CN116272739A - Continuous polymerization device and method for poly (m-phenylene isophthalamide) - Google Patents
Continuous polymerization device and method for poly (m-phenylene isophthalamide) Download PDFInfo
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 250
- 238000000034 method Methods 0.000 title claims abstract description 54
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 title claims description 34
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 141
- 238000002156 mixing Methods 0.000 claims abstract description 57
- 238000001914 filtration Methods 0.000 claims abstract description 56
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- 238000004140 cleaning Methods 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- -1 polymetaphenylene isophthalamide Polymers 0.000 claims abstract description 12
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 211
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 208
- 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 143
- 239000000463 material Substances 0.000 claims description 123
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 117
- 239000000243 solution Substances 0.000 claims description 105
- 238000003860 storage Methods 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 239000000047 product Substances 0.000 claims description 45
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 42
- 238000004090 dissolution Methods 0.000 claims description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 33
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 33
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 33
- 235000019270 ammonium chloride Nutrition 0.000 claims description 21
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- 238000002347 injection Methods 0.000 claims description 14
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- 238000001816 cooling Methods 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 10
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 9
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
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- 238000010992 reflux Methods 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000000087 stabilizing effect Effects 0.000 claims description 3
- 239000000523 sample Substances 0.000 claims 1
- 238000009987 spinning Methods 0.000 abstract description 23
- 238000003756 stirring Methods 0.000 abstract description 22
- 239000004760 aramid Substances 0.000 abstract description 15
- 229920003235 aromatic polyamide Polymers 0.000 abstract description 12
- 238000012546 transfer Methods 0.000 abstract description 12
- 229920006231 aramid fiber Polymers 0.000 abstract description 7
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- 238000012369 In process control Methods 0.000 description 67
- 210000004544 dc2 Anatomy 0.000 description 67
- 238000004190 ion pair chromatography Methods 0.000 description 67
- 229910021529 ammonia Inorganic materials 0.000 description 38
- 208000012886 Vertigo Diseases 0.000 description 22
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
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- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 102100027340 Slit homolog 2 protein Human genes 0.000 description 3
- 101710133576 Slit homolog 2 protein Proteins 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- 230000008018 melting Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
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- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
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- 150000008430 aromatic amides Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide 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
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- 230000007774 longterm Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
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- 230000001376 precipitating effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 230000009897 systematic effect Effects 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
- B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/0004—Processes in series
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyamides (AREA)
Abstract
The invention relates to a continuous polymerization device and a continuous polymerization method of polymetaphenylene isophthalamide. The device comprises a prepolymerization unit, a primary neutralization unit, a final polymerization unit and a secondary neutralization unit in sequence, wherein the prepolymerization unit is matched with a dynamic tubular reactor by utilizing a premixer, a microchannel reactor and a dynamic tubular reactor, so that the heat transfer and mixing efficiency problems in the continuous polymerization process are solved; the continuous filtration of the neutralization products is realized by adopting a plurality of parallel dynamic self-cleaning filters in the primary neutralization unit; in the final polymerization stage, a final polymerization reactor with self-cleaning or strong mixing and stirring functions is adopted to solve the mixing problem of high-viscosity polymer liquid. The product polymerization liquid obtained by the method has few impurities and uniform viscosity, is suitable for continuously preparing meta-aramid spinning dope in a large scale, has good mechanical properties, and can greatly improve the quality of meta-aramid fibers.
Description
Technical Field
The invention relates to a continuous polymerization device and a method for poly (m-phenylene isophthalamide), belonging to the field of polymer reaction engineering.
Background
Meta-aramid is a special fiber composed of poly (m-phenylene isophthalamide) (PMIA for short), 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.
The polymerization of PMIA is a key ring in the production of meta-aramid fiber, and at present, a low-temperature solution polycondensation method is generally adopted, namely, monomer m-phenylenediamine (MPD) and isophthaloyl chloride (IPC) are spontaneously polymerized in a solvent N, N-dimethylacetamide (DMAc) to generate PMIA polymer. The PMIA polymerization system is simple, the polymerization process is simple and easy to operate, industrial production is realized in China for decades, industrial mass production is realized in China, and the reaction has the characteristics of large reaction heat release amount, multiple side reactions, strong reaction corrosiveness and the like, so that the PMIA polymerization system is faced with a plurality of very complex problems in actual industrial production; on the other hand, unstable polymerization (or obvious difference among batches) caused by batch polymerization is an important difficult problem for restricting the development of meta-aramid in China.
The batch polymerization of PMIA is to add most of IPC into MPD/DMAc solution in batch to react in the pre-polymerization stage, so as to keep the polymerization temperature not too high, reduce the occurrence of side reaction and make IPC and MPD fully and uniformly mixed for a long time. In the neutralization stage, liquid ammonia (ammonia gas) is added to neutralize hydrogen chloride generated by the prepolymerization, and generated ammonium chloride is crystallized and separated out and removed by filter pressing. In the final polymerization stage, adding a small amount of residual IPC to continue polymerization, finally adding an alkaline organic matter to neutralize a small amount of hydrogen chloride generated by final polymerization, finally adjusting the viscosity of a polymerization system, filtering and defoaming, and then entering a spinning stage.
There have been a great deal of literature reports on batch polymerization of PMIA. For example, the batch polymerization process of PMIA is described in detail in both patent documents 1 and 2. As can be seen from the batch polymerization process, the polymerization of PMIA was completed by batch polymerization for a long period of time (5 hours or more), and the operation was complicated and the batch was unstable.
A variety of continuous polymerization schemes have been reported. Wherein a tubular reactor or a twin screw extruder is used as a PMIA polymerization main reactor in order to solve the problems of monomer mixing and reaction heat transfer in PMIA continuous polymerization. For example, patent document 3 discloses a method in which PMIA is prepolymerized by a tubular reactor and then subjected to neutralization and cyclic filtration. This solution is continuous prepolymerization without problems, but the recycling and neutralization after filtration by a filter press have a serious effect on the continuous polymerization. It is well known that the equimolar ratio of the monomers required for the step-wise polymerization is very demanding, whereas the process of filtering the ammonium chloride particles by pressure filtration in this solution severely damages the prepolymer flow and the prepolymer stability. That is, in the subsequent polymerization reaction, the amount of the additional IPC is difficult to be added in stoichiometric proportion. This is because pressure filtration is a discontinuous and unstable filtration process. The flow rate of the prepolymer is unstable, the prepolymer also continues to react during the neutralization and filtration, and the inconsistent residence time of the prepolymer caused by filter pressing can lead to difficult continuous and accurate addition of IPC in the subsequent polymerization, thereby causing polymerization fluctuation. Further, patent document 4 uses a twin screw extruder as a final polymerization reactor to complete polymerization in the latter half of PMIA. The double screw extruder has self-cleaning function, good mixing and reaction heat transfer effect, but high cost and complex structure. Moreover, this solution does not allow continuous operation of the prepolymerization and neutralization process, so that continuous polymerization of PMIA is not completely achieved.
In order to facilitate the continuous polymerization operation, a polymerization scheme in which IPC is added at one time has also been reported many times (for example, patent document 5). However, the biggest problem of the polymerization scheme with one-time addition of IPC is that the exothermic amount of reaction is large in the initial stage of polymerization, and the heat transfer of reaction is a great challenge, which is particularly disadvantageous for industrial mass production; in order to reduce the damage to the polymerization continuity caused by the hydrogen chloride neutralization step, neutralization of hydrogen chloride with an inorganic base or an alkali metal oxide (e.g., calcium hydroxide or calcium oxide) is widely used (for example, patent document 6). However, neutralization of hydrogen chloride with such materials produces water, which upon hydrolysis of the acid chloride reduces the molecular weight of the PMIA polymer and broadens the molecular weight distribution of the polymer; in addition, the chloride salt generated by neutralization can have obvious tackifying effect on PMIA polymer solution, on one hand, the subsequent spinning is obviously influenced, and on the other hand, the process of removing the chloride salt from the filament bundles is relatively complicated.
From the above analysis, it can be seen that the development of meta-aramid field has a real and urgent need to investigate new industrially available continuous polymerization schemes of PMIA.
Citation literature:
patent document 1: CN103113576a;
patent document 2: CN103497328A;
Patent document 3: CN109400873a;
patent document 4: CN1443882a;
patent document 5: CN101736431a;
patent document 6: CN100455706C.
Disclosure of Invention
Problems to be solved by the invention
The prior art solutions still have some problems or drawbacks, such as:
1) The reaction heat transfer becomes a big problem by adding IPC once, and for the polymerization production line of thousands of tons of industrial grade annual production, the current polymerization reactor is difficult to ensure the monomer mixing efficiency and the heat transfer efficiency at the same time. For example, a twin-screw extruder (kneader) is an aromatic amide polymerization reactor widely used at present, but the mixing and heat transfer effects of twin screws are poor due to low material viscosity in the PMIA prepolymerization stage; the tubular reactor has good mixing effect in the prepolymerization stage, but heat transfer and yield are difficult to be compatible;
2) Although the alkali metal oxide is used for neutralizing the hydrogen chloride, the filtering link does not exist, but the chloride generated by neutralization can be brought to a spinning working section, so that the complexity of spinning operation is greatly increased, and the meta-aramid spinning solution with high salt is very difficult to spin the high Jiang Jianwei aramid;
3) In the ammonia neutralization hydrogen chloride scheme, ammonium chloride is filtered again until the polymerization end point, and the viscosity of the polymerization solution is high at this time, so that the generated ammonium chloride particles are fine, and the filtering is difficult.
Long-term industrial application practices prove that in order to realize continuous polymerization of meta-aramid, the following problems must be solved:
1) The problem of continuous addition, efficient mixing and reaction heat transfer of the monomer IPC in the prepolymerization stage;
2) The continuous stable filtration problem in the ammonia neutralization stage;
3) Continuous and efficient addition and mixing of residual IPC and alkaline organic matters in the final polymerization reaction stage;
4) And the viscosity of the spinning solution is automatically adjusted before entering the spinning working section.
Solution for solving the problem
Aiming at the problems, the inventor of the invention has conducted intensive researches for a long time, and provides a continuous polymerization device and a continuous polymerization method of poly (m-phenylene isophthalamide), which solve the problems of continuous and efficient mixing and reaction heat transfer of IPC (IPC) by adopting a mode of combining a premixer, a microchannel mixer and a tubular reactor in a prepolymerization stage; further, in the ammonia neutralization stage, a plurality of self-cleaning filters connected in parallel are adopted to realize continuous and stable filtration of ammonium chloride, so that the flow stability of polymer liquid is ensured; further, in the final polymerization stage, a final polymerization reactor with self-cleaning or strong mixing and stirring functions is adopted to solve the problem of mixing the high-viscosity PMIA polymer liquid with IPC and a neutralizer; further, finally, the viscosity of the spinning solution is automatically detected and regulated by an online viscometer. Through the series of targeted improvement measures, the meta-aramid fiber is stably and continuously polymerized.
Specifically, the present invention solves the technical problems of the present invention by the following means.
[1] A continuous polymerization device of poly (m-phenylene isophthalamide) sequentially comprises a prepolymerization unit, a primary neutralization unit, a final polymerization unit and a secondary neutralization unit, wherein
The prepolymerization unit comprises a premixer, a microchannel reactor and a dynamic tubular reactor which are sequentially connected, wherein the premixer is provided with an m-phenylenediamine solution inlet and an m-phthaloyl chloride melt inlet;
the primary neutralization unit comprises a gas-liquid mixer, a primary neutralization reactor and a primary filter which are sequentially connected, wherein an ammonia gas inlet is further formed in the gas-liquid mixer, and the ammonia gas inlet is connected with an ammonia gas storage tank; the primary filter comprises more than two dynamic self-cleaning filters which are arranged in parallel;
the final polymerization unit comprises a final polymerization reactor, wherein the final polymerization reactor is a continuous reactor, an isophthaloyl dichloride melt inlet is arranged on the final polymerization reactor, and the isophthaloyl dichloride melt inlet is connected with an isophthaloyl dichloride melt storage tank;
the secondary neutralization unit comprises a secondary neutralization reactor and a secondary filter which are sequentially connected, wherein an alkaline organic matter inlet is further formed in the secondary neutralization reactor, and the alkaline organic matter inlet is connected with an alkaline organic matter storage tank.
[2] The apparatus according to [1], wherein a metaphenylene diamine batching unit and an isophthaloyl chloride batching unit are further included upstream of the prepolymerization unit, wherein
The m-phenylenediamine dosing unit comprises a m-phenylenediamine dissolution tank, a m-phenylenediamine solution temporary storage tank, a first overhead tank and a m-phenylenediamine solution meter which are connected in sequence; wherein the outlet of the m-phenylenediamine solution meter is connected with the m-phenylenediamine solution inlet of the premixer; preferably, the first high-level tank is provided with a return pipeline connected to the m-phenylenediamine solution temporary storage tank, and the return pipeline is used for keeping the liquid level in the first high-level tank constant;
the isophthaloyl dichloride batching unit comprises an isophthaloyl dichloride melter, an isophthaloyl dichloride melt storage tank, a second overhead tank and an isophthaloyl dichloride melt meter; the outlet of the intermediate phthaloyl chloride melt meter is connected with the isophthaloyl chloride melt inlet of the pre-mixer; preferably, a reflux pipeline connected to the isophthaloyl dichloride melt storage tank is arranged on the second head tank, and the reflux pipeline is used for keeping the liquid level in the second head tank constant;
the m-phenylenediamine batching unit and the m-phthaloyl chloride batching unit are also provided with inert gas protection systems.
[3] The apparatus according to [2], wherein the m-phenylenediamine solution temporary storage tank is provided with a cooling jacket; a heat exchanger is arranged between the m-phenylenediamine solution temporary storage tank and the first high-level tank; the isophthaloyl dichloride storage tank and the second head tank are provided with heat preservation devices.
[4] The apparatus according to any one of [1] to [3], wherein the primary neutralization unit further comprises an ammonia gas feed metering and controller for stabilizing an ammonia gas feed amount.
[5] The apparatus of any one of [1] to [3], wherein the final polymerization unit further comprises a viscosity detector configured to detect a viscosity value of the final polymerization reactor outlet material and feed back to the isophthaloyl chloride melt feed controller, and an isophthaloyl chloride melt feed controller that adjusts a feed rate of isophthaloyl chloride according to the viscosity value fed back by the viscosity detector.
[6] The apparatus of any one of [1] to [3], wherein the secondary filter comprises two or more filters connected in parallel; the premixer is a co-injection mixer or a counter-injection mixer; the gas-liquid mixer is a gas-liquid mixing pump; the final polymerization reactor is a continuous tubular reactor, a LIST reactor or a double-screw reactor; the primary neutralization reactor and the secondary neutralization reactor are dynamic tubular reactors.
[7] A continuous polymerization process of polymetaphenylene isophthalamide, wherein the process comprises a prepolymerization step, a primary neutralization step, a final polymerization step and a secondary neutralization step in this order, and optionally further comprises a compounding step before the prepolymerization step, wherein
The batching step comprises continuously metering and feeding a m-phenylenediamine solution and an m-phthaloyl chloride melt;
the pre-polymerization step comprises the steps of sequentially pre-mixing m-phenylenediamine and isophthaloyl chloride, carrying out primary pre-polymerization and secondary pre-polymerization to obtain a pre-polymerization product containing a polymetaphenylene isophthalamide oligomer and hydrogen chloride, wherein the primary pre-polymerization is carried out in a micro-channel reactor, and the secondary pre-polymerization is carried out in a dynamic tubular reactor;
the primary neutralization step comprises the steps of contacting a prepolymerization product with ammonia gas to neutralize hydrogen chloride therein and filtering the neutralized product to remove ammonium chloride generated by neutralization, so as to obtain primary neutralization filtrate, wherein the filtering is performed in a dynamic self-cleaning filter; wherein, the pH value of the neutralized product is preferably monitored, and the dosage of ammonia gas is adjusted according to the pH value, so that the pH value of the neutralized product is 5.0-5.5;
the final polymerization step comprises the steps of enabling a primary neutralization filtrate to be in contact with m-phthaloyl chloride melt for final polymerization reaction to obtain a final polymerization product containing poly m-phthaloyl m-phenylenediamine polymer and hydrogen chloride, wherein the viscosity of the final polymerization product is preferably monitored, and the dosage of the m-phthaloyl chloride is adjusted according to the viscosity of the final polymerization product;
The secondary neutralization step includes contacting the final polymerization product with a basic organic compound to neutralize the hydrogen chloride therein.
[8] The method according to [7], wherein,
in the batching step, the dosage ratio of the isophthaloyl dichloride to the m-phenylenediamine in terms of mole is (0.80-0.95): 1, a step of; the concentration of the m-phenylenediamine solution is 0.8-1.1 mol/L, and the temperature is-10-0 ℃; the temperature of the isophthaloyl dichloride melt is 55-65 ℃;
in the pre-polymerization step, the pre-mixing time is 1-5 s, the residence time of the materials in the micro-channel reactor is 0.5-5 min, the residence time of the materials in the dynamic tubular reactor is 5-30 min, and the reaction temperature in the micro-channel reactor and the dynamic tubular reactor is below 20 ℃;
in the primary neutralization step, the dosage ratio of ammonia gas to the isophthaloyl dichloride in the prepolymerization step is (1.90-1.99): 1, a step of;
in the final polymerization step, the dosage ratio of the isophthaloyl dichloride to the m-phenylenediamine in the pre-polymerization step is (0.045-0.250) in terms of mole: 1, a step of; the reaction temperature in the final polymerization reactor is-10-50 ℃; the residence time of the materials in the final polymerization reactor is 5-60 min; the viscosity of the final polymerization product is 30-100 Pa.s;
In the secondary neutralization step, the dosage of the alkaline organic matters is 2.01 to 2.10 times of the molar quantity of the added isophthaloyl dichloride in the final polymerization step.
[9] A continuous polymerization process of polymetaphenylene isophthalamide, wherein the polymerization is carried out by the apparatus of any one of [1] to [6 ].
[10] The method according to [9], wherein the temperature of the material in the primary neutralization unit neutralization reactor is 30 ℃ or lower, and the material residence time is 60 to 120min; the temperature of the materials in the secondary neutralization unit neutralization reactor is below 50 ℃, and the material residence time is 20-40 min.
ADVANTAGEOUS EFFECTS OF INVENTION
The continuous polymerization device and method for the poly (m-phenylene isophthalamide) have compact polymerization equipment, stable and controllable conditions, high raw material utilization rate and high production efficiency, and can realize stable and continuous polymerization of meta-aramid fibers.
Specifically, compared with the prior art, the continuous polymerization device and method of the poly (m-phenylene isophthalamide) have the following beneficial effects:
1) The problems of heat transfer and mixing efficiency in the continuous polymerization process are solved by utilizing the cooperation of the premixer, the micro-channel reactor and the dynamic tubular reactor;
2) The continuous filtration of the neutralization product is realized by adopting a plurality of parallel dynamic self-cleaning filters, and filter residues can be used for preparing meta-aramid fibrids, so that the utilization rate of raw materials is improved;
3) In the final polymerization stage, a final polymerization reactor with self-cleaning or strong mixing and stirring functions is adopted to solve the mixing problem of high-viscosity polymer liquid; the viscosity of the spinning solution is regulated and controlled in real time by using an online viscometer;
4) The product polymerization liquid has few impurities and uniform viscosity, can be adjusted in real time within a certain range according to the requirement, can be directly used for spinning after defoamation, and is suitable for continuously preparing meta-aramid spinning stock solution in a large scale;
5) The fiber prepared from the continuous polymerization spinning solution has good mechanical properties, can greatly improve the quality of meta-aramid fiber, and particularly has good improving effect on the quality and stability of meta-aramid fiber filaments and aramid paper.
Drawings
FIGS. 1-4 are schematic illustrations of apparatus configurations and process flows in embodiments of the present invention;
FIG. 5 is a schematic view of a premixer structure in one embodiment of the present invention.
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 this specification, the terms "connected," "connected," or the like, as used with respect to various components of a device or apparatus, mean that material may be transferred from one component to another, including the case where the components are directly connected or not directly connected, and, for the case where the components are not directly connected, may be connected by pipes, or via other components, etc.
In this specification, the term "sequentially" as used with respect to the individual components of the apparatus or device means that material can pass through the components in the order described.
In this specification, the description of "upstream" or "downstream" with respect to the relative positions of the various components of the apparatus or device is based on the description of the direction of flow of the material when the apparatus or device is in operation.
In the present specification, unless explicitly stated otherwise, "m-phenylenediamine solution" means an N, N-dimethylacetamide solution of m-phenylenediamine.
"percent" or "%" as used in this specification means mole percent or mole percent unless otherwise specified.
In the present specification, a numerical range indicated by "above" or "below" is a numerical range including the present number.
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 continuous polymerization apparatus for polymetaphenylene isophthalamide, which comprises a prepolymerization unit, a primary neutralization unit, a finishing unit and a secondary neutralization unit in this order, wherein
The prepolymerization unit comprises a premixer, a microchannel reactor and a dynamic tubular reactor which are sequentially connected, wherein the premixer is provided with an m-phenylenediamine solution inlet and an m-phthaloyl chloride melt inlet;
the primary neutralization unit comprises a gas-liquid mixer, a primary neutralization reactor and a primary filter which are sequentially connected, wherein an ammonia gas inlet is further formed in the gas-liquid mixer, and the ammonia gas inlet is connected with an ammonia gas storage tank; the primary filter comprises more than two dynamic self-cleaning filters which are arranged in parallel;
the final polymerization unit comprises a final polymerization reactor, wherein the final polymerization reactor is a continuous reactor, an isophthaloyl dichloride melt inlet is arranged on the final polymerization reactor, and the isophthaloyl dichloride melt inlet is connected with an isophthaloyl dichloride melt storage tank;
The secondary neutralization unit comprises a secondary neutralization reactor and a secondary filter which are sequentially connected, wherein an alkaline organic matter inlet is further formed in the secondary neutralization reactor, and the alkaline organic matter inlet is connected with an alkaline organic matter storage tank.
In one embodiment, the apparatus of the present invention further comprises a metaphenylene diamine batching unit and an isophthaloyl chloride batching unit upstream of the prepolymerization unit.
The individual components of the device according to the invention are described below.
Batching unit
In one embodiment, the m-phenylenediamine dosing unit comprises a m-phenylenediamine dissolution tank, a m-phenylenediamine solution temporary storage tank, a first high-level tank and a m-phenylenediamine solution meter which are connected in sequence; wherein the outlet of the m-phenylenediamine solution meter is connected with the m-phenylenediamine solution inlet of the premixer.
In one embodiment, a return line connected to the meta-phenylenediamine solution holding tank is provided on the first head tank for keeping the liquid level in the first head tank constant. The first high-level tank is used for keeping the pressure and flow of the m-phenylenediamine solution stable. In a preferred embodiment, the first high-level tank and the pulse-free delivery pump connected with the first high-level tank are combined to keep the pressure and flow rate of the m-phenylenediamine solution stable to the greatest extent.
In one embodiment, a solvent inlet and a m-phenylenediamine inlet are arranged on the m-phenylenediamine dissolution tank, the solvent inlet is connected with a solvent storage tank, the m-phenylenediamine inlet is connected with a m-phenylenediamine melter, and the inlet of the m-phenylenediamine melter is connected with a m-phenylenediamine feeder. The m-phenylenediamine feeder preferably comprises a metering pump and/or a flow meter.
In one embodiment, a m-phenylenediamine dissolution mixer is arranged upstream of the m-phenylenediamine dissolution tank, a solvent inlet and a m-phenylenediamine inlet are arranged on the m-phenylenediamine dissolution mixer, the solvent inlet is connected with a solvent storage tank, the m-phenylenediamine inlet is connected with a m-phenylenediamine melter, and the inlet of the m-phenylenediamine melter is connected with a m-phenylenediamine feeder. The m-phenylenediamine feeder preferably comprises a metering pump and/or a flow meter.
In one embodiment, the m-phenylenediamine dissolution tank may be formed by sequentially connecting two or more m-phenylenediamine dissolution vessels in series so that the m-phenylenediamine is sufficiently dissolved.
In one embodiment, one or more of the m-phenylenediamine dissolution tank (part or all of the plurality of m-phenylenediamine dissolution vessels, preferably at least the most downstream m-phenylenediamine dissolution vessel) and the m-phenylenediamine solution temporary storage tank is further equipped with a m-phenylenediamine concentration meter to detect (preferably continuously detect) the concentration of m-phenylenediamine.
In one embodiment, the m-phenylenediamine dissolution tank and/or the m-phenylenediamine solution temporary storage tank is provided with a cooling jacket for cooling the m-phenylenediamine solution.
In one embodiment, a heat exchanger is further arranged between the m-phenylenediamine solution temporary storage tank and the first high-level tank, and the heat exchanger is used for further cooling the m-phenylenediamine solution, so that the m-phenylenediamine solution is further cooled and maintained in a low-temperature state, and the temperature of the m-phenylenediamine solution is prevented from being too high after the m-phenylenediamine solution is mixed with the m-phthaloyl chloride melt.
In one embodiment, the m-phenylenediamine solution meter comprises a metering pump and/or a flow meter.
In one embodiment, the isophthaloyl dichloride dosing unit comprises an isophthaloyl dichloride melter, an isophthaloyl dichloride melt tank, a second head tank, and an isophthaloyl dichloride melt meter; the outlet of the intermediate phthaloyl chloride melt meter is connected with the isophthaloyl chloride melt inlet of the pre-mixer.
In one embodiment, the second head tank is provided with a return line connected to the isophthaloyl dichloride melt tank, the return line being used to keep the liquid level in the second head tank constant. The second overhead tank also serves to stabilize the pressure and flow of isophthaloyl dichloride.
In one embodiment, the isophthaloyl dichloride melt storage tank and the second head tank are equipped with a holding device for holding the isophthaloyl dichloride melt in a molten state.
In one embodiment, the m-phenylenediamine and/or isophthaloyl dichloride dosing units are also provided with an inert gas protection system to prevent moisture absorption or deterioration of the m-phenylenediamine and isophthaloyl dichloride in contact with air during operation of the apparatus.
Prepolymerization unit
In the device, the prepolymerization unit comprises a premixer, a microchannel reactor and a dynamic tubular reactor which are connected in sequence, wherein the premixer is provided with an m-phenylenediamine solution inlet and an m-phthaloyl chloride melt inlet.
The pre-mixer has the function of preliminarily mixing the m-phenylenediamine solution and the m-phthaloyl chloride melt, so that the m-phenylenediamine solution and the m-phthaloyl chloride melt are fully mixed in a short time, the stability of polymerization reaction is facilitated, the heat dissipation efficiency is high, and the polymerization efficiency can be greatly improved.
In a preferred embodiment, the premixer is a co-injection mixer or a counter-injection mixer.
In one embodiment, the premixer is a co-injection mixer. In a preferred embodiment, a schematic structure of a co-injection mixer used in the apparatus of the present invention is shown in FIG. 5, the mixer comprising a isophthaloyl dichloride injection system 1 and a m-phenylenediamine solution injection slit 2, the m-phenylenediamine solution injection slit 2 being connected to a m-phenylenediamine solution flow passage 4 formed by a space between an outer wall 3 of the mixer and an inner barrel 5 of the mixer, the interior of the inner barrel 5 of the mixer being formed with a mixing chamber 6. When the device is operated, the m-phthaloyl chloride melt A is sprayed into the mixing cavity 6 from the phthaloyl chloride spraying system 1, the m-phenylenediamine solution B enters the mixing cavity 6 from the m-phenylenediamine solution spraying slit 2, and the two materials are mixed in the mixing cavity 6.
In one embodiment, the microchannel reactor may be made of polytetrafluoroethylene, stainless steel or nickel-based alloy to withstand corrosion from hydrogen chloride generated by the reaction.
The present invention is not particularly limited to the specific construction of the microchannel reactor, and those skilled in the art will understand that since the microchannel reactor is already a mature industrial device, microchannel reactors of different internal structures can be used under conditions of ensuring flow rate and satisfying non-blocking materials, controllable temperature, etc.
The present invention is not particularly limited with respect to the specific construction, materials, dimensions, etc. of the dynamic tubular reactor, and any suitable dynamic tubular reactor in the art may be used. In one embodiment, the tube diameter and length of the dynamic tube reactor are selected based on the flow rate of the prepolymerization solution. In one embodiment, the dynamic tubular reactor is equipped with stirring means which are capable of stable continuous stirring and mixing of the polymer mass and stable delivery to the outlet, in this embodiment the stirring paddles are preferably rotated at a speed of 50 to 300rpm.
The device can realize the efficient mixing of the isophthaloyl dichloride melt and the m-phenylenediamine solution and the effective removal of the reaction heat by combining the pre-polymerization unit, the micro-channel reactor and the dynamic tubular reactor, thereby being beneficial to improving the uniformity of the molecular weight of the product and the spinning performance of the polymer solution.
The reasons for achieving the above effects include, but are not limited to: because the solidification point of the isophthaloyl dichloride is about 45 ℃, the low-temperature solution of the m-phenylenediamine is easy to solidify, if the solution is directly fed into the microchannel reactor without passing through the premixer, the internal channel of the microchannel reactor is blocked, and if the solution is directly fed into the tubular reactor without passing through the premixer and the microchannel reactor, the qualified polymer material is difficult to obtain because of poor mixing effect of the tubular reactor. Furthermore, it is still difficult to mix the two monomers to a microscopically homogeneous state using a premixer, and thus a microchannel reactor is provided downstream of the premixer to allow further mixing of the two monomers.
In a preferred embodiment, both the premixer and the microchannel reactor are equipped with cooling means to ensure removal of heat of reaction.
Primary neutralization unit
In the device, the primary neutralization unit comprises a gas-liquid mixer, a primary neutralization reactor and a primary filter which are sequentially connected, wherein an ammonia gas inlet is further formed in the gas-liquid mixer, the ammonia gas inlet is connected with an ammonia gas storage tank, and the primary filter comprises more than two dynamic self-cleaning filters which are arranged in parallel.
In one embodiment, the primary neutralization unit further comprises an ammonia feed metering and controller for stabilizing the ammonia feed. In a specific embodiment, the ammonia feeding metering and controlling device comprises an ammonia mass flowmeter and an electromagnetic valve, wherein the instantaneous flow and the accumulated flow of the ammonia are metered through the ammonia mass flowmeter, the flow of the ammonia is automatically controlled by interlocking the electromagnetic valve and the ammonia mass flowmeter, and the stability of the flow of the ammonia is ensured.
Specifically, the theoretical amount of hydrogen chloride generated by polymerization is calculated according to the material ratio of the prepolymerization unit, and then the theoretical amount of ammonia is calculated according to the theoretical amount. And measuring the ammonia flow by using an ammonia mass flowmeter, and adjusting the opening of a valve to adjust the ammonia flow once the deviation of the ammonia flow from a set value is detected.
The present invention is not particularly limited to gas-liquid mixers, and commercially mature continuous gas-liquid mixer types can be used, including but not limited to jet gas-liquid mixers, static gas-liquid mixers, and the like. The size of the mixer may be specifically selected based on the gas-liquid flow rate. In one embodiment, the gas-liquid mixer is a gas-liquid mixing pump.
In one embodiment, the primary filter is equipped with a differential pressure monitoring system to monitor the differential pressure between the material inlet and the material outlet of the dynamic self-cleaning filter.
When the device is in operation, one part of the two or more dynamic self-cleaning filters are in an operation state (namely, a state of filtering materials), and the other dynamic self-cleaning filters are in a cleaning or standby state. When the differential pressure monitoring system detects that the differential pressure of the dynamic self-cleaning filter in the running state is higher than a set value, the dynamic self-cleaning filter is switched to a cleaning state, and one or more of the dynamic self-cleaning filters in the standby state are switched to the running state.
In the cleaning state, the dynamic self-cleaning filter is cleaned by a solvent (preferably the solvent used for polymerization), and the filter residue obtained by cleaning can be used for preparing fibrids.
In one embodiment, the dynamic self-cleaning filter is selected from the group consisting of scraper, brush, and disc self-cleaning filters, and rotary press filters.
In one embodiment, the dynamic self-cleaning filter is a disc-type self-cleaning filter. The disc type self-cleaning filter uses a cleaning disc with a spring to move up and down in a filter screen so as to remove filter residues on the filter screen. The filtrate is filtered from top to bottom by a filter screen from inside to outside, and filter residues are trapped on the surface of the filter screen and are removed by a cleaning disc and then are collected in a collecting chamber. More specifically, during the downward movement of the disc, all the filter residues are removed by the disc to the collection chamber, during the upward movement of the disc, the filter residues are removed from the surface of the filter screen, and the fluid then drives the filter residues through the disc into the collection chamber.
In other embodiments, the dynamic self-cleaning filter is a scraper or brush self-cleaning filter, which operates on a principle similar to a disc-type self-cleaning filter.
The device of the invention can fully ensure the filtration efficiency and enable the device to continuously operate by using more than two dynamic self-cleaning filters which are arranged in parallel as the primary filter.
Final aggregation unit
In the device, the final polymerization unit comprises a final polymerization reactor, wherein the final polymerization reactor is a continuous reactor, and is further provided with an isophthaloyl dichloride melt inlet which is connected with an isophthaloyl dichloride melt storage tank.
The final polymerization unit can be equipped with a separate isophthaloyl dichloride melt storage tank, or can share the isophthaloyl dichloride melt storage tank with the batching unit.
In one embodiment, the final polymerization unit further comprises a viscosity detector configured to detect a viscosity value of the final polymerization reactor outlet material and feed back to the isophthaloyl dichloride melt feed controller, and the isophthaloyl dichloride melt feed controller adjusts the amount of isophthaloyl dichloride feed based on the viscosity value fed back by the viscosity detector.
Specifically, when the viscosity value fed back by the viscosity detector is below the threshold value, the isophthaloyl dichloride melt feed controller will automatically increase the feed rate of isophthaloyl dichloride until it reaches above the threshold value.
In one embodiment, the final polymerization mixer is a continuous tube reactor, a twin screw reactor, or a LIST reactor.
Secondary neutralization unit
In the device, the secondary neutralization unit comprises a secondary neutralization reactor and a secondary filter which are sequentially connected, wherein the secondary neutralization reactor is also provided with an alkaline organic matter inlet, and the alkaline organic matter inlet is connected with an alkaline organic matter storage tank.
In one embodiment, the secondary neutralization reactor is a dynamic tubular reactor.
In one embodiment, the secondary filter comprises more than two filters in parallel, which are preferably equipped with a pressure differential monitoring system to monitor the pressure differential between the material inlet and the material outlet of the filter.
When the device is in operation, one part of the two or more filters connected in parallel is in an operation state (namely, a state of filtering materials), and the other filters are in a cleaning or standby state. When the differential pressure monitoring system detects that the differential pressure of the filter in the running state is higher than a set value, the filter is switched to a cleaning state, and one or more of the filters in the standby state are switched to the running state.
In the washed state, the filter is washed with a solvent, preferably the solvent used for polymerization, and the filter residue obtained by washing can be used for preparing fibrids.
At the time of the secondary filtration, the polymerization reaction has been completed, and thus the present invention is not particularly limited to the secondary filter, and may be any suitable filter known in the art.
In one embodiment, the secondary filter comprises more than two filter presses in parallel. In the secondary filtering stage, the polymerization reaction is completed, more than two filter presses connected in parallel can be used as secondary filters, so that the operation continuity of the whole device can be ensured, and the cost can be reduced.
< continuous polymerization Process >
It is another object of the present invention to provide a continuous polymerization process of polymetaphenylene isophthalamide comprising a prepolymerization step, a primary neutralization step, a final polymerization step and a secondary neutralization step in this order, and optionally comprising a compounding step before the prepolymerization step, wherein
The batching step comprises continuously metering and feeding an N, N-dimethylacetamide solution of m-phenylenediamine and an m-phthaloyl chloride melt;
the pre-polymerization step comprises the steps of sequentially pre-mixing m-phenylenediamine and isophthaloyl chloride, carrying out primary pre-polymerization and secondary pre-polymerization to obtain a pre-polymerization product containing a polymetaphenylene isophthalamide oligomer and hydrogen chloride, wherein the primary pre-polymerization is carried out in a micro-channel reactor, and the secondary pre-polymerization is carried out in a dynamic tubular reactor;
The primary neutralization step comprises the steps of contacting a prepolymerization product with ammonia gas to neutralize hydrogen chloride therein and filtering the neutralized product to remove ammonium chloride generated by neutralization, so as to obtain primary neutralization filtrate, wherein the filtering is performed in a dynamic self-cleaning filter; wherein, the pH value of the neutralized product is preferably monitored, and the dosage of ammonia gas is adjusted according to the pH value, so that the pH value of the neutralized product is kept between 5.0 and 5.5;
the final polymerization step comprises the steps of enabling primary neutralization filtrate to be in contact with m-phthaloyl chloride melt to carry out a final polymerization reaction to obtain a final polymerization product containing poly m-phthaloyl m-phenylenediamine polymer and hydrogen chloride, wherein the final polymerization reaction is preferably carried out in a final polymerization reactor, and the final polymerization reactor is a tubular reactor, a LIST reactor or a double-screw reactor; wherein the viscosity of the final polymerization product is preferably monitored and the amount of isophthaloyl dichloride is adjusted according to the viscosity of the final polymerization product;
the secondary neutralization step includes contacting the final polymerization product with a basic organic compound to neutralize the hydrogen chloride therein.
In one embodiment, the present invention provides a continuous polymerization process of polymetaphenylene isophthalamide using the apparatus of the present invention.
The individual steps of the method of the invention are described in detail below.
Batching step
In one embodiment, the compounding step further comprises preparing a solution of m-phenylenediamine in N, N-dimethylacetamide and a melt of isophthaloyl dichloride.
In one embodiment, the m-phenylenediamine solution is prepared by melting and adding m-phenylenediamine to N, N-dimethylacetamide (preferably dehydrated, preferably having a water content of 150ppm or less, more preferably 100ppm or less) and dissolving the same, preferably at a concentration of 0.8 to 1.1mol/L.
In a preferred embodiment, the m-phenylenediamine solution is cooled after dissolution, preferably at a temperature of-10 to 0 ℃. More preferably, the cooling is performed in two steps, first cooling the m-phenylenediamine solution to 0 to 20 ℃ and then cooling to-10 to 0 ℃.
In one embodiment, the isophthaloyl chloride melt is prepared by heating and melting isophthaloyl chloride, preferably at a temperature of 55 to 65 ℃.
In one embodiment, in the dosing step, the molar feed rate ratio of isophthaloyl dichloride to metaphenylene diamine is made to be (0.80 to 0.95) by said metering: 1.
in an embodiment of the method according to the invention, which is carried out with the device according to the invention, the dosing step is carried out in a dosing unit.
In one embodiment, N-dimethylacetamide which is preferably dehydrated is continuously fed into a m-phenylenediamine dissolution tank, and meanwhile m-phenylenediamine is continuously fed into the m-phenylenediamine dissolution tank, the m-phenylenediamine solution in the m-phenylenediamine dissolution tank is conveyed to a m-phenylenediamine temporary storage tank, and the material in the m-phenylenediamine temporary storage tank is conveyed to a first high-level tank and then enters a m-phenylenediamine meter for metering; and simultaneously, melting the isophthaloyl dichloride through an isophthaloyl dichloride melter, feeding the isophthaloyl dichloride into an isophthaloyl dichloride melt storage tank, and then entering a second overhead tank and then entering an isophthaloyl dichloride melt meter.
In one embodiment, the m-phenylenediamine is melted by a m-phenylenediamine melter and then enters a m-phenylenediamine dissolution tank, and the temperature of the m-phenylenediamine melt is 70-90 ℃.
In one embodiment, the dehydrated N, N-dimethylacetamide has a water content of 150ppm or less, preferably 100ppm or less.
In one embodiment, the concentration of the m-phenylenediamine solution metered into the m-phenylenediamine meter is from 0.8 to 1.1mol/L and the temperature is from-10 to 0 ℃.
In one embodiment, the temperature of the isophthaloyl chloride melt entering the isophthaloyl chloride melt meter is from 55 to 65 ℃.
Prepolymerization step
In one embodiment, the pre-polymerization step comprises sequentially pre-mixing m-phenylenediamine with isophthaloyl chloride, a primary pre-polymerization and a secondary pre-polymerization to obtain a pre-polymerization product comprising an oligomer of polymetaphthaloyl metaphenylene diamine and hydrogen chloride, wherein the pre-mixing is performed in a pre-mixer (preferably a co-jet mixer or a counter-jet mixer), the primary pre-polymerization is performed in a microchannel reactor, and the secondary pre-polymerization is performed in a dynamic tubular reactor.
In the present specification, the "poly (m-phenylene isophthalamide) oligomer" refers to poly (m-phenylene isophthalamide) having a degree of polymerization of 20 or less.
In an embodiment in which the process of the invention is carried out using the apparatus of the invention, this step is carried out in a prepolymerization unit into which the metered amounts of the m-phenylenediamine solution and the isophthaloyl chloride melt are continuously fed.
In one embodiment, the m-phenylenediamine solution and the isophthaloyl dichloride melt are mixed sequentially in a premixer and then flowed into a microchannel reactor for a first prepolymerization and then into a dynamic tube reactor for a second prepolymerization.
In one embodiment, the molar ratio of isophthaloyl dichloride to metaphenylene diamine fed into the prepolymerization unit per unit time (i.e. the ratio of the molar feed rate of isophthaloyl dichloride to the molar feed rate of metaphenylene diamine) is in the range of (0.80 to 0.95): 1.
In one embodiment, the residence time of the material in the premixer is from 1 to 5 seconds.
In one embodiment, the residence time of the material in the microchannel reactor is from 0.5 to 5 minutes.
In one embodiment, the residence time of the material in the dynamic tubular reactor is from 5 to 30 minutes.
In one embodiment, the reaction temperature in the microchannel reactor and the dynamic tube reactor is 20 ℃ or less, preferably 0 ℃ or more.
Primary neutralization step
In one embodiment, the ratio of the amount of ammonia gas used in the primary neutralization step to the amount of isophthaloyl dichloride used in the prepolymerization step is from 1.90 to 1.99: 1.
in one embodiment, the pH of the once neutralized product is measured and the flow of ammonia is adjusted based on the pH to maintain the pH of the neutralized product between 5.0 and 5.5.
In one embodiment, more than two parallel dynamic self-cleaning filters are utilized to filter the product after primary neutralization, wherein the pressure difference between the material inlet and the material outlet of the dynamic self-cleaning filter for filtering is continuously detected, when the pressure difference is higher than a set value, the dynamic self-cleaning filter is switched into a cleaning state, and other dynamic self-cleaning filters are started for filtering.
In an embodiment in which the process of the invention is carried out using the apparatus of the invention, this step is carried out in a one-time neutralization unit.
In one embodiment, the material flowing out of the dynamic tubular reactor of the prepolymerization unit enters a gas-liquid mixer, ammonia gas is fed into the gas-liquid mixer at the same time, the mixed material enters a primary neutralization reactor for neutralization reaction so as to neutralize hydrogen chloride generated in the prepolymerization, and the neutralized material enters a primary filter for filtration to remove ammonium chloride.
In one embodiment, the ratio of the molar feed rate of ammonia to the molar feed rate of phthaloyl chloride in the middle of the pre-polymerization unit is (1.90 to 1.99): 1.
in one embodiment, the temperature of the material in the primary neutralization reactor is below 30 ℃ and the material residence time is 60 to 120 minutes.
In one embodiment, the ammonia gas is fed at a pressure of 0.07MPa or less.
In one embodiment, the pH of the once neutralized product is detected and the flow of ammonia is adjusted by an ammonia feed metering and controller based on the pH to maintain the pH of the neutralized product between 5.0 and 5.5. In a specific embodiment, the instantaneous flow and the accumulated flow of the ammonia gas are measured by an ammonia gas mass flow meter, and the flow of the ammonia gas is automatically controlled by interlocking an electromagnetic valve and the ammonia gas mass flow meter according to the detected pH.
In one embodiment, the filtration accuracy of the primary filtration (i.e., the filtration accuracy of the dynamic self-cleaning filter) is 10 to 50 μm.
In one embodiment, a differential pressure monitoring system is utilized to monitor the differential pressure between the material inlet and the material outlet of the dynamic self-cleaning filter, and when the differential pressure is above a set point, the filter is switched. Preferably, the set value is 0.5-0.8 MPa.
Final polymerization step
The final polymerization step comprises the steps of enabling primary neutralization filtrate to contact with m-phthaloyl chloride melt to carry out a final polymerization reaction to obtain a final polymerization product containing poly m-phthaloyl m-phenylenediamine polymer and hydrogen chloride, wherein the final polymerization reaction is carried out in a final polymerization reactor, and the final polymerization reactor is a continuous reactor; wherein the viscosity of the final polymerization product is monitored and the amount of isophthaloyl dichloride is adjusted according to the viscosity of the final polymerization product.
In the present specification, the "poly (m-phenylene isophthalamide) polymer" refers to poly (m-phenylene isophthalamide) having a degree of polymerization of more than 20.
In one embodiment, the ratio of the amount of isophthaloyl dichloride used in the final polymerization step to the amount of isophthalamide used in the pre-polymerization step is (0.045 to 0.250): 1.
in one embodiment, the reaction temperature in the finishing reactor is below 30 ℃.
In one embodiment, the residence time of the material in the finishing reactor is from 5 to 60 minutes.
In one embodiment, the final polymerization product has a viscosity of 30 to 100 Pa.s;
in embodiments where the process of the invention is carried out using the apparatus of the invention, this step is carried out in a finishing unit.
In one embodiment, the once neutralized mass is continuously fed to a final polymerization reactor while the phthaloyl chloride melt is continuously fed to the final polymerization reactor for polymerization.
In one embodiment, the ratio of the molar feed rate of isophthaloyl chloride to the molar feed rate of isophthalamide to the prepolymerization unit is from 0.045 to 0.250): 1.
in one embodiment, the reaction temperature in the finishing reactor is below 30 ℃.
In one embodiment, the residence time of the material in the finishing reactor is from 5 to 60 minutes.
In one embodiment, the outlet material viscosity of the finishing reactor is from 30 to 100 Pa.s.
In one embodiment, the viscosity value of the final polymerization reactor outlet material is detected by a viscosity detector and fed back to an isophthaloyl dichloride melt feed controller, when the viscosity value fed back by the viscosity detector is higher than a predetermined value, the isophthaloyl dichloride melt feed controller automatically decreases the feed rate of isophthaloyl dichloride, and when the viscosity value fed back by the viscosity detector is lower than a predetermined value, the isophthaloyl dichloride melt feed controller automatically increases the feed rate of isophthaloyl dichloride. Preferably, the predetermined value is 30 to 100pa·s.
Secondary neutralization step
The secondary neutralization step includes contacting the final polymerization product with a basic organic compound to neutralize the hydrogen chloride therein
In one embodiment, the basic organic compound is used in an amount of 2.01 to 2.10 times the amount of phthaloyl chloride used in the middle of the final polymerization step on a molar basis.
In one embodiment, the basic organic compound is one or more selected from pyridine, diethylamine, triethylamine.
In an embodiment in which the process of the invention is carried out using the apparatus of the invention, this step is carried out in a secondary neutralization unit.
In one embodiment, the material flowing out of the final polymerization reactor is continuously fed into a secondary neutralization reactor, and simultaneously, the alkaline organic matters are continuously fed into the secondary neutralization reactor, the mixed material is fed into the neutralization reactor for neutralization reaction so as to neutralize hydrogen chloride generated in the final polymerization reaction, and the neutralized material is fed into a secondary filter for filtration.
In one embodiment, the basic organic compound is fed in an amount of 2.01 to 2.10 times the amount of phthaloyl chloride used in the intermediate step of final polymerization on a molar basis.
In one embodiment, the material residence time in the neutralization reactor is from 2 to 5 minutes.
In one embodiment, a differential pressure monitoring system is used to monitor the differential pressure between the material inlet and the material outlet of the secondary filter, and when the differential pressure is above a set point, the filter is switched. Preferably, the set value is 0.5-0.8 MPa.
In one embodiment, the twice filtered material is defoamed.
The product obtained by the method can be directly used as spinning dope.
The apparatus and method of the present invention are described in detail below with reference to the accompanying drawings.
FIG. 1 is a schematic illustration of an apparatus and method according to one embodiment of the present invention. As shown in FIG. 1, the prepolymerization unit of the device comprises a premixer, a microchannel reactor and a dynamic tubular reactor which are connected in sequence, wherein the premixer is provided with an m-phenylenediamine solution inlet and an m-phthaloyl chloride melt inlet; the primary neutralization unit comprises a gas-liquid mixer, a primary neutralization reactor and a primary filter which are sequentially connected, wherein an ammonia gas inlet is further formed in the gas-liquid mixer, and the ammonia gas inlet is connected with an ammonia gas storage tank; the final polymerization unit comprises a final polymerization reactor, and an isophthaloyl dichloride melt inlet is arranged on the final polymerization reactor and is connected with an isophthaloyl dichloride melt storage tank; the secondary neutralization unit comprises a secondary neutralization reactor and a secondary filter which are sequentially connected, wherein an alkaline organic matter inlet is further formed in the secondary neutralization reactor, and the alkaline organic matter inlet is connected with an alkaline organic matter storage tank.
FIG. 2 is a schematic view of an apparatus and a method according to another embodiment of the present invention, which comprises an m-phenylenediamine dosing unit and an m-phthaloyl chloride dosing unit upstream of the prepolymerization unit, wherein the m-phenylenediamine dosing unit comprises an m-phenylenediamine dissolution tank, an m-phenylenediamine solution temporary storage tank, a first overhead tank and an m-phenylenediamine solution meter, which are sequentially connected, as compared with the apparatus shown in FIG. 1; wherein the outlet of the m-phenylenediamine solution meter is connected with the m-phenylenediamine solution inlet of the premixer; the first overhead tank is provided with a return pipeline connected to the m-phenylenediamine solution temporary storage tank; the isophthaloyl dichloride batching unit comprises an isophthaloyl dichloride melter, an isophthaloyl dichloride melt storage tank, a second overhead tank and an isophthaloyl dichloride melt meter; the outlet of the intermediate phthaloyl chloride melt meter is connected with the isophthaloyl chloride melt inlet of the pre-mixer; and a reflux pipeline connected to the isophthaloyl dichloride melt storage tank is arranged on the second overhead tank.
Fig. 3 is a schematic view of an apparatus and method according to another embodiment of the present invention, which further includes a pH monitor for monitoring the output of the primary neutralization reactor, as compared to the apparatus shown in fig. 1.
Fig. 4 is a schematic diagram of an apparatus and method according to another embodiment of the present invention, which further comprises a m-phenylenediamine dosing unit and an m-phthaloyl chloride dosing unit, and a pH monitor for monitoring the output material of the primary neutralization reactor, as compared to the apparatus shown in fig. 1, see in particular the description of fig. 2 and 3.
In the process according to the invention carried out with the apparatus according to the invention, the material is passed through the individual components of the apparatus in succession as indicated by the arrows in fig. 1 to 4.
The detailed description of the apparatus and method of the present invention given above and the preferred embodiments also apply to the apparatus and method shown in figures 1 to 4.
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.
Example 1:
(1) And (3) batching: the batching comprises two processes of continuous dissolution of m-phenylenediamine and preparation of m-phthaloyl chloride. Wherein the continuous dissolving process of the phenylenediamine is as follows: the molten (80 ℃) m-phenylenediamine (MPD) and the dehydrated (water content 70 ppm) DMAc are quantitatively, continuously and stably conveyed into a dissolution mixer by a metering pump and a flowmeter respectively for continuous mixing, wherein the MPD flow is 183.84kg/h and the DMAc flow is 1592.90kg/h. The mixed materials automatically flow into a first m-phenylenediamine dissolving tank with stirring for continuous dissolution. The retention time of the m-phenylenediamine in the dissolving tank is about 10 min; and then continuously conveyed to a second dissolving tank with stirring for continuous dissolution. The second dissolving tank is provided with a m-phenylenediamine concentration meter for continuously detecting the m-phenylenediamine concentration. The residence time of the m-phenylenediamine in the second dissolving tank is about 10 min; and then continuously conveying the mixture to a temporary storage tank with stirring for storage. The temporary storage tank is also provided with a m-phenylenediamine concentration meter for continuously detecting the m-phenylenediamine concentration; the MPD concentration after complete dissolution was 1mol/L. Meanwhile, the temporary storage tank is provided with a jacket for cooling, and the m-phenylenediamine solution is cooled to 0 ℃. The m-phenylenediamine solution in the temporary storage tank is further cooled to-10 ℃ by a heat exchanger and is continuously pumped into the first high-level tank. The m-phenylenediamine solution in the first high-level tank is quantitatively, continuously and stably conveyed into a pre-mixer of the pre-polymerization unit through a metering pump and a flowmeter; and (3) the redundant m-phenylenediamine solution in the first high-level tank flows back to the m-phenylenediamine temporary storage tank through a return pipe. The preparation process of isophthaloyl dichloride (IPC) is as follows: continuously pumping the IPC melt (60 ℃) stored in a storage tank into a second high-level tank (high-level tank jacket heat preservation 60 ℃) under the protection of nitrogen; the IPC melt in the second overhead tank is quantitatively, continuously and stably conveyed into a pre-mixer of the pre-polymerization unit through a metering pump and a flowmeter; and the redundant IPC melt in the second high-level tank flows back to the IPC storage tank through a return pipe.
(2) Prepolymerization: the m-phenylenediamine low-temperature solution and the m-phthaloyl chloride melt are quantitatively, continuously and stably conveyed into a pre-mixer of a pre-polymerization unit for mixing through a metering pump and a flowmeter; the premixer is a co-injection mixer. The IPC molar flow is 0.95 times of MPD by regulating the flow. Specifically, the m-phenylenediamine solution was 1776.74kg/h and the isophthaloyl dichloride melt was 327.88kg/h. The residence time of the mixture in the premixer is 1s, then the mixture is continuously flowed into a micro-channel reactor for primary prepolymerization, the reaction temperature in the micro-channel reactor is 0 ℃, and the residence time of the material in the micro-channel reactor is 1min; continuously feeding the material subjected to the first-stage prepolymerization into a dynamic tubular reactor for the second-stage prepolymerization, wherein the reaction temperature in the dynamic tubular reactor is 10 ℃, the stirring speed is 300rpm, and the residence time is 20min.
(3) Primary neutralization: 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 of the ammonia is controlled at 53.8kg/h (1.96 times of the molar flow of IPC added in the prepolymerization) through an ammonia feeding metering and controller. The mixed materials in the gas-liquid mixing pump flow into a dynamic tubular reactor for primary neutralization, and the hydrogen chloride generated by the prepolymerization reaction reacts to generate ammonium chloride and gradually crystallizes and precipitates out. The reaction temperature in the dynamic tube reactor was 25℃and the residence time was 60min. And sampling and measuring the pH value of the material at the outlet of the dynamic tubular reactor, and controlling the pH value of the material at the outlet of the dynamic tubular reactor to be about 5.5 by finely adjusting the ammonia flow through ammonia feeding metering and a controller.
(4) And (3) primary filtration: the material after primary neutralization flows into three scraper type self-cleaning filters (two-purpose one-purpose) which are arranged in parallel for filtering, and the ammonium chloride particles with the particle size larger than 30 mu m are trapped. When the pressure difference between the front and the back of a certain filter screen is larger than 0.7MPa, the filter is switched to a standby filter, and the filter is cleaned by dried DMAc. The viscous ammonium chloride-containing filter residue precipitated from the bottom of the filter is continuously discharged through an external discharge pipeline. The discharge pressure is kept constant by the regulator valve.
(5) And (3) final polymerization: the filtered materials are continuously fed into a LIST reactor, and simultaneously IPC melt is continuously and stably pumped into the reactor for mixing reaction after being metered by a flowmeter. The amount of IPC added was 16.50kg/h (the final molar ratio of all IPC added to MPD was 0.998:1). The reaction temperature is 30 ℃ and the reaction time is 10min. The LIST reactor outlet continuously monitors the viscosity of the material after final polymerization reaction through an online viscometer, and feeds back to the IPC melt feed controller to finely adjust the IPC melt flow. The viscosity of the final material can be controlled at 50.+ -.2 Pa.s when the device is operating stably.
(6) Secondary neutralization: the material after final polymerization is continuously conveyed into a dynamic tubular reactor for secondary neutralization by a discharge screw of the LIST reactor, a neutralizing agent diethylamine for secondary neutralization is continuously pumped into the dynamic tubular reactor through a metering pump to be mixed with the material after final polymerization so as to neutralize hydrogen chloride generated by the final polymerization, the addition amount of the diethylamine is 12.10kg/h, and the retention time of the material in the dynamic tubular reactor is 15min. The pH value of the material after the secondary neutralization is about 7.
(7) And (3) secondary filtration: and (5) the material after secondary neutralization is subjected to secondary filtration by using a filter press, and the material after secondary filtration is sent into a storage tank for storage. And then the fiber can be directly used for spinning after the working procedures of filtering and defoaming in a spinning working section and the like.
Example 2:
(1) And (5) batching. The batching comprises two processes of continuous dissolution of m-phenylenediamine and preparation of m-phthaloyl chloride. Wherein the continuous dissolving process of the phenylenediamine is as follows: the molten (80 ℃) m-phenylenediamine (MPD) and the dehydrated (water content 90 ppm) DMAc are quantitatively, continuously and stably conveyed into a dissolution mixer by a metering pump and a flowmeter respectively for continuous mixing, wherein the MPD flow is 165.46kg/h and the DMAc flow is 1592.90kg/h. The mixed materials automatically flow into a first m-phenylenediamine dissolving tank with stirring for continuous dissolution. The retention time of the m-phenylenediamine in the dissolving tank is about 10 min; and then continuously conveyed to a second dissolving tank with stirring for continuous dissolution. The second dissolving tank is provided with a m-phenylenediamine concentration meter for continuously detecting the m-phenylenediamine concentration. The residence time of the m-phenylenediamine in the second dissolving tank is about 10 min; and then continuously conveying the mixture to a temporary storage tank with stirring for storage. The temporary storage tank is also provided with a m-phenylenediamine concentration meter for continuously detecting the m-phenylenediamine concentration; the MPD concentration after complete dissolution was 0.9mol/L. Meanwhile, the temporary storage tank is provided with a jacket for cooling, and the m-phenylenediamine solution is cooled to 10 ℃. The m-phenylenediamine solution in the temporary storage tank is further cooled to-5 ℃ by a heat exchanger and is continuously pumped into the first high-level tank. The m-phenylenediamine solution in the first high-level tank is quantitatively, continuously and stably conveyed into a pre-mixer of the pre-polymerization unit through a metering pump and a flowmeter; and (3) the redundant m-phenylenediamine solution in the first high-level tank flows back to the m-phenylenediamine temporary storage tank through a return pipe. The preparation process of isophthaloyl dichloride (IPC) is as follows: continuously pumping the IPC melt (60 ℃) stored in a storage tank into a second high-level tank (high-level tank jacket heat preservation 60 ℃) under the protection of nitrogen; the IPC melt in the second overhead tank is quantitatively, continuously and stably conveyed into a pre-mixer of the pre-polymerization unit through a metering pump and a flowmeter; and the redundant IPC melt in the second high-level tank flows back to the IPC storage tank through a return pipe.
(2) Prepolymerization: the m-phenylenediamine low-temperature solution and the m-phthaloyl chloride melt are quantitatively, continuously and stably conveyed into a pre-mixer of a pre-polymerization unit for mixing through a metering pump and a flowmeter; the premixer is a co-injection mixer. The IPC molar flow is 0.90 times of MPD by regulating the flow. Specifically, the m-phenylenediamine solution was 1758.36kg/h and the isophthaloyl dichloride melt was 279.56kg/h. The residence time of the mixture in the premixer is 1s, then the mixture is continuously flowed into a micro-channel reactor for primary prepolymerization, the reaction temperature in the micro-channel reactor is 5 ℃, and the residence time of the material in the micro-channel reactor is 2min; continuously feeding the material subjected to the first-stage prepolymerization into a dynamic tubular reactor for second-stage prepolymerization, wherein the reaction temperature in the dynamic tubular reactor is 5 ℃, the stirring speed is 200rpm, and the residence time is 30min.
(3) Primary neutralization: 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 of the ammonia is controlled at 44.5kg/h (1.9 times of the molar flow of IPC added in the prepolymerization) through an ammonia feeding metering and controller. The mixed materials in the gas-liquid mixing pump flow into a dynamic tubular reactor for primary neutralization, and the hydrogen chloride generated by the prepolymerization reaction reacts to generate ammonium chloride and gradually crystallizes and precipitates out. The reaction temperature in the dynamic tube reactor was 20℃and the residence time was 90min. And sampling and measuring the pH value of the material at the outlet of the dynamic tubular reactor, and controlling the pH value of the material at the outlet of the dynamic tubular reactor to be about 5.0 by finely adjusting the flow of ammonia through ammonia feeding metering and a controller.
(4) And (3) primary filtration: the material after primary neutralization flows into 2 rotary pressurizing filters which are arranged in parallel for filtering, and the ammonium chloride particles with the particle size larger than 30 mu m are retained. The rotary filter is continuously operated, and the filter cloth is automatically cleaned and regenerated. And automatically and continuously discharging the filtered ammonium chloride filter residue.
(5) And (3) final polymerization: continuously feeding the filtered materials into a dynamic tubular reactor, and continuously and stably pumping the IPC melt into the reactor for mixing reaction after metering by a flowmeter. The amount of IPC added was 29.51kg/h (the final molar ratio of all IPC added to MPD was 0.995:1). The reaction temperature is 20 ℃ and the reaction time is 20min. The viscosity of the material after final polymerization reaction is continuously monitored by an online viscometer at the outlet of the dynamic tubular reactor and is fed back to an IPC melt feeding controller to finely adjust the IPC melt flow. The viscosity of the final material can be controlled to 40+ -2 Pa.s when the device is stably operated.
(6) Secondary neutralization: the material after final polymerization is pushed by a stirring paddle of a dynamic tubular reactor to be continuously conveyed into the dynamic tubular reactor for secondary neutralization, and a neutralizing agent diethylamine for secondary neutralization is continuously pumped into the dynamic tubular reactor through a metering pump to be mixed with the material after final polymerization so as to neutralize hydrogen chloride generated by the final polymerization, wherein the addition amount of the diethylamine is 21.55kg/h, and the retention time of the material in the dynamic tubular reactor is 20min. The pH value of the neutralized material is about 7.5.
(7) And (3) secondary filtration: and (5) the material after secondary neutralization is subjected to secondary filtration by using a filter press, and the material after secondary filtration is sent into a storage tank for storage. And then the fiber can be directly used for spinning after the working procedures of filtering and defoaming in a spinning working section and the like.
Example 3:
(1) And (5) batching. The batching comprises two processes of continuous dissolution of m-phenylenediamine and preparation of m-phthaloyl chloride. Wherein the continuous dissolving process of the phenylenediamine is as follows: the molten (80 ℃) m-phenylenediamine (MPD) and the dehydrated (water content: 50 ppm) DMAc are quantitatively, continuously and stably fed into a dissolution mixer by a metering pump and a flowmeter, respectively, and continuously mixed, wherein the MPD flow rate is 147.07kg/h and the DMAc flow rate is 1592.90kg/h. The mixed materials automatically flow into a first m-phenylenediamine dissolving tank with stirring for continuous dissolution. The retention time of the m-phenylenediamine in the dissolving tank is about 10 min; and then continuously conveyed to a second dissolving tank with stirring for continuous dissolution. The second dissolving tank is provided with a m-phenylenediamine concentration meter for continuously detecting the m-phenylenediamine concentration. The residence time of the m-phenylenediamine in the second dissolving tank is about 10 min; and then continuously conveying the mixture to a temporary storage tank with stirring for storage. The temporary storage tank is also provided with a m-phenylenediamine concentration meter for continuously detecting the m-phenylenediamine concentration; the MPD concentration after complete dissolution was 0.8mol/L. Meanwhile, the temporary storage tank is provided with a jacket for cooling, and the m-phenylenediamine solution is cooled to 10 ℃. The m-phenylenediamine solution in the temporary storage tank is further cooled to 0 ℃ through a heat exchanger and is continuously pumped into the first high-level tank. The m-phenylenediamine solution in the first high-level tank is quantitatively, continuously and stably conveyed into a pre-mixer of the pre-polymerization unit through a metering pump and a flowmeter; and (3) the redundant m-phenylenediamine solution in the first high-level tank flows back to the m-phenylenediamine temporary storage tank through a return pipe. The preparation process of isophthaloyl dichloride (IPC) is as follows: continuously pumping the IPC melt (65 ℃) stored in the storage tank into a second high-level tank (high-level tank outer jacket heat preservation 65 ℃) under the protection of nitrogen; the IPC melt in the second overhead tank is quantitatively, continuously and stably conveyed into a pre-mixer of the pre-polymerization unit through a metering pump and a flowmeter; and the redundant IPC melt in the second high-level tank flows back to the IPC storage tank through a return pipe.
(2) Prepolymerization: the m-phenylenediamine low-temperature solution and the m-phthaloyl chloride melt are quantitatively, continuously and stably conveyed into a pre-mixer of a pre-polymerization unit for mixing through a metering pump and a flowmeter; the premixer is a co-injection mixer. The IPC molar flow is 0.8 times of MPD by regulating the flow. Specifically, the m-phenylenediamine solution was 1739.97kg/h and the isophthaloyl dichloride melt was 220.89kg/h. The residence time of the mixture in the pre-mixer is 3s, then the mixture is continuously flowed into the micro-channel reactor for primary pre-polymerization, the reaction temperature in the micro-channel reactor is 5 ℃, and the residence time of the material in the micro-channel reactor is 3min; continuously feeding the material subjected to the first-stage prepolymerization into a dynamic tubular reactor for the second-stage prepolymerization, wherein the reaction temperature in the dynamic tubular reactor is 15 ℃, the stirring speed is 300rpm, and the residence time is 15min.
(3) Primary neutralization: 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 of the ammonia is controlled at 36.2kg/h (1.95 times of the molar flow of IPC added in the prepolymerization) through an ammonia feeding metering and controller. The mixed materials in the gas-liquid mixing pump flow into a dynamic tubular reactor for primary neutralization, and the hydrogen chloride generated by the prepolymerization reaction reacts to generate ammonium chloride and gradually crystallizes and precipitates out. The reaction temperature in the dynamic tube reactor was 15℃and the residence time was 120min. And sampling and measuring the pH value of the material at the outlet of the dynamic tubular reactor, and controlling the pH value of the material at the outlet of the dynamic tubular reactor to be about 5.5 by finely adjusting the ammonia flow through ammonia feeding metering and a controller.
(4) And (3) primary filtration: the material after primary neutralization flows into three scraper type self-cleaning filters (two-purpose one-purpose) which are arranged in parallel for filtering, and the ammonium chloride particles with the particle size larger than 30 mu m are trapped. When the pressure difference between the front and the back of a certain filter screen is larger than 0.7MPa, the filter is switched to a standby filter, and the filter is cleaned by dried DMAc. The viscous ammonium chloride-containing filter residue precipitated from the bottom of the filter is continuously discharged through an external discharge pipeline. The discharge pressure is kept constant by the regulator valve.
(5) And (3) final polymerization: the filtered materials are continuously fed into a double-screw reactor, and IPC melt is continuously and stably pumped into the reactor for mixing reaction after being metered by a flowmeter. The amount of IPC added was 52.45kg/h (the final molar ratio of all IPCs added to the molar ratio of MPD was 0.990:1). The reaction temperature is 30 ℃ and the reaction time is 30min. The viscosity of the material after final polymerization reaction is continuously monitored by an online viscometer at the outlet of the double-screw reactor and is fed back to an IPC melt feeding controller to finely adjust the IPC melt flow. When the device is stably operated, the viscosity of the material after final polymerization can be controlled to be 30+/-2 Pa.s.
(6) Secondary neutralization: continuously conveying the material subjected to final polymerization into a dynamic tubular reactor for secondary neutralization, continuously pumping a secondary neutralizing agent diethylamine into the dynamic tubular reactor through a metering pump, and mixing with the material subjected to final polymerization to neutralize hydrogen chloride generated by the final polymerization, wherein the addition amount of the diethylamine is 38.05kg/h, and the residence time of the material in the dynamic tubular reactor is 10min. The pH value of the neutralized material is about 7.
(7) And (3) secondary filtration: and (5) the material after secondary neutralization is subjected to secondary filtration by using a filter press, and the material after secondary filtration is sent into a storage tank for storage. And then the fiber can be directly used for spinning after the working procedures of filtering and defoaming in a spinning working section and the like.
Comparative example 1:
the meta-aramid polymerization liquid was prepared by using a batch polymerization apparatus which was relatively mature at present, and using a polymerization process flow which was almost the same as example 1 (no means was exactly the same, especially in terms of temperature control), and finally the viscosity stability of the polymerization liquids of different batches was examined. The batch polymerization process is as follows:
(1) And (5) batching. The batching comprises two processes of m-phenylenediamine dissolution and m-phthaloyl chloride preparation. Wherein the dissolving process of the phenylenediamine is as follows: 1592.90kg of dehydrated DMAc (water content: 70 ppm) was injected into a m-phenylenediamine dissolution vessel by a metering pump and a flowmeter, and the dissolution vessel was always purged with nitrogen for protection. Then, 183.84kg of m-phenylenediamine (MPD) in a molten state (80 ℃ C.) was fed into a m-phenylenediamine dissolution vessel under stirring to be dissolved. The MPD concentration after complete dissolution was 1mol/L. The dissolution vessel was cooled with a jacket, and the dissolved m-phenylenediamine solution was cooled to-10 ℃. All of which are then fed to a batch prepolymerization reactor in preparation for polymerization. The preparation process of isophthaloyl dichloride (IPC) is as follows: continuously pumping the IPC melt (60 ℃) stored in a storage tank into an IPC overhead tank (an overhead tank outer jacket keeps warm at 60 ℃) under the protection of nitrogen; the IPC melt in the overhead tank is fed to a batch prepolymerization reactor by a gear pump to prepare for polymerization. And the redundant IPC melt in the overhead tank flows back to the IPC storage tank through a return pipe.
(2) Prepolymerization: the IPC melt was added to the m-phenylenediamine low temperature solution to begin the polymerization reaction. The stirrer in the prepolymerization reactor mixes the two uniformly, and the heat exchanger controls the polymerization temperature to be not more than 10 ℃. Once IPC is added too quickly, the addition of IPC is stopped until the temperature falls to within 10 ℃ and then the addition of IPC is continued. The number of moles of IPC added at the end was 0.95 times that of MPD. Specifically, the m-phenylenediamine solution was 1776.74kg, and the m-phthaloyl chloride melt was 327.88kg. The reaction time from IPC addition to pre-coalescence beam control was 120min.
(3) Primary neutralization: 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, reacting hydrogen chloride generated by the prepolymerization reaction to generate ammonium chloride, and gradually crystallizing and precipitating. 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.
(4) And (3) primary filtration: 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 to filter-press the ammonium chloride into dry filter residues and discharging the filter residues.
(5) And (3) final polymerization: and collecting the filtered filtrate into a final polymerization reaction kettle, uniformly stirring the filtrate after the isostatic filtering is finished, removing materials for amino-terminated analysis, and calculating the addition amount of the final polymerization IPC according to the specific content of the amino-terminated. The addition amount of IPC is 16.5+ -0.5 kg, the reaction temperature is 30 ℃, and the reaction time is 10min. The outlet of the final polymerization reactor was monitored for the viscosity of the post-final polymerization material by an on-line viscometer.
(6) Secondary neutralization: and adding diethylamine into a final polymerization reaction kettle after finishing the final polymerization, and carrying out secondary neutralization. The addition amount of diethylamine is 12.1+/-0.3 kg, and the secondary neutralization time is 15min. The pH value of the neutralized material is about 7.
(7) And (3) secondary filtration: and (5) the material after secondary neutralization is subjected to secondary filtration by using a filter press, and the material after secondary filtration is sent into a storage tank for storage. And then the fiber can be directly used for spinning after the working procedures of filtering and defoaming in a spinning working section and the like.
Polymerization stability evaluation: the polymerization of five batches was repeated under the same conditions in the above manner, and the final polymerization had the following viscosities: 57 The average value was calculated to be 50.8.+ -. 7 Pa.s for 53, 46, 55, 43 Pa.s.
Comparative example 2
In the same manner as in example 1, except that a premixer was not used in the prepolymerization unit.
In the step (2), the low-temperature solution of m-phenylenediamine and the melt of m-phthaloyl chloride are quantitatively, continuously and stably conveyed into a micro-channel reactor of a prepolymerization unit through a metering pump and a flowmeter for carrying out primary prepolymerization. The IPC molar flow is 0.95 times of MPD by regulating the flow. Specifically, the m-phenylenediamine solution was 1776.74kg/h and the isophthaloyl dichloride melt was 327.88kg/h. The reaction temperature in the microchannel reactor is 0 ℃, and the residence time of the materials in the microchannel reactor is 1min; continuously feeding the material subjected to the first-stage prepolymerization into a dynamic tubular reactor for the second-stage prepolymerization, wherein the reaction temperature in the dynamic tubular reactor is 10 ℃, the stirring speed is 300rpm, and the residence time is 20min.
Comparative example 3
The same procedure as in example 1 was followed except that the pre-mixer was replaced in the pre-polymerization unit with a simple tee connected at the feed inlet of the microreactor.
Polymerization stability evaluation: in comparative example 2, in the case of using the micro-channel reactor as a mixer without premixing, the micro-reactor was blocked quickly (within 1 min); in comparative example 3, a simple tee joint was used instead of a pre-mixer to connect to the material inlet of the microreactor, so that the microreactor was gradually blocked within 30 minutes under the same conditions, and the pre-polymerization was difficult to continue.
From the above evaluation results, it is found that the present invention solves the problem of IPC continuous and efficient mixing and reaction heat transfer by combining the premixer, the microchannel mixer and the tubular reactor in the prepolymerization stage, thereby enabling the continuous polymerization process of PMIA to proceed smoothly.
Industrial applicability
The continuous polymerization device and method of the poly (m-phenylene isophthalamide) can be widely applied to the industry for producing meta-aramid materials such as meta-aramid fibers.
Claims (10)
1. A continuous polymerization device of poly (m-phenylene isophthalamide) is characterized by comprising a prepolymerization unit, a primary neutralization unit, a final polymerization unit and a secondary neutralization unit in sequence, wherein
The prepolymerization unit comprises a premixer, a microchannel reactor and a dynamic tubular reactor which are sequentially connected, wherein the premixer is provided with an m-phenylenediamine solution inlet and an m-phthaloyl chloride melt inlet;
the primary neutralization unit comprises a gas-liquid mixer, a primary neutralization reactor and a primary filter which are sequentially connected, wherein an ammonia gas inlet is further formed in the gas-liquid mixer, and the ammonia gas inlet is connected with an ammonia gas storage tank; the primary filter comprises more than two dynamic self-cleaning filters which are arranged in parallel;
The final polymerization unit comprises a final polymerization reactor, wherein the final polymerization reactor is a continuous reactor, an isophthaloyl dichloride melt inlet is arranged on the final polymerization reactor, and the isophthaloyl dichloride melt inlet is connected with an isophthaloyl dichloride melt storage tank;
the secondary neutralization unit comprises a secondary neutralization reactor and a secondary filter which are sequentially connected, wherein an alkaline organic matter inlet is further formed in the secondary neutralization reactor, and the alkaline organic matter inlet is connected with an alkaline organic matter storage tank.
2. The apparatus according to claim 1, further comprising an m-phenylenediamine dosing unit and an m-phthaloyl chloride dosing unit upstream of the prepolymerization unit, wherein
The m-phenylenediamine dosing unit comprises a m-phenylenediamine dissolution tank, a m-phenylenediamine solution temporary storage tank, a first overhead tank and a m-phenylenediamine solution meter which are connected in sequence; wherein the outlet of the m-phenylenediamine solution meter is connected with the m-phenylenediamine solution inlet of the premixer; preferably, the first high-level tank is provided with a return pipeline connected to the m-phenylenediamine solution temporary storage tank, and the return pipeline is used for keeping the liquid level in the first high-level tank constant;
the isophthaloyl dichloride batching unit comprises an isophthaloyl dichloride melter, an isophthaloyl dichloride melt storage tank, a second overhead tank and an isophthaloyl dichloride melt meter; the outlet of the intermediate phthaloyl chloride melt meter is connected with the isophthaloyl chloride melt inlet of the pre-mixer; preferably, a reflux pipeline connected to the isophthaloyl dichloride melt storage tank is arranged on the second head tank, and the reflux pipeline is used for keeping the liquid level in the second head tank constant;
The m-phenylenediamine batching unit and the m-phthaloyl chloride batching unit are also provided with inert gas protection systems.
3. The apparatus according to claim 2, wherein the m-phenylenediamine solution temporary storage tank is provided with a cooling jacket; a heat exchanger is arranged between the m-phenylenediamine solution temporary storage tank and the first high-level tank; the isophthaloyl dichloride storage tank and the second head tank are provided with heat preservation devices.
4. A device according to any one of claims 1 to 3, wherein: the primary neutralization unit further comprises an ammonia gas feeding metering and controller, and the ammonia gas feeding metering and controller is used for stabilizing the ammonia gas feeding amount.
5. A device according to any one of claims 1 to 3, wherein: the final polymerization unit further comprises a viscosity detector and an isophthaloyl dichloride melt feed controller, wherein the viscosity detector is configured to detect the viscosity value of the material at the outlet of the final polymerization reactor and feed back the viscosity value to the isophthaloyl dichloride melt feed controller, and the isophthaloyl dichloride melt feed controller adjusts the feed rate of isophthaloyl dichloride according to the viscosity value fed back by the viscosity detector.
6. A device according to any one of claims 1 to 3, wherein: the secondary filter comprises more than two filters which are connected in parallel; the premixer is a co-injection mixer or a counter-injection mixer; the gas-liquid mixer is a gas-liquid mixing pump; the final polymerization reactor is a continuous tubular reactor, a LIST reactor or a double-screw reactor; the primary neutralization reactor and the secondary neutralization reactor are dynamic tubular reactors.
7. A continuous polymerization process of polymetaphenylene isophthalamide, characterized in that the process comprises a prepolymerization step, a primary neutralization step, a final polymerization step and a secondary neutralization step in this order, and optionally a compounding step before the prepolymerization step, wherein
The batching step comprises continuously metering and feeding a m-phenylenediamine solution and an m-phthaloyl chloride melt;
the pre-polymerization step comprises the steps of sequentially pre-mixing m-phenylenediamine and isophthaloyl chloride, carrying out primary pre-polymerization and secondary pre-polymerization to obtain a pre-polymerization product containing a polymetaphenylene isophthalamide oligomer and hydrogen chloride, wherein the primary pre-polymerization is carried out in a micro-channel reactor, and the secondary pre-polymerization is carried out in a dynamic tubular reactor;
the primary neutralization step comprises the steps of contacting a prepolymerization product with ammonia gas to neutralize hydrogen chloride therein and filtering the neutralized product to remove ammonium chloride generated by neutralization, so as to obtain primary neutralization filtrate, wherein the filtering is performed in a dynamic self-cleaning filter; wherein, the pH value of the neutralized product is preferably monitored, and the dosage of ammonia gas is adjusted according to the pH value, so that the pH value of the neutralized product is 5.0-5.5;
The final polymerization step comprises the steps of enabling a primary neutralization filtrate to be in contact with m-phthaloyl chloride melt for final polymerization reaction to obtain a final polymerization product containing poly m-phthaloyl m-phenylenediamine polymer and hydrogen chloride, wherein the viscosity of the final polymerization product is preferably monitored, and the dosage of the m-phthaloyl chloride is adjusted according to the viscosity of the final polymerization product;
the secondary neutralization step includes contacting the final polymerization product with a basic organic compound to neutralize the hydrogen chloride therein.
8. The method of claim 7, wherein the step of determining the position of the probe is performed,
in the batching step, the dosage ratio of the isophthaloyl dichloride to the m-phenylenediamine in terms of mole is (0.80-0.95): 1, a step of; the concentration of the m-phenylenediamine solution is 0.8-1.1 mol/L, and the temperature is-10-0 ℃; the temperature of the isophthaloyl dichloride melt is 55-65 ℃;
in the pre-polymerization step, the pre-mixing time is 1-5 s, the residence time of the materials in the micro-channel reactor is 0.5-5 min, the residence time of the materials in the dynamic tubular reactor is 5-30 min, and the reaction temperature in the micro-channel reactor and the dynamic tubular reactor is below 20 ℃;
in the primary neutralization step, the dosage ratio of ammonia gas to the isophthaloyl dichloride in the prepolymerization step is (1.90-1.99): 1, a step of;
In the final polymerization step, the dosage ratio of the isophthaloyl dichloride to the m-phenylenediamine in the pre-polymerization step is (0.045-0.250) in terms of mole: 1, a step of; the reaction temperature in the final polymerization reactor is-10-50 ℃; the residence time of the materials in the final polymerization reactor is 5-60 min; the viscosity of the final polymerization product is 30-100 Pa.s;
in the secondary neutralization step, the dosage of the alkaline organic matters is 2.01 to 2.10 times of the molar quantity of the added isophthaloyl dichloride in the final polymerization step.
9. A continuous polymerization process of polymetaphenylene isophthalamide, characterized in that the process is carried out by means of the apparatus as claimed in any one of claims 1 to 6.
10. The method according to claim 9, wherein the temperature of the material in the primary neutralization unit neutralization reactor is below 30 ℃ and the material residence time is 60-120 min; the temperature of the materials in the secondary neutralization unit neutralization reactor is below 50 ℃, and the material residence time is 20-40 min.
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