CN116284756A - Method for preparing bio-based semi-aromatic polyamide based on micro-reaction device - Google Patents
Method for preparing bio-based semi-aromatic polyamide based on micro-reaction device Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 32
- 229920006012 semi-aromatic polyamide Polymers 0.000 title claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 46
- 239000011259 mixed solution Substances 0.000 claims abstract description 40
- 150000004985 diamines Chemical class 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 238000005086 pumping Methods 0.000 claims abstract description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000012546 transfer Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 16
- -1 furanyl dicarboxylic acid Chemical compound 0.000 claims description 13
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 8
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 claims description 5
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 5
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 claims description 4
- DRMPQIAQICUZEA-UHFFFAOYSA-N 2-[5-(carboxymethyl)furan-2-yl]acetic acid Chemical compound OC(=O)CC1=CC=C(CC(O)=O)O1 DRMPQIAQICUZEA-UHFFFAOYSA-N 0.000 claims description 4
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims description 2
- HVLOWHVZLUWIGX-UHFFFAOYSA-N 2-[5-(2-aminoethyl)furan-2-yl]ethanamine Chemical compound NCCC1=CC=C(CCN)O1 HVLOWHVZLUWIGX-UHFFFAOYSA-N 0.000 claims description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 2
- VKLGKDZCKSMSHG-UHFFFAOYSA-N [5-(aminomethyl)furan-2-yl]methanamine Chemical compound NCC1=CC=C(CN)O1 VKLGKDZCKSMSHG-UHFFFAOYSA-N 0.000 claims description 2
- JOTDFEIYNHTJHZ-UHFFFAOYSA-N furan-2,4-dicarboxylic acid Chemical compound OC(=O)C1=COC(C(O)=O)=C1 JOTDFEIYNHTJHZ-UHFFFAOYSA-N 0.000 claims description 2
- SYLAFCZSYRXBJF-UHFFFAOYSA-N furan-3,4-dicarboxylic acid Chemical compound OC(=O)C1=COC=C1C(O)=O SYLAFCZSYRXBJF-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 abstract description 18
- 229920002647 polyamide Polymers 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 7
- 239000012530 fluid Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 13
- 238000006068 polycondensation reaction Methods 0.000 description 12
- 238000007069 methylation reaction Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920000414 polyfuran Polymers 0.000 description 4
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920006021 bio-based polyamide Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- FXJUUMGKLWHCNZ-UHFFFAOYSA-N dimethyl furan-2,3-dicarboxylate Chemical compound COC(=O)C=1C=COC=1C(=O)OC FXJUUMGKLWHCNZ-UHFFFAOYSA-N 0.000 description 3
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
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- 229910000619 316 stainless steel Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
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- DTQVDTLACAAQTR-DYCDLGHISA-N trifluoroacetic acid-d1 Chemical compound [2H]OC(=O)C(F)(F)F DTQVDTLACAAQTR-DYCDLGHISA-N 0.000 description 2
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
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Images
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- 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
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
-
- 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
- C08G69/46—Post-polymerisation treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyamides (AREA)
Abstract
The invention belongs to the technical field of polyamide material synthesis, and relates to a method for preparing bio-based semi-aromatic polyamide based on a micro-reaction device. Dissolving dicarboxylic acid and a catalyst in a solvent to obtain a first mixed solution; dissolving diamine in a solvent to obtain a second mixed solution; respectively and simultaneously pumping the first mixed solution and the second mixed solution into a micro-mixer in a micro-reaction device for mixing, and pumping the mixed solution into a low-temperature prepolymerization micro-reactor in the micro-reaction device for prepolymerization reaction after mixing; after the prepolymerization reaction is finished, continuously pumping the reaction liquid into a high-temperature polymerization microreactor in a microreaction device to carry out polymerization reaction, and after the reaction is finished, carrying out post-treatment on the reaction liquid to obtain the bio-based semi-aromatic polyamide. The micromixer in the microchannel reaction device is selected from cascade stirred tank reactors coupled by an external force field, so that the mixing performance of the polymerized viscous fluid is effectively enhanced, and the mass transfer performance among monomers is improved, thereby improving the quality of products.
Description
Technical Field
The invention belongs to the technical field of polyamide material synthesis, and relates to a method for preparing bio-based semi-aromatic polyamide based on a micro-reaction device.
Background
Polyamide (PA), also called nylon, is the most important polymer material containing amide groups in the molecular main chain, has excellent properties such as good mechanical properties, heat resistance, wear resistance and easy processing, and is widely applied to the fields of electronics, automobiles and aviation, and becomes the most widely used variety of five general materials. In general, polyamides are prepared from dicarboxylic acids and diamines or caprolactam and related cyclic amides by stepwise polycondensation. Among the many PA materials, PA6 and PA66 are most widely used, accounting for over 90% of the total PA yield. At present, most of the raw materials of the PA products come from petroleum, and along with the development of green chemical industry, the technology of replacing the traditional petroleum-based PA with bio-based PA is developed into a hot spot for research in recent years, and has wide market application prospect in the fields of plastics, packaging, manufacturing, medicine and the like.
The bio-based polyamide is prepared from biomass renewable resources serving as raw materials, and is used for synthesizing a precursor of the polyamide through biological, chemical, physical and other means, and then the polyamide is synthesized into the PA through polymerization reaction, so that the bio-based polyamide has the characteristics of being green, environment-friendly, renewable in raw materials and the like. The polymerization reaction method mainly comprises a melting and solution polycondensation method, wherein the melting polycondensation method generally needs a high-temperature environment to reach the melting temperature of a product, and byproducts are removed under low pressure to drive the polycondensation reaction to move, which not only needs excessive energy input, but also induces a plurality of side reactions, such as thermal cracking decarboxylation of carboxylic acid, self-condensation and cyclization of diamine, and the like. These side reactions not only lead to the formation of low molecular weight products, but also can impair the properties of the polymeric material. The solution polycondensation method can effectively reduce the volatilization of monomers and the occurrence of byproducts, and obtain a polymerization product with higher molecular weight.
Aiming at the reaction characteristics of high heat transfer requirement, side reaction, low molecular weight of the product and the like in the existing polyamide synthesis technology, the method brings good opportunity for strengthening the reaction by a micro-reactor technology. The micro characteristic size and the special structural design provide large specific surface area and high-efficiency heat transfer-mass transfer/mixing performance, can also realize accurate feeding control and intrinsically safe production according to stoichiometry, effectively realize polycondensation reaction between diamine and dicarboxylic acid, effectively realize timely removal of byproducts through process regulation and control, and are effective means for avoiding side reaction and improving reaction yield and selectivity.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art, namely, the melt polycondensation technology and the defects of the traditional kettle type stirring reactor, and provides a method for preparing bio-based semi-aromatic polyamide based on a micro-reaction device.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention discloses a method for preparing bio-based semi-aromatic polyamide based on a micro-reaction device, which comprises the following steps:
(1) Dissolving dicarboxylic acid and a catalyst in a solvent to obtain a first mixed solution; dissolving diamine in a solvent to obtain a second mixed solution;
(2) Pumping the first mixed solution and the second mixed solution obtained in the step (1) into a micro mixer in a micro reaction device respectively and simultaneously for mixing, and pumping the mixed solution into a low-temperature prepolymerization micro reactor in the micro reaction device for prepolymerization reaction after mixing; after the prepolymerization reaction is finished, continuously pumping the reaction liquid into a high-temperature polymerization microreactor in a microreaction device to carry out polymerization reaction, and after the reaction is finished, carrying out post-treatment on the reaction liquid to obtain the bio-based semi-aromatic polyamide.
In some embodiments, in step (1), the dicarboxylic acid is a furanyl dicarboxylic acid monomer or a furanyl dicarboxylic acid ester derivative; the furanyl dicarboxylic acid monomer is any one or the combination of a plurality of 2, 5-furandicarboxylic acid, 2, 4-furandicarboxylic acid, 3, 4-furandicarboxylic acid and 2, 5-furandiacetic acid; the furyl dicarboxylic acid ester derivative is any one or a combination of more than one of 2, 5-dimethyl furandicarboxylate, 2, 4-dimethyl furandicarboxylate and 3, 4-dimethyl furandicarboxylate; the catalyst is any one or the combination of a plurality of 1, 8-diazabicyclo undec-7-ene, N-methyl-1, 5, 7-triazabicyclo [4, 0] dec-5-ene, N-diisopropylethylamine, pyridine and isopropyl titanate; the solvent is any one or the combination of a plurality of N-methyl pyrrolidone, dimethylformamide, dimethyl sulfoxide, diphenyl ether, 2-methylnaphthalene and 1, 2-dichlorobenzene; the diamine is any one or a combination of more than one of 1, 5-pentanediamine, 1, 8-octanediamine, 1, 10-decanediamine, 2, 5-furandimethylamine and 2, 5-furandiethylamine.
In some embodiments, preferably, in step (1), the dicarboxylic acid is a furanyl dicarboxylic acid ester derivative; the furyl dicarboxylic ester derivative is 2, 5-dimethyl furandicarboxylate; the catalyst is N-methyl-1, 5, 7-triazabicyclo [4, 0] dec-5-ene or 1, 8-diazabicyclo undec-7-ene; the solvent is N-methyl pyrrolidone; the diamine is 1, 5-pentanediamine or 1, 10-decanediamine.
In some embodiments, in step (1), the concentration of dicarboxylic acid in the first mixed solution is 0.25-2 mol/L; the mol ratio of the catalyst to the dicarboxylic acid is 1% -10%: 1, a step of; the concentration of diamine in the second mixed solution is 0.25-7 mol/L.
In some embodiments, preferably, in the step (1), the concentration of dicarboxylic acid in the first mixed solution is 1-1.5 mol/L; the mol ratio of the catalyst to the dicarboxylic acid is 6% -9%: 1, a step of; the concentration of diamine in the second mixed solution is 5.3-5.6 mol/L.
In some embodiments, in step (2), the first mixture is pumped into a micromixer in the microreaction device at a flow rate of 0.01 to 5mL/min; the flow rate of the second mixed liquid pumped into the micro mixer in the micro reaction device is 0.01-5 mL/min.
In some embodiments, preferably, in step (2), the flow rate of the first mixture pumped into the micromixer in the microreaction device is 0.05 to 0.15mL/min; the flow rate of the second mixed liquid pumped into the micro mixer in the micro reaction device is 0.01-0.05 mL/min.
In some embodiments, more preferably, in step (2), the flow rate of the first mixture pumped into the micromixer in the microreaction device is 0.1mL/min; the flow rate of the second mixture pumped into the micromixer in the microreaction device was 0.02mL/min.
In some embodiments, in step (2), when the first mixed solution and the second mixed solution are simultaneously pumped into the micro mixer in the micro reaction device, the molar ratio of diamine to dicarboxylic acid is 1-1.4: 1.
in some embodiments, preferably, in step (2), when the first mixed solution and the second mixed solution are simultaneously pumped into the micro mixer in the micro reaction device, the molar ratio of diamine to dicarboxylic acid is 1:1.
in some embodiments, in step (2), the volume of the low temperature prepolymerization microreactor is from 2 to 20mL; the volume of the high-temperature polymerization micro-reactor is 2-20 mL; the prepolymerization reaction is carried out at a reaction temperature of 50-110 ℃ and a reaction pressure of 1-10 bar; the polymerization reaction is carried out at a reaction temperature of 110-190 ℃ and a reaction pressure of 1-10 bar.
In some embodiments, preferably, in step (2), the volume of the low temperature prepolymerization microreactor is from 3 to 10mL; the volume of the high-temperature polymerization micro-reactor is 3-10 mL; the prepolymerization reaction is carried out at the reaction temperature of 70-100 ℃; the polymerization reaction is carried out at a reaction temperature of 140-160 ℃.
In some embodiments, the microreactor means comprises a diacid storage tank, a diamine storage tank, a diacid transfer pump, a diamine transfer pump, a micromixer, a low temperature prepolymerization microreactor, a high temperature polymerization microreactor, and a product handling collection means; the dibasic acid storage tank is connected with the dibasic acid conveying pump through a pipeline; the diamine storage tank is connected with the diamine delivery pump through a pipeline; the dibasic acid conveying pump and the diamine conveying pump are connected in parallel through a pipeline and then connected with the micromixer; the micro-mixer, the low-temperature pre-polymerization micro-reactor, the high-temperature polymerization micro-reactor and the product treatment collection device are sequentially connected in series through a pipeline.
In some embodiments, the low temperature prepolymerization microreactor type is any one or a combination of two of a stainless steel tube microchannel reactor and a packed reactor comprising a static mixing structure; the number of the low-temperature prepolymerization microreactors can be 1 or more, when the number is selected to be more, the low-temperature prepolymerization microreactors are connected in series, and the types of the low-temperature prepolymerization microreactors can be the same or different.
In some embodiments, the high temperature polymerization microreactor type is any one or a combination of two of a stainless steel tube microchannel reactor and a packed reactor comprising a static mixing structure; the number of the high-temperature polymerization microreactors can be 1 or more, when the number is selected to be more, the high-temperature polymerization microreactors are connected in series, and the types of the high-temperature polymerization microreactors can be the same or different.
In some embodiments, the micromixer is a cascade stirred tank reactor coupled by an external force field; the hydraulic diameter of the micromixer is 0.1-3 mm.
In some embodiments, the external force field coupled cascade stirred tank reactors are connected in series by 4-10 stirred tank reactors through microchannel tubes, the volume of a single stirred tank reactor being 0.2-2 mL.
The cascade stirring kettle type reactor based on the coupling of the external force fields is a miniature kettle type reactor based on high-speed stirring, and reaction materials meet plug flow conditions when flowing in the reactor, so that the mixing reinforcement of viscous polymerization fluid is realized, and the polycondensation reaction performance is further improved.
In some embodiments, a back pressure valve is provided on the tubing between the transfer pump and the micromixer; the low-temperature prepolymerization microreactor is heated by a jacketed heat exchanger or by an oil bath; the high temperature polymerization microreactor is heated by a jacketed heat exchanger or by an oil bath.
The conveying pump is a syringe pump, and the model is Lei Fu TYD 01-01.
Wherein, the stirring mode of the cascade stirring kettle type reactor coupled by the external force field is magnetic stirring.
The cascade stirred tank reactor coupled by the external force field is manufactured through Formlabs 3D printing.
Wherein, by-products such as alcohols or water produced by a high temperature section in the high temperature polymerization micro-reactor overflows in a gas form, a gas-liquid slug flow is formed in the micro-channel, and polycondensation balance is driven to move forward by controlling gas-liquid fluid flow and transmission behavior reinforcement, so as to drive further reaction.
In some embodiments, the post-treatment of the reaction solution after the reaction is finished is specifically as follows: and (3) dropwise adding the reaction solution into excessive acetone or dichloromethane to perform precipitation, performing solid-liquid separation, fully washing a solid part with water, and drying to obtain the bio-based semi-aromatic polyamide solid product.
The beneficial effects are that:
(1) Compared with an intermittent kettle stirring method, the micro-reaction device provided by the invention can realize continuous preparation of polyamide, can realize rapid mixing of monomers, has accurate and controllable reaction time, improves reaction efficiency, effectively reduces incomplete reaction and the like, and more importantly, the polyamide obtained by the preparation method provided by the invention has higher molecular weight and narrow molecular weight distribution.
(2) Compared with the traditional melt polycondensation process which requires a high-temperature environment (about 260 ℃) to reach the melting temperature of the product, the solution polymerization method of the invention requires low reaction temperature, has good heat transfer performance, effectively avoids side reactions such as thermal pyrolysis decarboxylation (> 190 ℃) of carboxylic acid, N-methylation of polyamide, self-condensation of diamine, cyclization of diamine and the like, wherein the N-methylation is a main factor influencing the performance of the polymer, does not need a vacuum environment, and is more beneficial to industrial operation implementation.
(3) The low-temperature prepolymerization and high-temperature polymerization two-stage polymerization technology can drive forward movement of the reversible reaction by removing byproducts, so that the reaction is more complete, and the yield of the process are further improved.
(4) The polymer product of the invention is semi-aromatic polyamide, the molecular main chain of which contains both aromatic rings and aliphatic chains, and has excellent thermal performance of the aromatic polyamide and good molding processability of the aliphatic polyamide.
(5) The reactor in the micro-reaction device has small volume, high automation control degree and good safety.
(6) The solution polycondensation method is easier to realize homogeneous mixing and temperature control, effectively reduces volatilization of monomers and generation of oligomers, and reduces occurrence of side reaction at low temperature to obtain a polymerization product with higher molecular weight. However, the composition of materials, physical parameters, and rheological behavior in the polymerization system change with monomer conversion, and when the fluid viscosity of the reaction solution increases, the mass transfer performance between monomers becomes poor, thereby affecting the yield and molecular weight of the target polymer. Therefore, the micromixer in the microchannel reaction device is selected from cascade stirred tank reactors coupled by an external force field, 4-10 stirred tank reactors are connected in series through a microchannel pipeline to form the cascade stirred tank reactors coupled by the external force field, so that the mixing performance of the polymerized viscous fluid is effectively enhanced, and the mass transfer performance among monomers is improved, thereby improving the quality of products.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is a schematic diagram showing the overall structure of a microreaction device according to the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum of the bio-based semi-aromatic polyamide obtained in example 1.
FIG. 3 is an infrared spectrum of the bio-based semi-aromatic polyamide obtained in example 1.
FIG. 4 is a nuclear magnetic spectrum of the bio-based furan-based semi-aromatic polyamide obtained in example 1 in deuterated-trifluoroacetic acid (used to calculate the N-methylation rate of the polymer).
FIG. 5 is a schematic diagram of the structure of a spiral micromixer used in comparative example 2.
Detailed Description
The invention will be better understood from the following examples.
The overall structure schematic diagram of the micro-reaction device is shown in figure 1, and the micro-reaction device comprises a dibasic acid conveying pump, a diamine conveying pump, a micro-mixer, a low-temperature prepolymerization micro-reactor and a high-temperature polymerization micro-reactor; the dibasic acid conveying pump and the diamine conveying pump are connected in parallel through a pipeline and then connected with the micromixer; the micro mixer, the low-temperature prepolymerization micro reactor and the high-temperature polymerization micro reactor are sequentially connected in series through a pipeline.
The product treatment and collection device is arranged in the follow-up flow of the high-temperature polymerization microreactor.
The delivery pump is an injection pump, and the model is Lei Fu TYD01-01 type.
The micromixer is selected from cascade stirred tank reactors coupled by an external force field, the cascade stirred tank reactors coupled by the external force field are connected in series by 5 stirred tank reactors through micro-channel pipelines, the volume of a single stirred tank reactor is 0.4mL, the hydraulic diameter is 1.5mm, the cascade stirred tank reactors coupled by the external force field are manufactured by Formlabs through 3D printing, and the stirring mode is magnetic stirring.
Wherein, a back pressure valve is arranged on the pipeline between the delivery pump and the micromixer.
Wherein the low-temperature prepolymerization microreactor is heated by an oil bath.
Wherein the high temperature polymerization microreactor is heated by an oil bath.
Wherein, the low-temperature prepolymerization micro-reactor is a stainless steel pipe type micro-channel reactor, the volume is 8.5mL, 3.4mL,316 stainless steel pipe, and the inner diameter is 1.5mm.
Wherein, the high temperature polymerization micro-reactor is a stainless steel tube type micro-channel reactor, the volume is 8.5mL, the 316 stainless steel tube, and the inner diameter is 1.5mm.
Wherein, by-products such as alcohols or water produced by a high temperature section in the high temperature polymerization micro-reactor overflows through a gas form, a gas-liquid slug flow is formed in the micro-channel, and polycondensation balance is driven to move forward through controlling gas-liquid fluid flow and transmission behavior reinforcement, further reaction is driven, and the reaction yield of polyamide is improved.
Example 1
(1) Under the protection of nitrogen, 0.022mol of dimethyl 2, 5-furandicarboxylate and N-methyl-1, 5, 7-triazabicyclo [4, 0] dec-5-ene (the addition amount is 6% of the molar amount of dimethyl furandicarboxylate monomer) are dissolved in 20mL of N-methylpyrrolidone, so as to obtain a first mixed solution. 0.022mol of 1, 5-pentanediamine was dissolved in 4mL of N-methylpyrrolidone, to obtain a second mixed solution.
(2) Under the pressure of 1bar, pumping the first mixed solution and the second mixed solution obtained in the step (1) into a micro-mixer in a micro-reaction device respectively through a dibasic acid conveying pump and a diamine conveying pump to be mixed, wherein the micro-mixer adopts a cascade stirring kettle type reactor (formed by connecting 5 stirring kettle type reactors in series through a micro-channel pipeline, the effective volume of the stirring kettle type reactor is 2 mL), and the stirring speed is 800rmp; wherein, the pumping flow rate of the first mixed solution is 0.1mL/min, the pumping flow rate of the second mixed solution is 0.02mL/min, and the molar ratio of 1, 5-pentanediamine to 2, 5-dimethyl furandicarboxylate is 1:1. after mixing, continuously pumping the reaction liquid into a low-temperature prepolymerization micro-reactor (8.5 mL) in a micro-reaction device to perform prepolymerization reaction at 90 ℃; after the prepolymerization reaction is finished, the reaction solution is continuously pumped into a high-temperature polymerization microreactor (8.5 mL) in a microreactor device to carry out polymerization reaction at 140 ℃, and by-products generated by the temperature rise overflow to drive further reaction.
After the reaction is finished, obtaining a light yellow viscous reaction liquid, slowly dripping the reaction liquid containing the polymer into acetone for precipitation, carrying out solid-liquid separation, fully washing a solid part with water to remove a solvent and unreacted monomers, and then carrying out vacuum drying at 60 ℃ to finally obtain the bio-based semi-aromatic polyamide (polyfuran diformyl pentanediamine) powder, wherein the purification yield is 90%, the number average molecular weight is 69310g/mol, the PDI is 1.1, the nuclear magnetic hydrogen spectrum of the product is shown in figure 2, and the infrared spectrum of the product is shown in figure 3.
The glass transition temperature of the polymer product is 138 ℃, and the maximum decomposition rate temperature is 448 ℃, which shows that the prepared bio-based semi-aromatic polyamide (poly furan diformyl pentanediamine) has excellent thermal stability.
FIG. 4 is a nuclear magnetic spectrum of a bio-based semi-aromatic polyamide (poly (furan dicarboxylic acid) pentamer) in deuterated-trifluoroacetic acid with a polymer N-methylation ratio of 1.6% calculated according to the formula and by integration.
N-methylation ratio (%) =100% (integral at 3.00ppm+integral at 3.09ppm+integral at 3.18ppm)/3
Example 2
(1) Under the protection of nitrogen, 0.022mol of dimethyl 2, 5-furandicarboxylate and 1, 8-diazabicyclo undec-7-ene (the addition amount is 8% of the molar amount of dimethyl furandicarboxylate monomer) are dissolved in 20mL of N-methylpyrrolidone, so as to obtain a first mixed solution; 0.022mol of 1, 10-decanediamine was dissolved in 4mL of N-methylpyrrolidone, to obtain a second mixed solution.
(2) Under the pressure of 1bar, pumping the first mixed solution and the second mixed solution obtained in the step (1) into a micro-mixer in a micro-reaction device respectively through a dibasic acid conveying pump and a diamine conveying pump to be mixed, wherein the micro-mixer adopts a cascade stirring kettle type reactor (formed by connecting 5 stirring kettle type reactors in series through a micro-channel pipeline, the effective volume of the stirring kettle type reactor is 2 mL), and the stirring speed is 800rmp; wherein, the pumping flow rate of the first mixed solution is 0.1mL/min, the pumping flow rate of the second mixed solution is 0.02mL/min, and the molar ratio of 1, 10-decanediamine to 2, 5-dimethyl furandicarboxylate is 1:1. after mixing, continuously pumping the reaction liquid into a low-temperature prepolymerization microreactor (3.4 mL) in a microreactor to perform prepolymerization reaction at 90 ℃; after the prepolymerization reaction is finished, the reaction solution is continuously pumped into a high-temperature polymerization microreactor (8.5 mL) in a microreactor device to carry out polymerization reaction at 150 ℃, and by-products generated by the temperature rise overflow to drive further reaction.
After the reaction is finished, obtaining a light yellow viscous reaction liquid, slowly dripping the reaction liquid containing the polymer into acetone for precipitation, carrying out solid-liquid separation, fully washing a solid part with water to remove a solvent and unreacted monomers, and then carrying out vacuum drying at 60 ℃ to finally obtain the bio-based semi-aromatic polyamide (polyfurandiformyldecanediamine) powder, wherein the purification yield is 86%, the number average molecular weight is 83310g/mol, the PDI is 1.2, and the N-methylation rate of the polymer is 1.76%.
Comparative example 1: preparation of biobased semi-aromatic polyamides by conventional methods
Under the protection of nitrogen, 0.022mol of dimethyl 2, 5-furandicarboxylate, 0.022mol of 1, 5-pentanediamine and N-methyl-1, 5, 7-triazabicyclo [4, 0] dec-5-ene (the addition amount is 6% of the molar amount of dimethyl furandicarboxylate monomer) are dissolved in 24mL of N-methylpyrrolidone, then the mixed solution is placed in a reaction bottle for prepolymerization at 70 ℃ for 1 hour, and then the reaction system is transferred into an oil bath placed at 140 ℃ for continuous polymerization for 5 hours.
Obtaining yellowish viscous reaction liquid after the reaction is finished, slowly dripping the reaction liquid containing the polymer into acetone for precipitation, carrying out solid-liquid separation, fully washing a solid part with water to remove a solvent and unreacted monomers, and then carrying out vacuum drying at 60 ℃ to finally obtain the bio-based semi-aromatic polyamide (polyfuran diformyl pentanediamine) powder, wherein the purification yield is 60%, the number average molecular weight is 46210g/mol, the molecular weight distribution index is 2.05, and the N-methylation rate of the polyamide is 8.04%.
Comparative example 2: by screw-type micromixers
The spiral micromixer of this embodiment is manufactured by 3D printing using Formlabs, the inside diameter of the channel is 3mm, the length of a single spiral sheet is 9mm, the thickness is 0.8mm, and the number of serial connection is 8, and the schematic structure is shown in fig. 5.
The preparation method is the same as in example 1, except that: replacing the cascade stirring kettle type reactor coupled by the external force field with a spiral micro-mixer; finally, the biobased semi-aromatic polyamide (poly furan diformyl pentanediamine) powder is obtained, the purification yield is 71 percent, the number average molecular weight is 56310g/mol, the PDI is 1.15, and the N-methylation rate of the polymer is calculated to be 1.82 percent. The final product yield and molecular weight were reduced compared to example 1 by mixing using a helical micromixer.
Compared with the method of the comparative example, the method for protecting the bio-based semi-aromatic polyamide shortens the polymerization reaction time, improves the yield of polymer products, improves the molecular weight of the polymer products, reduces the distribution index and the N-methylation rate, and has obvious advantages.
The invention provides a method for preparing bio-based semi-aromatic polyamide based on a micro-reaction device, and the method for realizing the technical scheme is a plurality of methods and approaches, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by one of ordinary skill in the art without departing from the principle of the invention, and the improvements and modifications should also be regarded as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (10)
1. A method for preparing bio-based semi-aromatic polyamide based on a micro-reaction device, which is characterized by comprising the following steps:
(1) Dissolving dicarboxylic acid and a catalyst in a solvent to obtain a first mixed solution; dissolving diamine in a solvent to obtain a second mixed solution;
(2) Pumping the first mixed solution and the second mixed solution obtained in the step (1) into a micro mixer in a micro reaction device respectively and simultaneously for mixing, and pumping the mixed solution into a low-temperature prepolymerization micro reactor in the micro reaction device for prepolymerization reaction after mixing; after the prepolymerization reaction is finished, continuously pumping the reaction liquid into a high-temperature polymerization microreactor in a microreaction device to carry out polymerization reaction, and after the reaction is finished, carrying out post-treatment on the reaction liquid to obtain the bio-based semi-aromatic polyamide.
2. The method according to claim 1, wherein in step (1), the dicarboxylic acid is a furanyl dicarboxylic acid monomer or a furanyl dicarboxylic acid ester derivative; the furanyl dicarboxylic acid monomer is any one or the combination of a plurality of 2, 5-furandicarboxylic acid, 2, 4-furandicarboxylic acid, 3, 4-furandicarboxylic acid and 2, 5-furandiacetic acid; the furyl dicarboxylic acid ester derivative is any one or a combination of more than one of 2, 5-dimethyl furandicarboxylate, 2, 4-dimethyl furandicarboxylate and 3, 4-dimethyl furandicarboxylate; the catalyst is any one or the combination of a plurality of 1, 8-diazabicyclo undec-7-ene, N-methyl-1, 5, 7-triazabicyclo [4, 0] dec-5-ene, N-diisopropylethylamine, pyridine and isopropyl titanate; the solvent is any one or the combination of a plurality of N-methyl pyrrolidone, dimethylformamide, dimethyl sulfoxide, diphenyl ether, 2-methylnaphthalene and 1, 2-dichlorobenzene; the diamine is any one or a combination of more than one of 1, 5-pentanediamine, 1, 8-octanediamine, 1, 10-decanediamine, 2, 5-furandimethylamine and 2, 5-furandiethylamine.
3. The method according to claim 1, wherein in the step (1), the concentration of dicarboxylic acid in the first mixed solution is 0.25 to 2mol/L; the mol ratio of the catalyst to the dicarboxylic acid is 1% -10%: 1, a step of; the concentration of diamine in the second mixed solution is 0.25-7 mol/L.
4. The method according to claim 1, wherein in step (2), the flow rate of the first mixture pumped into the micromixer in the microreaction device is 0.01 to 5mL/min; the flow rate of the second mixed liquid pumped into the micro mixer in the micro reaction device is 0.01-5 mL/min.
5. The method according to claim 1, wherein in the step (2), when the first mixed solution and the second mixed solution are simultaneously pumped into the micromixer in the microreactor device, the molar ratio of diamine to dicarboxylic acid is 1 to 1.4:1.
6. the method according to claim 1, wherein in the step (2), the volume of the low-temperature prepolymerization microreactor is 2 to 20mL; the volume of the high-temperature polymerization micro-reactor is 2-20 mL; the prepolymerization reaction is carried out at a reaction temperature of 50-110 ℃ and a reaction pressure of 1-10 bar; the polymerization reaction is carried out at a reaction temperature of 110-190 ℃ and a reaction pressure of 1-10 bar.
7. The method of claim 1, wherein the microreactor means comprises a diacid storage tank, a diamine storage tank, a diacid transfer pump, a diamine transfer pump, a micromixer, a low temperature prepolymerization microreactor, a high temperature polymerization microreactor, and a product handling collection means; the dibasic acid storage tank is connected with the dibasic acid conveying pump through a pipeline; the diamine storage tank is connected with the diamine delivery pump through a pipeline; the dibasic acid conveying pump and the diamine conveying pump are connected in parallel through a pipeline and then connected with the micromixer; the micro-mixer, the low-temperature pre-polymerization micro-reactor, the high-temperature polymerization micro-reactor and the product treatment collection device are sequentially connected in series through a pipeline.
8. The method of claim 7, wherein the low temperature prepolymerization microreactor is any one or a combination of two of a stainless steel tube microchannel reactor and a packed reactor comprising a static mixing structure; the high-temperature polymerization micro-reactor is any one or the combination of two of a stainless steel pipe type micro-channel reactor and a filling reactor containing a static mixing structure; the micromixer is a cascade stirring kettle type reactor coupled by an external force field; the hydraulic diameter of the micromixer is 0.1-3 mm.
9. The method according to claim 8, wherein the cascade stirred tank reactors coupled by the external force field are connected in series by 4 to 10 stirred tank reactors through a microchannel tube, and the volume of a single stirred tank reactor is 0.2 to 2mL.
10. The method of claim 7, wherein a back pressure valve is provided on the conduit between the transfer pump and the micromixer; the low-temperature prepolymerization microreactor is heated by a jacketed heat exchanger or by an oil bath; the high temperature polymerization microreactor is heated by a jacketed heat exchanger or by an oil bath.
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