CN115850543B - Anionic polymerization continuous polymerization process for methyl methacrylate - Google Patents
Anionic polymerization continuous polymerization process for methyl methacrylate Download PDFInfo
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- CN115850543B CN115850543B CN202211150054.7A CN202211150054A CN115850543B CN 115850543 B CN115850543 B CN 115850543B CN 202211150054 A CN202211150054 A CN 202211150054A CN 115850543 B CN115850543 B CN 115850543B
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title abstract description 44
- 238000006116 polymerization reaction Methods 0.000 title abstract description 39
- 238000010539 anionic addition polymerization reaction Methods 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 122
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 59
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 57
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 103
- 239000000463 material Substances 0.000 claims description 97
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 17
- 230000001105 regulatory effect Effects 0.000 claims description 15
- 150000003863 ammonium salts Chemical class 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000001308 synthesis method Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 25
- 238000012546 transfer Methods 0.000 abstract description 10
- 238000010924 continuous production Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 29
- 230000001276 controlling effect Effects 0.000 description 28
- 238000009826 distribution Methods 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 15
- 238000005086 pumping Methods 0.000 description 7
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000009194 climbing Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 229920005372 Plexiglas® Polymers 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- -1 aryl ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a continuous polymerization process for anionic polymerization of methyl methacrylate, and belongs to the technical field of preparation of polymethyl methacrylate high polymer materials. The invention solves the problems of mass and heat transfer and the like caused by rapid heat release due to the rapid polymerization rate of a high-activity catalyst system in the existing polymethyl methacrylate polymerization process. The polymerization reaction adopts the micro-channel reactor to realize the polymerization of MMA catalyzed by the high-activity catalyst system at normal temperature and normal pressure, thereby greatly improving the polymerization reaction time and basically completing the 30s polymerization reaction. In addition, the single pass conversion rate of MMA monomer in the reaction process is high and can reach more than 90%, which is favorable for the subsequent step of removing low, and has obvious energy conservation and consumption reduction. In addition, the polymerization process is simple, the processes of removing monomers and removing ash of the catalyst are omitted, the equipment investment is small, and the method is suitable for large-scale continuous production of polymethyl methacrylate.
Description
Technical Field
The invention relates to a continuous polymerization process for anionic polymerization of methyl methacrylate, and belongs to the technical field of preparation of polymethyl methacrylate high polymer materials.
Background
Polymethyl methacrylate (PMMA), also known as acrylic, acrylic or plexiglass, is polymerized from Methyl Methacrylate (MMA). PMMA has excellent light transmittance, good apparent glossiness, excellent weather resistance, light weight, high definition, extremely strong impact resistance and good post-processing performance. Because of low price, energy conservation and environmental protection, the material has successfully replaced glass and is widely applied to traffic, sanitary ware, advertising light boxes, medical science, optics, IT industries and the like.
The existing polymethyl methacrylate polymerization method comprises free radical polymerization, anion polymerization and living free radical polymerization, the polymerization technology comprises three processes of suspension polymerization, solution polymerization and bulk polymerization, the suspension polymerization process is the main process of small-scale intermittent production, and the solution polymerization and the bulk polymerization process are adopted for large-scale continuous production.
The suspension polymerization uses water as a continuous phase, the viscosity of the system is low, the material viscosity is not greatly changed in the reaction process, the polymerization reaction heat is easy to remove, the temperature is easy to control, the production operation is safer, the process flow is short, the method can be directly used for molding processing, the technology is mature, the equipment investment cost is low, and the method is the most traditional method adopted in all countries of the world. However, suspension polymerization has low productivity, is not suitable for large-scale continuous production, and requires complicated steps such as filtration, washing, drying and the like in the manufacturing process, so that the production efficiency is reduced. Because of the problems of poor purity of the product and a large amount of sewage, the product cannot meet the requirements of product quality and environmental protection, and the product is gradually eliminated.
The solution polymerization method has low viscosity of the polymerization system, easy control of mass transfer and heat transfer, stable control of operation conditions, large-scale continuous production and no sewage treatment problem. However, the polymerization system contains a large amount of solvent, so that the monomer concentration is low, the polymerization rate is low, and the equipment utilization rate and the production capacity are low; the polymer solution needs to be subjected to post-treatment processes such as multi-stage flash evaporation devolatilization, granulation and the like to obtain a resin product; meanwhile, a large amount of removed solvent and unreacted monomers need to be rectified and purified, and are recovered and reused, so that the energy consumption of post-treatment is high, and the production cost is increased.
The bulk polymerization method is continuous production, advanced in production technology, purer in product, high in transparency, low in energy consumption for post-treatment, and applicable to the market of high-end PMMA products, and only a small amount of unreacted monomers need to be recovered. However, the viscosity of the polymerization system is high, and the mass transfer and heat transfer are relatively difficult to control, so that the requirements on equipment and the technological operation process are severe.
The polymerization process adopted by the polymerization method ensures the safety and conversion rate problems in the polymerization engineering by using a high-pressure reaction kettle. However, for high conversion and high activity polymerization systems, the viscosity of the high conversion polymerization system increases dramatically, resulting in serious pole climbing. Therefore, for a high activity and high conversion system, a continuous polymerization process is provided, which can greatly reduce the preparation cost and improve the production efficiency. In addition, providing a process for preparing polymethyl methacrylate with mild reaction conditions, simple operation, high molecular weight and narrow molecular weight distribution is a problem to be solved by those skilled in the art.
Disclosure of Invention
Aiming at the problems of rapid increase in viscosity, pole climbing phenomenon and the like caused by mass transfer and heat transfer initiated by rapid heat release when the traditional reaction equipment is used for synthesizing polymethyl methacrylate by using a high-conversion-rate high-activity catalyst system, the invention provides a continuous production method of PMMA with high efficiency, high quality and narrow molecular weight distribution.
The invention aims to provide a preparation method of polymethyl methacrylate, which takes methyl methacrylate as a monomer raw material in an organic solvent, and carries out anionic polymerization under the catalysis of a catalyst consisting of potassium tert-butoxide and ammonium salt to obtain the polymethyl methacrylate.
Further defined, the molar ratio of potassium tert-butoxide to ammonium salt is (1-4): 1.
further defined, the volume ratio of toluene to MMA is (1 to 4): 1.
further defined, the polymerization temperature is 40℃to 80 ℃.
Further defined, the catalyst is used in an amount of 100 to 500ppm.
The second object of the invention is to provide a method for preparing polymethyl methacrylate by using a microchannel reactor, wherein the microchannel reactor comprises a reaction module group, and the reaction module group comprises one unit reaction module or is formed by combining more than two unit reaction modules in series;
the synthesis method comprises the following steps:
s1, mixing a catalyst and dissolving the catalyst in an organic solvent to obtain a material A for later use;
s2, dissolving MMA in an organic solvent to obtain a material B for later use;
s3, conveying the material A and the material B to a reaction module group of the microchannel reactor respectively by using a feed pump, reacting the reaction feed liquid at normal temperature, wherein the total residence time of the reaction feed liquid in the reaction module group is 0.1-30 min, and discharging from the tail end of the reaction module group after the reaction is finished to obtain polymethyl methacrylate.
Further defined, the catalyst includes potassium tert-butoxide and ammonium salts.
Further defined, the molar ratio of potassium tert-butoxide to ammonium salt is (1-4): 1.
further defined, the molar ratio of potassium tert-butoxide to ammonium salt is (1-2): 1.
further defined, the ammonium salt is an alkyl ammonium salt.
Further defined, the ammonium salt is one or more of tetrabutylammonium bromide, tetrabutylammonium chloride, or other alkyl and aryl ammonium salts mixed in any proportion.
Further defined, the organic solvent is toluene.
Further defined, the volume ratio of toluene to MMA is (1-4): 1.
further defined, the volume ratio of toluene to MMA is (2-3): 1.
further defined, the amount of catalyst is controlled by adjusting the feed flow rates of feed A and feed B using a feed pump, the catalyst amount being 100 to 1500ppm.
Further defined, the catalyst is used in an amount of 300 to 1500ppm.
Further defined, the total residence time of the reactant feed in the reaction module group is 0.1 to 1min.
Further, the room temperature condition is 22 to 40 ℃.
Further defined, the ambient temperature condition is 24 ℃.
Further limited, the tail end of the reaction module group is connected with vacuum equipment, so that the vacuum degree can be reduced while the viscosity of the polymerization reaction system is increased, and the high-viscosity product can be continuously discharged.
Further limited, the vacuum degree during discharging is 0.005-0.1 MPa.
Further defined, the vacuum degree is 0.01 to 0.05MPa.
It is a further object of the present invention to provide polymethyl methacrylate obtained by the above-mentioned production method, wherein the molecular weight of the polymethyl methacrylate molecule is 10000 to 300000g/mol.
Further limited, the obtained polymethyl methacrylate can be used in the fields of automobile lamps, liquid crystal display light guide plates, decorative lamps, advertising lamp boxes and the like.
The method for preparing polymethyl methacrylate by the micro-channel reactor provided by the invention is realized by adopting the micro-channel reactor, and the problems of high polymerization rate, mass transfer, heat transfer and the like caused by rapid heat release of a high-activity catalyst system are effectively solved. Compared with the prior art, the application has the following beneficial effects:
(1) The invention realizes continuous production of polymethyl methacrylate, has simple polymerization process and small equipment investment, and is suitable for large-scale production.
(2) The invention adopts a feeding pump with a flowmeter for feeding, controls the catalyst dosage through the flow rate, adopts a micro-channel reactor cooled by external circulating water for the polymerization reactor, and the tail end of the reactor is connected with vacuum equipment, thereby omitting the steps of monomer removal and purification and catalyst removal, having high monomer conversion rate, low volatile content and saving energy consumption, and being particularly suitable for continuous production of PMMA with high quality and narrow molecular weight distribution (molecular weight distribution of 1.5-3).
(3) The invention adopts potassium tert-butoxide and organic ammonium salt as methyl methacrylate anionic polymerization catalyst, the catalyst has high catalyst activity and small side reaction, has better tolerance to oxygen, and the addition of ammonium salt can effectively inhibit the side reaction of 'back biting' and 'chain transfer' in the polymerization process, thereby improving the single pass conversion rate of MMA monomer and the controllability of polymerization reaction.
(4) The polymerization condition of polymethyl methacrylate in the preparation method provided by the invention is normal temperature and pressure, and the single-pass conversion rate of MMA monomer is high and can reach more than 90% due to the potassium tert-butoxide and ammonium salt catalytic system, thereby being beneficial to the subsequent step of removing low, reducing volatile matters of products and improving the product quality; compared with the existing anionic polymerization system and process, the polymerization time is shorter, the polymerization is completed basically for 30 seconds, the residue of the organic base catalyst does not affect the physical properties of the product, the catalyst deashing step in the continuous polymerization process can be omitted, the polymerization process is effectively simplified, and the problems of high temperature and high pressure continuous polymerization conditions, low monomer conversion rate, low deashing energy consumption caused by the increase of the viscosity of the system in the later stage of the polymerization reaction and the like in the existing PMMA polymerization process are solved.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The reaction module group of the microchannel reactor used in the following examples is formed by combining two unit reaction modules in series. The feeding adopts a feeding pump with a flowmeter, the micro-channel reactor adopts external circulating water cooling, and the tail end of the reactor is connected with vacuum equipment.
Example 1:
the number average molecular weight of the PMMA polymer prepared in this example was 80000g/mol, using a molar ratio of potassium tert-butoxide, tetrabutylammonium bromide and MMA of 1:1:800.
the preparation process is as follows:
s1, uniformly mixing potassium tert-butoxide (135 mg,1 equivalent) and tetrabutylammonium bromide (400 mg,1 equivalent) with toluene (200 mL) to obtain a material A;
s2, mixing MMA (100 mL) and toluene (100 mL) uniformly to obtain a material B;
s3, conveying the material A and the material B to a reaction module group of the microchannel reactor by using a feed pump respectively, regulating the flow rate of the feed pump to enable the material A and the material B to be fed simultaneously, enabling the feed rate to be 10mL/min and 10mL/min respectively, reacting at normal temperature, controlling the total residence time of the reaction feed liquid in the reaction module group to be 7.2S, controlling the temperature of the two unit reaction modules to be 31 ℃ and 27 ℃ respectively, setting the pump pressure of a reaction terminal vacuum device to be 2MPa, discharging, and obtaining the high molecular weight PMMA, wherein the GPC molecular weight is 65200g/mol, the molecular weight distribution is 1.85, the monomer conversion rate is 93.0%, and the volatile matter is 0.50%.
Example 2:
the number average molecular weight of the PMMA polymer prepared in this example was 80000g/mol, using a molar ratio of potassium tert-butoxide, tetrabutylammonium bromide and MMA of 1:1:800.
the preparation process is as follows:
s1, uniformly mixing potassium tert-butoxide (135 mg,1 equivalent) and tetrabutylammonium bromide (400 mg,1 equivalent) with toluene (200 mL) to obtain a material A;
s2, mixing MMA (100 mL) and toluene (100 mL) uniformly to obtain a material B;
s3, conveying the material A and the material B to a reaction module group of a microchannel reactor respectively by using a feed pump, regulating the flow rate of the feed pump to enable the material A and the material B to be fed simultaneously, enabling the feed rate to be 10mL/min and 10mL/min respectively, reacting at normal temperature, controlling the total residence time of the reaction feed liquid in the reaction module group to be 7.2S, controlling the temperature of the two unit reaction modules to be 30 ℃ and 29 ℃ respectively, setting the pump pressure of a reaction terminal vacuum device to be 2.8MPa, discharging, and obtaining the high molecular weight PMMA, wherein the GPC molecular weight is 62200g/mol, the molecular weight distribution is 1.77, the monomer conversion rate is 94.9%, and the volatile matter is 0.30%.
Example 3:
the number average molecular weight of the PMMA polymer prepared in this example was 80000g/mol, using a molar ratio of potassium tert-butoxide, tetrabutylammonium bromide and MMA of 1:1:800.
the preparation process is as follows:
s1, uniformly mixing potassium tert-butoxide (135 mg,1 equivalent) and tetrabutylammonium bromide (400 mg,1 equivalent) with toluene (200 mL) to obtain a material A;
s2, mixing MMA (100 mL) and toluene (100 mL) uniformly to obtain a material B;
s3, conveying the material A and the material B to a reaction module group of a microchannel reactor respectively by using a feed pump, regulating the flow rate of the feed pump to enable the material A and the material B to be fed simultaneously, enabling the feed rate to be 15mL/min and 15mL/min respectively, reacting at normal temperature, controlling the total residence time of the reaction feed liquid in the reaction module group to be 4.8S, controlling the temperature of the two unit reaction modules to be 24 ℃ and 32 ℃ respectively, setting the pumping pressure of a reaction terminal vacuum device to be 2.9MPa, discharging, and obtaining the high molecular weight PMMA, wherein the GPC molecular weight is 70400g/mol, the molecular weight distribution is 1.83, the monomer conversion rate is 96.2%, and the volatile matter is 0.30%.
Example 4:
the number average molecular weight of the PMMA polymer prepared in this example was 80000g/mol, using a molar ratio of potassium tert-butoxide, tetrabutylammonium bromide and MMA of 1:1:800.
the preparation process is as follows:
s1, uniformly mixing potassium tert-butoxide (135 mg,1 equivalent) and tetrabutylammonium bromide (400 mg,1 equivalent) with toluene (200 mL) to obtain a material A;
s2, mixing MMA (100 mL) and toluene (100 mL) uniformly to obtain a material B;
s3, conveying the material A and the material B to a reaction module group of the microchannel reactor by using a feed pump respectively, regulating the flow rate of the feed pump to enable the material A and the material B to be fed simultaneously, enabling the feed rate to be 15mL/min and 15mL/min respectively, reacting at normal temperature, controlling the total residence time of the reaction feed liquid in the reaction module group to be 4.8S, controlling the temperature of the two unit reaction modules to be 24 ℃ and 32 ℃ respectively, setting the pumping pressure of a reaction terminal vacuum device to be 3.3MPa, discharging, and obtaining the high molecular weight PMMA, wherein the GPC molecular weight is 70400g/mol, the molecular weight distribution is 1.85, the monomer conversion rate is 96.4%, and the volatile matter is 0.30%.
Example 5:
the number average molecular weight of the PMMA polymer prepared in this example was 80000g/mol, using a molar ratio of potassium tert-butoxide, tetrabutylammonium bromide and MMA of 1:1:800.
the preparation process is as follows:
s1, uniformly mixing potassium tert-butoxide (135 mg,1 equivalent) and tetrabutylammonium bromide (400 mg,1 equivalent) with toluene (200 mL) to obtain a material A;
s2, mixing MMA (100 mL) and toluene (100 mL) uniformly to obtain a material B;
s3, conveying the material A and the material B to a reaction module group of the microchannel reactor by using a feed pump respectively, regulating the flow rate of the feed pump to enable the material A and the material B to be fed simultaneously, enabling the feed rate to be 20mL/min and 20mL/min respectively, reacting at normal temperature, controlling the total residence time of the reaction feed liquid in the reaction module group to be 3.6S, controlling the temperature of the two unit reaction modules to be 22 ℃ and 44 ℃ respectively, setting the pump pressure of a reaction terminal vacuum device to be 3.6MPa, discharging, and obtaining the high molecular weight PMMA, wherein the GPC molecular weight is 68400g/mol, the molecular weight distribution is 1.85, the monomer conversion rate is 95.1%, and the volatile matter is 0.30%.
Example 6:
the number average molecular weight of the PMMA polymer prepared in this example was 80000g/mol, using a molar ratio of potassium tert-butoxide, tetrabutylammonium bromide and MMA of 1:1:800.
the preparation process is as follows:
s1, uniformly mixing potassium tert-butoxide (135 mg,1 equivalent) and tetrabutylammonium bromide (400 mg,1 equivalent) with toluene (200 mL) to obtain a material A;
s2, mixing MMA (100 mL) and toluene (100 mL) uniformly to obtain a material B;
s3, conveying the material A and the material B to a reaction module group of a microchannel reactor respectively by using a feed pump, regulating the flow rate of the feed pump to enable the material A and the material B to be fed simultaneously, enabling the feed rate to be 20mL/min and 20mL/min respectively, reacting at normal temperature, controlling the total residence time of the reaction feed liquid in the reaction module group to be 3.6S, controlling the temperature of the two unit reaction modules to be 22 ℃ and 41 ℃ respectively, setting the pump pressure of a reaction terminal vacuum device to be 3.9MPa, discharging, and obtaining the high molecular weight PMMA, wherein the GPC molecular weight is 70200g/mol, the molecular weight distribution is 1.82, the monomer conversion rate is 95.0%, and the volatile matter is 0.30%.
Example 7:
the number average molecular weight of the PMMA polymer prepared in this example was 80000g/mol, using a molar ratio of potassium tert-butoxide, tetrabutylammonium bromide and MMA of 1:1:800.
the preparation process is as follows:
s1, uniformly mixing potassium tert-butoxide (135 mg,1 equivalent) and tetrabutylammonium bromide (400 mg,1 equivalent) with toluene (200 mL) to obtain a material A;
s2, mixing MMA (100 mL) and toluene (100 mL) uniformly to obtain a material B;
s3, conveying the material A and the material B to a reaction module group of a microchannel reactor respectively by using a feed pump, regulating the flow rate of the feed pump to enable the material A and the material B to be fed simultaneously, enabling the feed rate to be 25mL/min and 25mL/min respectively, reacting at normal temperature, controlling the total residence time of the reaction feed liquid in the reaction module group to be 2.9S, controlling the temperature of the two unit reaction modules to be 23 ℃ and 42 ℃ respectively, setting the pumping pressure of a reaction end vacuum device to be 4.2MPa, discharging, and obtaining high molecular weight PMMA, wherein the GPC molecular weight is 65600g/mol, the molecular weight distribution is 1.84, the monomer conversion rate is 92.9%, and the volatile matter is 0.50%.
Example 8:
the number average molecular weight of the PMMA polymer prepared in this example was 80000g/mol, using a molar ratio of potassium tert-butoxide, tetrabutylammonium bromide and MMA of 1:1:800.
the preparation process is as follows:
s1, uniformly mixing potassium tert-butoxide (135 mg,1 equivalent) and tetrabutylammonium bromide (400 mg,1 equivalent) with toluene (200 mL) to obtain a material A;
s2, mixing MMA (100 mL) and toluene (100 mL) uniformly to obtain a material B;
s3, conveying the material A and the material B to a reaction module group of a microchannel reactor respectively by using a feed pump, regulating the flow rate of the feed pump to enable the material A and the material B to be fed simultaneously, enabling the feed rate to be 25mL/min and 25mL/min respectively, reacting at normal temperature, controlling the total residence time of the reaction feed liquid in the reaction module group to be 2.9S, controlling the temperature of the two unit reaction modules to be 23 ℃ and 42 ℃ respectively, setting the pump pressure of a reaction end vacuum device to be 4.2MPa, discharging, and obtaining the high molecular weight PMMA, wherein the GPC molecular weight is 63100g/mol, the molecular weight distribution is 1.92, the monomer conversion rate is 93.4%, and the volatile matter is 0.50%.
Example 9:
the present example was designed to prepare PMMA polymer having a number average molecular weight of 160000g/mol using a molar ratio of potassium tert-butoxide, tetrabutylammonium bromide and MMA of 1:1:1600.
the preparation process is as follows:
s1, uniformly mixing potassium tert-butoxide (135 mg,1 equivalent) and tetrabutylammonium bromide (400 mg,1 equivalent) with toluene (300 mL) to obtain a material A;
s2, mixing MMA (200 mL) and toluene (100 mL) uniformly to obtain a material B;
s3, conveying the material A and the material B to a reaction module group of the microchannel reactor by using a feed pump respectively, regulating the flow rate of the feed pump to enable the material A and the material B to be fed simultaneously, enabling the feed rate to be 20mL/min and 10mL/min respectively, reacting at normal temperature, controlling the total residence time of the reaction feed liquid in the reaction module group to be 4.8S, controlling the temperature of the two unit reaction modules to be 24 ℃ and 36 ℃ respectively, setting the pump pressure of a reaction terminal vacuum device to be 2.8MPa, discharging, and obtaining the high molecular weight PMMA, wherein the GPC molecular weight is 60800g/mol, the molecular weight distribution is 1.83, the monomer conversion rate is 43.4%, and the volatile matter is 0.80%.
Example 10:
the present example was designed to prepare PMMA polymer having a number average molecular weight of 160000g/mol using a molar ratio of potassium tert-butoxide, tetrabutylammonium bromide and MMA of 1:1:1600.
the preparation process is as follows:
s1, uniformly mixing potassium tert-butoxide (135 mg,1 equivalent) and tetrabutylammonium bromide (400 mg,1 equivalent) with toluene (300 mL) to obtain a material A;
s2, mixing MMA (200 mL) and toluene (100 mL) uniformly to obtain a material B;
s3, conveying the material A and the material B to a reaction module group of the microchannel reactor by using a feed pump respectively, regulating the flow rate of the feed pump to enable the material A and the material B to be fed simultaneously, enabling the feed rate to be 20mL/min and 10mL/min respectively, reacting at normal temperature, controlling the total residence time of the reaction feed liquid in the reaction module group to be 4.8S, controlling the temperature of the two unit reaction modules to be 24 ℃ and 36 ℃ respectively, setting the pumping pressure of a reaction terminal vacuum device to be 3.1MPa, discharging, and obtaining the high molecular weight PMMA, wherein the GPC molecular weight is 57700g/mol, the molecular weight distribution is 1.82, the monomer conversion rate is 37.0%, and the volatile matter is 0.80%.
Example 11:
the present example was designed to prepare PMMA polymer having a number average molecular weight of 160000g/mol using a molar ratio of potassium tert-butoxide, tetrabutylammonium bromide and MMA of 1:1:1600.
the preparation process is as follows:
s1, uniformly mixing potassium tert-butoxide (135 mg,1 equivalent) and tetrabutylammonium bromide (400 mg,1 equivalent) with toluene (300 mL) to obtain a material A;
s2, mixing MMA (200 mL) and toluene (100 mL) uniformly to obtain a material B;
s3, conveying the material A and the material B to a reaction module group of a microchannel reactor respectively by using a feed pump, regulating the flow rate of the feed pump to enable the material A and the material B to be fed simultaneously, enabling the feed rate to be 10mL/min and 5mL/min respectively, reacting at normal temperature, controlling the total residence time of the reaction feed liquid in the reaction module group to be 9.6S, controlling the temperature of the two unit reaction modules to be 24 ℃ and 33 ℃ respectively, setting the pump pressure of a reaction terminal vacuum device to be 2.8MPa, discharging, and obtaining the high molecular weight PMMA, wherein the GPC molecular weight is 75400g/mol, the molecular weight distribution is 1.94, the monomer conversion rate is 72.0%, and the volatile matter is 0.50%.
Example 12:
the number average molecular weight of the PMMA polymer prepared in this example was 80000g/mol, using a molar ratio of potassium tert-butoxide, tetrabutylammonium bromide and MMA of 1:1:800.
the preparation process is as follows:
s1, uniformly mixing potassium tert-butoxide (135 mg,1 equivalent) and tetrabutylammonium bromide (400 mg,1 equivalent) with toluene (200 mL) to obtain a material A;
s2, mixing MMA (100 mL) and toluene (100 mL) uniformly to obtain a material B;
s3, conveying the material A and the material B to a reaction module group of the microchannel reactor by using a feed pump respectively, regulating the flow rate of the feed pump to enable the material A and the material B to be fed simultaneously, enabling the feed rate to be 30mL/min and 10mL/min respectively, reacting at normal temperature, controlling the total residence time of the reaction feed liquid in the reaction module group to be 40S, controlling the temperature of the two unit reaction modules to be 24 ℃ and 33 ℃ respectively, setting the pumping pressure of a reaction terminal vacuum device to be 2.8MPa, discharging, and obtaining the high molecular weight PMMA, wherein the GPC molecular weight is 61300g/mol, the molecular weight distribution is 1.87, the monomer conversion rate is 97.0%, and the volatile matter is 0.20%.
Example 13:
the number average molecular weight of the PMMA polymer prepared in this example was 80000g/mol, using a molar ratio of potassium tert-butoxide, tetrabutylammonium bromide and MMA of 1:1:800.
the preparation process is as follows:
s1, uniformly mixing potassium tert-butoxide (135 mg,1 equivalent) and tetrabutylammonium bromide (400 mg,1 equivalent) with toluene (150 mL) to obtain a material A;
s2, mixing MMA (100 mL) and toluene (50 mL) uniformly to obtain a material B;
s3, conveying the material A and the material B to a reaction module group of the microchannel reactor by using a feed pump respectively, regulating the flow rate of the feed pump to enable the material A and the material B to be fed simultaneously, enabling the feed rate to be 20mL/min and 10mL/min respectively, reacting at normal temperature, controlling the total residence time of the reaction feed liquid in the reaction module group to be 40S, controlling the temperature of the two unit reaction modules to be 24 ℃ and 36 ℃ respectively, setting the pumping pressure of a reaction terminal vacuum device to be 2.9MPa, discharging, and obtaining the high molecular weight PMMA, wherein the GPC molecular weight is 39400g/mol, the molecular weight distribution is 1.83, the monomer conversion rate is 98.0%, and the volatile matter is 0.10%.
Example 14:
the number average molecular weight of the PMMA polymer prepared in this example was 80000g/mol, using a molar ratio of potassium tert-butoxide, tetrabutylammonium bromide and MMA of 1:1:800.
the preparation process is as follows:
s1, uniformly mixing potassium tert-butoxide (135 mg,1 equivalent) and tetrabutylammonium bromide (400 mg,1 equivalent) with toluene (200 mL) to obtain a material A;
s2, mixing MMA (100 mL) and toluene (100 mL) uniformly to obtain a material B;
s3, conveying the material A and the material B to a reaction module group of the microchannel reactor respectively by using a feed pump, regulating the flow rate of the feed pump to enable the material A and the material B to be fed simultaneously, enabling the feed rate to be 30mL/min and 10mL/min respectively, reacting at normal temperature, controlling the total residence time of the reaction feed liquid in the reaction module group to be 40S, controlling the temperature of the two unit reaction modules to be 24 ℃ and 33 ℃ respectively, setting the pumping pressure of a reaction terminal vacuum device to be 2.8MPa, discharging, and obtaining the high molecular weight PMMA, wherein the GPC molecular weight is 65600g/mol, the molecular weight distribution is 1.86, the monomer conversion rate is 99.0%, and the volatile component is 0%.
While the invention has been described in terms of preferred embodiments, it is not intended to be limited thereto, but rather to enable any person skilled in the art to make various changes and modifications without departing from the spirit and scope of the present invention, which is therefore to be limited only by the appended claims.
Claims (4)
1. The preparation method of polymethyl methacrylate is characterized by being carried out in a micro-channel reactor, wherein the micro-channel reactor comprises a reaction module group, and the reaction module group comprises one unit reaction module or is formed by combining more than two unit reaction modules in series;
the synthesis method comprises the following steps:
s1, mixing a catalyst and dissolving the catalyst in an organic solvent to obtain a material A for later use;
catalysts include potassium tert-butoxide and ammonium salts;
the molar ratio of the potassium tert-butoxide to the ammonium salt is (1-4): 1, a step of;
s2, dissolving MMA in an organic solvent to obtain a material B for later use;
s3, conveying the material A and the material B to a reaction module group of the microchannel reactor respectively by using a feed pump, reacting the reaction feed liquid at normal temperature, wherein the total residence time of the reaction feed liquid in the reaction module group is 0.1-30 min, and discharging from the tail end of the reaction module group after the reaction is finished to obtain polymethyl methacrylate;
and regulating the feeding flow rates of the material A and the material B by using a feeding pump to control the dosage of the catalyst, wherein the dosage of the catalyst is 300-1500 ppm.
2. The method for preparing polymethyl methacrylate according to claim 1, wherein the molar ratio of potassium tert-butoxide to ammonium salt is (1-2): 1.
3. the method for producing polymethyl methacrylate according to claim 1, wherein the organic solvent is toluene, and the volume ratio of toluene to MMA is (1 to 4): 1.
4. the method for producing polymethyl methacrylate according to claim 3, wherein the volume ratio of toluene to MMA is (2 to 3): 1.
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| CN109021161A (en) * | 2018-07-03 | 2018-12-18 | 山东柳湾新材料有限公司 | A kind of method that microchannel plate should synthesize GMA acrylic resin |
| CN109942733A (en) * | 2018-10-26 | 2019-06-28 | 复旦大学 | A kind of method that continuous flow moves synthetic polymer |
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| KR20150143680A (en) * | 2013-04-16 | 2015-12-23 | 바스프 에스이 | Continuous process for the manufacture of highly-branched polymers based on c3-c8 monoethylenically unsaturated mono- or dicarboxylic acid or on the anhydrides and salts thereof |
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| CN109021161A (en) * | 2018-07-03 | 2018-12-18 | 山东柳湾新材料有限公司 | A kind of method that microchannel plate should synthesize GMA acrylic resin |
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