner conventional in the art, for example, vacuum continuous deaeration or the like.
In one embodiment, the polymerization solution (final polymerization reaction solution) is filtered to remove impurities therein, such as pipe corrosions, welding slag, and gels, etc., which adhere to the pipe walls due to long-term production. Filtration may be carried out in a manner conventional in the art, such as wick-type continuous filtration, and the like.
In one embodiment, the apparatus used for defoaming and filtering uses a corrosion resistant material for the parts in contact with the polymerization liquid (the final polymerization reaction liquid) to avoid corrosion of the apparatus by hydrogen chloride.
The description and preferred embodiments given above with respect to the poly (m-phenylene isophthalamide) solution and the meta-aramid spinning dope are correspondingly applicable to the preparation method of the poly (m-phenylene isophthalamide) solution or the meta-aramid spinning dope of the present invention.
An object of the present invention is to provide a method for preparing meta-aramid fiber, comprising the steps of:
spinning by using the meta-aramid spinning solution to obtain a primary spun fiber, and then washing the primary spun fiber with water, and optionally drying, oiling and winding to obtain the meta-aramid fiber; wherein the spinning process uses an aqueous alkali solution as the coagulation bath.
Specifically, during spinning, the spinning dope of the present invention is passed through a spinneret, and the discharged fibers are coagulated in a coagulation bath to obtain as-spun fibers. Since the spinning dope contains hydrogen chloride without undergoing a neutralization treatment, an aqueous alkali solution is used as a coagulation bath.
In one embodiment, the aqueous alkali is preferably at least one selected from the group consisting of aqueous sodium hydroxide and aqueous potassium hydroxide, more preferably aqueous sodium hydroxide.
In one embodiment, the aqueous alkali solution has a mass concentration of 0.1 to 1%
The present invention is not particularly limited to the spinning process, and may be any suitable spinning process known in the art, such as wet spinning or dry-jet wet spinning.
In one embodiment, a wet spinning process is used for the purpose of high throughput and low production costs.
In one embodiment, a dry-jet wet spinning process is used for the purpose of obtaining high strength fibers.
In one embodiment, the method for preparing meta-aramid fiber of the present invention further includes a step of recovering a solvent from a spinning waste liquid generated from a coagulation bath and a water washing, the step of recovering a solvent including:
neutralizing the spinning waste liquid by using alkali, extracting by using an extracting agent, performing reduced pressure distillation on an organic phase, and rectifying heavy components obtained by the reduced pressure distillation.
In the embodiment of the spinning dope containing the cosolvent salt, the solvent recovery step further comprises adding sodium carbonate to the extracted aqueous phase (raffinate phase), separating the precipitate, and adding hydrochloric acid to the precipitate for reduction to lithium chloride for recycling.
In the step of solvent recovery, the polymerization byproduct hydrogen chloride is neutralized to avoid corrosion to production equipment and pollution to the solvent; extracting with an extractant to obtain an organic phase containing the solvent and an aqueous phase substantially free of the solvent; the organic phase is distilled under reduced pressure, the extractant is separated from the organic phase, and the separated extractant can be recycled; and (3) rectifying the heavy component separated from the extractant to obtain a recovered solvent with high purity (more than 99%). The recovered solvent can be used for preparing spinning dope to achieve the purpose of recycling.
In one embodiment, the base used for neutralization is an alkali or alkaline earth hydroxide, such as one or more selected from sodium hydroxide, potassium hydroxide, calcium hydroxide. The pH of the neutralized waste liquid is 7.5-8.5.
In one embodiment, the extractant is one or more selected from chlorinated hydrocarbons, esters and ethers solvents, preferably one or more selected from trichloromethane, trichloroethylene, butyl acetate, isopropyl ether.
In a specific embodiment, the method for preparing meta-aramid fiber of the present invention further comprises a step of preparing a spinning dope using the method of the present invention, wherein the step of preparing the spinning dope and the step of spinning are continuously performed. In this embodiment, the resulting dope is continuously fed into a spinning device.
The meta-aramid fiber with excellent mechanical property and stable quality can be obtained by the method.
In one embodiment, the meta-aramid fiber produced by the process of the present invention has a tensile strength of 4.0g/d or more, preferably 4.5g/d or more.
In one embodiment, the meta-aramid fiber obtained by the preparation method of the present invention has an elongation at break of 20% or more, preferably 25% or more.
In one embodiment, the meta-aramid fiber produced by the process of the present invention has an elastic modulus of 100g/d or more, preferably 105d/g or more, more preferably 110g/d or more.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The mechanical properties of the finished fibers obtained in the examples below were tested according to GB/T14337-2022, the drawing device being a constant speed elongation type single fiber drawing instrument.
Example 1:
(1) Polymerization: the MPD solid powder and the dehydrated DMPU (water content: 70 ppm) were continuously fed to a dissolution apparatus (volume: 5 m) with stirring and nitrogen protection 3 ) Is dissolved in the solvent. DMPU feed rate was 3185.8kg/h and MPD feed rate was 367.68kg/h. The dissolution temperature is about 15 ℃, and the retention time of the materials in the dissolution device (about 30min of dissolution time). The dissolved m-phenylenediamine solution is cooled to the temperature of minus 10 ℃, and then quantitatively, continuously and stably conveyed into a tubular prepolymerization reactor through a metering pump and a flowmeter; the IPC melt (60 ℃) is quantitatively, continuously and stably conveyed into a tubular prepolymerization reactor through a metering pump and a flowmeter to carry out prepolymerization reaction with MPD; the feeding speed of MPD solution is 1776.74kg/h, the feeding speed of IPC melt is 327.88kg/h, and the IPC molar flow is 0.95 times of MPD by regulating the flow. The residence time of the material in the tube reactor was about 10min, the prepolymerization temperature was 20℃and the stirring speed was 300rpm.
The prepolymerization reaction liquid after the prepolymerization is directly pushed into a final polymerization twin-screw reactor, meanwhile, the IPC melt is continuously and stably pumped into the twin-screw reactor for final polymerization after being metered by a flowmeter, the feeding amount of the IPC is 17.95kg/h (the ratio of the sum of the feeding mole numbers of the IPC in the prepolymerization and final polymerization stages to the feeding mole number of the MPD is 1.002:1). The final polymerization temperature was 40℃and the reaction time was 5min.
The viscosity of the final polymerization reaction liquid obtained after the final polymerization reaction is continuously monitored through an online viscometer at the outlet of the double-screw reactor and is fed back to an IPC flowmeter added in the final polymerization to finely adjust the IPC melt flow. The viscosity of the final polymerization reaction solution can be controlled to 40.+ -. 1.5 Pa.s when the apparatus is stably operated.
The final polymerization reaction liquid is directly subjected to continuous filtration and deaeration treatment to obtain spinning solution.
(2) Spinning: the obtained spinning dope is fed to a spinning device. The spinning adopts wet spinning, the spinning speed is 30m/min, the coagulating bath adopts sodium hydroxide aqueous solution with the mass concentration of 1%, and the temperature is 10 ℃. The nascent fiber is coiled into a fiber finished product through the links of subsequent washing, drying, hot drawing, oiling, coiling and the like.
The mechanical properties of the obtained finished fiber are as follows: the tensile strength was 4.5g/d, the elongation at break was 30%, and the elastic modulus was 115g/d.
(3) And (3) recovering a solvent: the pH of the spinning waste liquid (waste liquid produced by coagulating bath and water washing) is adjusted to about 8 after being neutralized by sodium hydroxide again, then chloroform is used for extraction, chloroform is separated from the extract by reduced pressure distillation, and the heavy component is rectified (vacuum degree-0.098 MPa, kettle bottom temperature 150 ℃) to obtain the pure solvent DMPU with purity of 99.5%.
Example 2:
(1) Polymerization: the MPD solid powder and the dehydrated DMI (water content: 50 ppm) were continuously fed to a dissolution apparatus (volume: 5 m) with stirring and nitrogen protection 3 ) Is dissolved in the solvent. DMPU feed rate was 3185.8kg/h and MPD feed rate was 330.92kg/h. The dissolution temperature is about 15 ℃, and the retention time of the materials in the dissolution device (about 30min of dissolution time). The dissolved m-phenylenediamine solution is cooled to the temperature of minus 10 ℃, and then quantitatively, continuously and stably conveyed into a tubular prepolymerization reactor through a metering pump and a flowmeter; the IPC melt (60 ℃) is quantitatively, continuously and stably conveyed into a tubular prepolymerization reactor through a metering pump and a flowmeter to carry out prepolymerization reaction with MPD; the feeding speed of MPD solution is 1758.36kg/h and the feeding speed of IPC melt is279.56kg/h, IPC molar flow was 0.90 times that of MPD. The residence time of the material in the tube reactor was about 8min, the prepolymerization temperature was 30℃and the stirring speed was 300rpm.
The prepolymerization reaction liquid after the prepolymerization is directly pushed into a final polymerization double-screw reactor, and simultaneously IPC melt is continuously and stably pumped into the double-screw reactor for final polymerization after being metered by a flowmeter. The feed rate of IPC was 33.25kg/h (the ratio of the number of moles of IPC fed to the number of moles of MPD fed in the prepolymerization and final polymerization stages: 1.007:1). The final polymerization temperature was 50℃and the reaction time was 5min.
The viscosity of the final polymerization reaction liquid obtained after the final polymerization reaction is continuously monitored through an online viscometer at the outlet of the double-screw reactor and is fed back to an IPC flowmeter added in the final polymerization to finely adjust the IPC melt flow. The viscosity of the final polymerization reaction solution can be controlled to 50.+ -.2 Pa.s when the apparatus is stably operated.
The final polymerization reaction liquid is directly subjected to continuous filtration and deaeration treatment to obtain spinning solution.
(2) Spinning: the obtained spinning dope is fed to a spinning device. The spinning adopts a dry-jet wet spinning method, the diameter of a spinning hole is 100 mu m, the spinning speed is 100m/min, the draft ratio is 3, the coagulating bath adopts a sodium hydroxide aqueous solution with the mass concentration of 0.5%, and the temperature is 5 ℃. The nascent fiber is coiled into a fiber finished product through the links of subsequent washing, drying, hot drawing, oiling, coiling and the like.
The mechanical properties of the obtained finished fiber are as follows: the tensile strength is 4.8g/d, the elongation at break is 25%, and the elastic modulus is 120g/d.
(3) And (3) recovering a solvent: the pH of the spinning waste liquid is adjusted to about 8 after the secondary neutralization treatment of sodium hydroxide, then chloroform is used for extraction, the chloroform is separated from the extract by reduced pressure distillation, and the heavy component is rectified (vacuum degree-0.098 MPa, kettle bottom temperature 120 ℃) to obtain the pure solvent DMI with purity of 99.9%.
Example 3:
(1) Polymerization: the MPD solid powder and the dehydrated DMPU and lithium chloride (2.7 wt.%) mixed solvent were continuously fed to a dissolution apparatus (volume 5 m) with stirring and nitrogen protection 3 ) In (a)And (5) dissolving. The solvent feed rate was 3275.8kg/h and the MPD feed rate was 367.68kg/h. The dissolution temperature is about 15 ℃, and the retention time of the materials in the dissolution device (about 30min of dissolution time). The dissolved m-phenylenediamine solution is cooled to-10 ℃, and then quantitatively, continuously and stably conveyed into a tubular prepolymerization reactor through a metering pump and a flowmeter. The IPC melt (60 ℃) is quantitatively, continuously and stably conveyed into a tubular prepolymerization reactor through a metering pump and a flowmeter to carry out prepolymerization reaction with MPD. The feeding speed of MPD solution is 1821.74kg/h, the feeding speed of IPC melt is 327.88kg/h, and the IPC molar flow is 0.95 times of MPD. The residence time of the material in the tube reactor was about 10min, the prepolymerization temperature was 20℃and the stirring speed was 300rpm.
The prepolymerization reaction liquid after the prepolymerization is directly pushed into a final polymerization double-screw reactor, and simultaneously IPC melt is continuously and stably pumped into the double-screw reactor for final polymerization after being metered by a flowmeter. The feed rate of IPC was 17.95kg/h (the ratio of the number of moles of IPC fed to the number of moles of MPD fed in the prepolymerization and final polymerization stages: 1.002:1). The final polymerization temperature was 40℃and the reaction time was 5min.
The viscosity of the material after final polymerization reaction is continuously monitored through an online viscometer at the outlet of the double-screw reactor, and is fed back to an IPC flowmeter added in final polymerization to finely adjust the IPC melt flow. The viscosity of the final polymerization reaction solution can be controlled to 35.+ -.1 Pa.s when the apparatus is stably operated.
The final polymerization reaction liquid is directly subjected to continuous filtration and deaeration treatment to obtain spinning solution.
(2) Spinning: the obtained spinning dope is fed to a spinning device. The spinning adopts wet spinning, the spinning speed is 30m/min, the coagulating bath adopts sodium hydroxide aqueous solution with the mass concentration of 1%, and the temperature is 10 ℃. The nascent fiber is coiled into a fiber finished product through the links of subsequent washing, drying, hot drawing, oiling, coiling and the like.
The mechanical properties of the obtained finished fiber are as follows: the tensile strength is 4.9g/d, the elongation at break is 30%, and the elastic modulus is 120g/d.
(3) And (3) recovering a solvent: the pH of the spinning waste liquid is adjusted to about 8 by neutralizing with sodium hydroxide, then chloroform is used for extraction, the chloroform is separated from the extract by reduced pressure distillation, and the heavy component is rectified (vacuum degree-0.098 MPa, bottom temperature 150 ℃) to obtain the pure solvent DMPU with purity of 99.1%. Adding sodium carbonate into the raffinate phase containing lithium chloride, separating and precipitating, and then adding hydrochloric acid to reduce the precipitate into pure lithium chloride for recycling.
Comparative example 1:
the same procedure as in example 1 was conducted except that DMAc was used as a solvent for polymerization, that the operations of neutralizing hydrogen chloride with liquid ammonia and removing ammonium chloride by press filtration were added after the prepolymerization, and that water was used as a coagulation bath, using the conventional batch polymerization apparatus.
(1) Batch polymerization: adding MPD solid powder into dehydrated DMPU (water content 70 ppm), stirring for dissolving, and stirring under nitrogen protection, wherein the volume of the dissolving kettle is 5m 3 Adding 3185.8kg DMPU, 367.68kg MPD, dissolving at 15 deg.C for 30min. The dissolved MPD solution is cooled to-10 ℃, and then quantitatively, continuously and stably conveyed into a tubular prepolymerization reactor through a metering pump and a flowmeter; the IPC melt (60 ℃) is quantitatively, continuously and stably conveyed into a tubular prepolymerization reactor through a metering pump and a flowmeter to carry out prepolymerization reaction with MPD solution; the MPD solution is 1776.74kg/h, the IPC melt is 327.88kg/h and the IPC molar flow is 0.95 times of the MPD by regulating the flow. The residence time of the polymerization system in the tube reactor was about 10min, the prepolymerization temperature was 20℃and the stirring speed was 300rpm.
After the prepolymerization reaction is finished, the material flows into a gas-liquid mixing pump through a delivery pump, meanwhile, ammonia volatilized by liquid ammonia is continuously introduced into the gas-liquid mixing pump, and the flow rate of the ammonia is controlled at 53.8kg/h (1.96 times of the molar flow rate of IPC added in the prepolymerization) through the delivery pump and a flowmeter. And (3) feeding the mixed materials in the gas-liquid mixing pump into a neutralization kettle for primary neutralization, neutralizing hydrogen chloride generated by the prepolymerization reaction to generate ammonium chloride, and crystallizing and precipitating gradually. The temperature of the neutralization kettle is controlled to be not more than 25 ℃ and the residence time is 60min. And sampling and measuring the pH value of the outlet material of the neutralization reactor, wherein the pH value of the neutralized outlet material is about 5.5.
The material after primary neutralization flows into three filter presses which are arranged in parallel for filtering, and the ammonium chloride particles with the particle size larger than 30 mu m are retained. And intermittently operating a single filter press, and discharging the filter residues which are filtered and pressed into a dry state by the retained ammonium chloride. And collecting the filtered filtrate into a final polymerization temporary storage tank, uniformly stirring the filtrate after the press filtration is finished, taking the material for terminal amino analysis, and calculating the addition amount of the final polymerization IPC according to the terminal amino content.
The materials in the final polymerization temporary storage tank are conveyed into a double-screw polymerization reactor serving as a final polymerization reactor, meanwhile, IPC melt is fed into the final polymerization reactor, the feeding amount of IPC is 17kg/h, the final polymerization reaction temperature is 40 ℃, and the reaction time is 10min. The outlet of the final polymerization reactor was monitored by an on-line viscometer for the viscosity of the post-final polymerization material at 40.+ -. 3 Pa.s.
The final polymerized polymer solution is directly filtered and defoamed continuously to obtain spinning solution.
(2) Spinning: the obtained spinning dope is fed to a spinning device. The spinning adopts wet spinning, the spinning speed is 30m/min, the coagulating bath adopts pure water, and the temperature is 10 ℃. The nascent fiber is coiled into a fiber finished product through the links of subsequent washing, drying, hot drawing, oiling, coiling and the like.
The mechanical properties of the fiber finished product are as follows: the tensile strength is 4.3g/d, the elongation at break is 35%, and the elastic modulus is 108g/d.
Comparative example 2
Continuous polymerization was carried out in exactly the same manner as in example 1 except that a theoretical amount of calcium hydroxide powder was added to the final polymerization reaction liquid to neutralize hydrogen chloride, and the final polymerization reaction liquid was stirred under nitrogen protection for about 5 hours to ensure that the neutralization reaction was completed, and then the neutralized final polymerization reaction liquid was subjected to continuous filtration and deaeration treatment to obtain a spinning dope.
Then spinning is carried out by adopting the same spinning technology as in comparative example 1, and the mechanical properties of the obtained finished fiber are as follows: the tensile strength is 3.8g/d, the elongation at break is 33%, and the elastic modulus is 98g/d.
Fiber performance stability evaluation: the fiber performance stability was measured by randomly sampling 5 times in 3 hours, and it was found that the mechanical property deviation of the fibers prepared in examples 1 and 2 was <5%, whereas the performance deviation of comparative example 1 was nearly 10%, whereas comparative example 2 was more than 15%, and the fiber bundle performance was inevitably significantly affected by the number of filaments produced by spinning.
Industrial applicability
The poly m-phenylene isophthalamide solution, the meta-aramid spinning solution and the preparation method thereof can be widely used for preparing various meta-aramid fibers in industry.
Claims (11)
1. The preparation method of the poly m-phenylene isophthalamide solution or meta-aramid spinning solution is characterized by comprising the following steps:
polymerizing m-phenylenediamine and m-phthaloyl chloride in a solvent to obtain a polymerization solution, and optionally defoaming and filtering the polymerization solution;
wherein the solvent comprises a compound represented by the following formula (1):
wherein R is 1 And R is 2 Independently of each other, methyl, ethyl or propyl, n being an integer from 1 to 5;
wherein the step of neutralizing the hydrogen chloride in the polymerization liquid is not included.
2. The preparation method of the meta-aramid fiber is characterized by comprising the following steps of:
spinning by using meta-aramid spinning stock solution to obtain as-spun fibers, and then washing the as-spun fibers with water and optionally drying, oiling and winding to obtain meta-aramid fibers;
wherein the spinning process uses an aqueous alkali solution as a coagulation bath,
wherein the meta-aramid spinning dope comprises a polyisophthaloyl metaphenylene diamine solution obtained by the method for preparing a polyisophthaloyl metaphenylene diamine solution according to claim 1, comprising polyisophthaloyl metaphenylene diamine and a solvent comprising a compound represented by the following formula (1):
wherein R is 1 And R is 2 Independently of each other, methyl, ethyl or propyl, n being an integer from 1 to 5.
3. The method for producing meta-aramid fiber according to claim 2, wherein the alkali in the alkali aqueous solution is at least one selected from sodium hydroxide and potassium hydroxide.
4. The method for producing a meta-aramid fiber as claimed in claim 2 or 3, further comprising a step of recovering a solvent from a spinning waste liquid generated by coagulation bath and water washing, the solvent recovering step comprising:
neutralizing the spinning waste liquid by using alkali, extracting by using an extracting agent, performing reduced pressure distillation on an organic phase, and rectifying heavy components obtained by the reduced pressure distillation.
5. A method for producing meta-aramid fiber according to claim 2 or 3, wherein in the formula (1), R 1 And R is 2 Independently of one another, methyl or ethyl, n being 1, 2 or 3.
6. The method for producing meta-aramid fiber of claim 5, wherein R 1 And R is 2 All represent methyl groups, and n is 1 or 2.
7. The method for producing a meta-aramid fiber according to claim 2 or 3, wherein the polyisophthaloyl metaphenylene diamine solution further contains a solubilizing salt which is one or more selected from halides of alkali metals or alkaline earth metals; the content of the auxiliary soluble salt is 0 to 5wt% relative to the solvent.
8. The method for preparing meta-aramid fiber of claim 7, wherein the solubilizing salt is one or more selected from the group consisting of chlorides of alkali metals or alkaline earth metals.
9. The method for preparing meta-aramid fiber of claim 8, wherein the solubilizing salt is one or more selected from the group consisting of calcium chloride and lithium chloride.
10. The method for producing a meta-aramid fiber according to claim 2 or 3, wherein the polymetaphenylene isophthalamide solution further contains hydrogen chloride, the content of which is 3 to 7wt%.
11. The method for producing a meta-aramid fiber according to claim 2 or 3, wherein the content of the m-phenylene isophthalamide in the m-phenylene isophthalamide solution is 14 to 22wt%; the viscosity of the poly (m-phenylene isophthalamide) solution is 10-80 Pa.s.
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