CN114133484A - Method for preparing acrylic resin by adopting tubular reactor - Google Patents
Method for preparing acrylic resin by adopting tubular reactor Download PDFInfo
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- CN114133484A CN114133484A CN202111496361.6A CN202111496361A CN114133484A CN 114133484 A CN114133484 A CN 114133484A CN 202111496361 A CN202111496361 A CN 202111496361A CN 114133484 A CN114133484 A CN 114133484A
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- acrylic resin
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- tubular reactor
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- propylene glycol
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- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 34
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000009826 distribution Methods 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 9
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims abstract description 9
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000012546 transfer Methods 0.000 claims description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 6
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 6
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- 230000014759 maintenance of location Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 3
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 3
- ZIKLJUUTSQYGQI-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxypropoxy)propane Chemical compound CCOCC(C)OCC(C)OCC ZIKLJUUTSQYGQI-UHFFFAOYSA-N 0.000 claims description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 3
- ODDDCGGSPAPBOS-UHFFFAOYSA-N 1-ethoxypropan-2-yl propanoate Chemical compound CCOCC(C)OC(=O)CC ODDDCGGSPAPBOS-UHFFFAOYSA-N 0.000 claims description 3
- DOVZUKKPYKRVIK-UHFFFAOYSA-N 1-methoxypropan-2-yl propanoate Chemical compound CCC(=O)OC(C)COC DOVZUKKPYKRVIK-UHFFFAOYSA-N 0.000 claims description 3
- MTVLEKBQSDTQGO-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propan-1-ol Chemical compound CCOC(C)COC(C)CO MTVLEKBQSDTQGO-UHFFFAOYSA-N 0.000 claims description 3
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 3
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 3
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 25
- 238000000576 coating method Methods 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 13
- 239000007787 solid Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013021 overheating Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000012987 RAFT agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- 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
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a method for preparing acrylic resin by adopting a tubular reactor, which comprises the following steps: acrylic acid, isooctyl acrylate, hydroxyethyl methacrylate and other monomers are used as raw materials, tert-butyl peroxybenzoate is used as an initiator and a solvent to carry out polymerization reaction in a tubular reactor according to a certain flow rate, and an acrylic resin product with low molecular weight and narrow distribution is prepared. The method has the advantages of simple process, easy control of reaction, high safety coefficient, economy, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of polymer preparation and application, and particularly relates to a method for synthesizing acrylic resin with narrow distribution by taking an acrylic monomer as a raw material and tert-butyl peroxybenzoate as an initiator and carrying out polymerization reaction on the acrylic monomer in a tubular reactor.
Background
The acrylic resin is a general name of polymers of acrylic acid, methacrylic acid and derivatives thereof, and has the advantages of color retention, light retention, weather resistance, corrosion resistance, pollution resistance and the like. Acrylic resins are currently widely used in many industries such as mechanical, electronic, architectural, leather finishing, paper making, printing and dyeing, industrial plastics and commodity finishing.
The development of the acrylate coating is the synthetic resin coating with the most types and the most comprehensive properties, and the acrylate coating has wide application and important use value. Increasingly stringent environmental regulations have greatly restricted the use of low solids acrylic coatings. At present, various low-pollution coatings such as high-solid coatings, water-based coatings, powder coatings and radiation curing coatings are produced, and one of the coatings with better effect and promising development is the high-solid coating. Because it can not only save solvent in the production and use of paint and reduce pollution, but also can utilize existent construction equipment and can be matched with existent paint system. Therefore, high-solid acrylic coatings have been developed.
The key to develop the high-solid acrylic coating is to synthesize low-viscosity high-solid acrylic resin. Because the resin is mainly used for preparing thermosetting coating, curing agents such as polyisocyanate and amino resin are required to be added for crosslinking reaction so as to improve the comprehensive performance of a coating film. Therefore, the high-solid acrylic resin should have both the conditions of low molecular weight and narrow distribution. Only by reducing the molecular weight of the acrylic resin, the solid content can be increased, and proper viscosity, solubility and workability can be obtained; only if the molecular weight distribution of the polymer is narrow can it be ensured that each low molecular weight polymer chain contains sufficient functional groups; if the molecular weight distribution of the resin is wide, the low molecular weight molecules are inevitably free of hydroxyl groups or less than two hydroxyl groups, and the low-functionality segments may not be completely connected into three-dimensional macromolecules during crosslinking and curing, and some of the low-functionality segments form terminal chains to plasticize a paint film, so that the surface drying and actual drying time of the paint film is prolonged, and the quality of the paint film is affected.
Atom Transfer Radical Polymerization (ATRP) and Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT) are commonly used to synthesize acrylic resins with narrow molecular weight distributions. However, there are disadvantages that the operation process is complicated and the RAFT agent is expensive, which limits industrial application.
Tubular reactors, also known as plug flow reactors, have been developed since 1940. The tubular reactor is tubular, has large length-diameter ratio and belongs to a continuous operation reactor. The method can be divided into 3 types of intermittent, continuous and semi-continuous modes according to different operation modes. Although stirred tank reactors are the most widely used in industry, stirred tank reactors are not suitable for rapid reactions requiring very short residence times and high intensity local mixing. Therefore, other intensive mixing reactors are successively considered in place of stirred tank reactors. The tubular reactor has the advantages of short feeding residence time, capability of realizing local mixing with certain strength, simple structure, convenient processing, large heat transfer area, high heat transfer coefficient, high pressure resistance, safety, high efficiency and the like.
The invention aims to provide a method for synthesizing acrylic resin by using a tubular reactor, aiming at overcoming the defects of the prior art, and synthesizing the acrylic resin with low molecular weight (the number average molecular weight is controlled within the range of 3000-6000) and narrow distribution (PDI is less than 2.70) by using the tubular reactor technology so as to achieve the aim of preparing high-solid paint.
Disclosure of Invention
The invention takes monomers such as acrylic acid, isooctyl acrylate and hydroxyethyl methacrylate as raw materials, tert-butyl peroxybenzoate as an initiator and a solvent to carry out polymerization reaction in a tubular reactor to prepare an acrylic resin product, and is characterized in that: the method comprises the following steps of (1),
(1) adding an initiator tert-butyl peroxybenzoate and an acrylic monomer into a solvent as reaction materials under stirring, and reducing the content of oxygen dissolved in a comonomer and the initiator to below 2ppm through a nitrogen system;
(2) introducing the materials into a pipeline reactor through a metering pump for reaction, controlling the set temperature by an external heat exchanger, using heat transfer oil as a heat exchange medium, and changing the retention time through flow control;
(3) and after the reaction process is finished, the product flows out from an outlet of the reactor, enters a cooling post-treatment process to obtain a reaction solution, and is dried to obtain an acrylic resin product, wherein the total yield of the product is about 90-96%.
Wherein the diluting solvent in the step (1) comprises one or more selected from butyl acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, diethylene glycol ethyl ether acetate and diethylene glycol butyl ether acetate.
Wherein the molar ratio of the initiator to the acrylic acid, the isooctyl acrylate and the hydroxyethyl methacrylate in the step (1) is 1: 1-1.5: 10-15: 20-30, and the total mass of the acrylic monomers and the mass of the solvent are 1: 1-2.
Wherein the flow rate of the reaction solution in the step (2) is 10mL/min to 50 mL/min.
Wherein the reaction residence time in the microchannel reactor in the step (2) is preferably 150-600 s, the reaction temperature is 150-250 ℃, and the pressure is 1-2.5 MPa.
The tubular reactor used in the invention comprises a batching tank, a raw material pump, a pressure gauge, a straight tubular reactor, an oil bath pot, a cooling coil, a back pressure valve and a product collecting tank. The thermocouple is arranged in the heat-conducting medium and can be used for measuring the actual temperature of the external heat-conducting medium. The module is made of monocrystalline silicon, special glass, ceramics, stainless steel or metal alloy coated with a corrosion-resistant coating, polytetrafluoroethylene and the like. The reaction system can resist corrosion and pressure, and the pressure resistance is different according to different materials. The diameter of the tubular reactor is 0.5 mm-10 mm.
In order to enable the polymer to have good light transmittance and good low viscosity and high solid content, the number average molecular weight of the acrylic resin obtained by the method is controlled within 3000-6000, and the molecular weight distribution is less than 2.70.
Compared with the prior art, the invention has the following main characteristics:
1. the invention adopts a tubular continuous flow reactor of continuous flow, the reaction time is shortened from a traditional plurality of hours to a plurality of minutes to more than ten minutes, and the reaction efficiency is obviously improved.
2. Because the raw materials are mixed well in the tubular reactor, the temperature is controlled accurately, the amount of the initiator can be greatly reduced in the reaction process, the generation of impurities is reduced, and the molecular weight distribution of the product is obviously narrowed.
3. The pipeline reactor used in the invention is made of stainless steel, the metering pump is made of polytetrafluoroethylene and titanium, the corrosion resistance is excellent, and the problem of serious equipment corrosion in a conventional reactor is avoided.
In the tubular reactor, the whole process of feeding, mixing and reaction is continuous flow reaction, so that the phenomenon that the device needs to be additionally configured and the leakage occurs in the transfer in the conventional intermittent reaction is avoided, the environment is protected, the safety is realized, and the production efficiency is high.
Drawings
FIG. 1 is a process flow diagram of the synthesis of acrylic resin products from acrylic monomers of the invention: 1-a batching tank, 2-a raw material pump, 3-a pressure gauge, 4-a tubular reactor, 5-an oil bath kettle, 6-a cooling coil, 7-a back pressure valve and 8-a product collecting tank;
FIG. 2 is a GPC curve of the synthetic acrylic resin in example 1;
FIG. 3 is a GPC curve of the synthetic acrylic resin in comparative example 1.
Detailed Description
The invention is further illustrated by the accompanying drawings and detailed description, but the invention is not limited thereto.
The invention takes monomers such as acrylic acid, isooctyl acrylate and hydroxyethyl methacrylate as raw materials, tert-butyl peroxybenzoate as an initiator and a solvent to carry out polymerization reaction in a tubular reactor to prepare an acrylic resin product, and is characterized in that: the method comprises the following steps of (1),
(1) adding an initiator tert-butyl peroxybenzoate and an acrylic monomer into a solvent as reaction materials under stirring, and reducing the content of oxygen dissolved in a comonomer and the initiator to below 2ppm through a nitrogen system;
(2) introducing the materials into a tubular reactor through a metering pump for reaction, controlling the set temperature by an external heat exchanger, using heat transfer oil as a heat exchange medium, and changing the retention time through flow control;
(3) and after the reaction process is finished, the product flows out from an outlet of the reactor, enters a cooling post-treatment process to obtain a reaction solution, and is dried to obtain an acrylic resin product, wherein the total yield of the product is about 90-96%.
Wherein the diluting solvent in the step (1) comprises one or more selected from butyl acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, diethylene glycol ethyl ether acetate and diethylene glycol butyl ether acetate.
Wherein the molar ratio of the initiator to the acrylic acid, the isooctyl acrylate and the hydroxyethyl methacrylate in the step (1) is 1: 1-1.5: 10-15: 20-30, and the total mass of the acrylic monomers and the mass of the solvent are 1: 1-2.
Wherein the flow rate of the reaction solution in the step (2) is as follows: 10 mL/min-50 mL/min.
Wherein the reaction residence time in the tubular reactor in the step (2) is 150-600 s, the reaction temperature is 150-250 ℃, and the pressure is 1-2.5 MPa.
Referring to fig. 1, the process flow of the present invention comprises the following steps: (1) firstly, introducing nitrogen into a batching tank 1 filled with acrylic monomers and initiator solution, and reducing the oxygen-containing mass dissolved in the solution to below 2 ppm; (2) opening a metering pump 2 to enable the solution to pass through a tubular reactor 4 for reaction at a certain flow rate, controlling the temperature through an oil bath pot 5, monitoring the system pressure through a pressure gauge 3 in the whole process, and adjusting the pipeline pressure through a back pressure valve 7; (3) and cooling the reaction liquid by a cooling coil 6, collecting and drying by a product collecting tank 8 to obtain an acrylic resin product, and testing the molecular weight and the release of the product by using GPC.
Example 1
In a jacketed charge tank 1, an acrylic monomer and a raw material such as t-butyl peroxybenzoate are preliminarily mixed. The polymerization monomer mixed solution was maintained at 10 ℃. The composition of the mixed solution is: 75g of methyl methacrylate, 98g of hydroxyethyl methacrylate, 3g of acrylic acid, 6g of tert-butyl peroxybenzoate and 300g of butyl acetate. The nitrogen gas is filled into the batching tank 1, the oxygen mixed in the monomer mixed solution is removed, and the oxygen mass in the monomer mixed solution is controlled to be reduced to below 2 ppm. The material is sent into a tubular reactor 4 by a raw material pump 2 at the speed of 22mL/min, the system pressure is monitored by a pressure gauge 3 in the whole process, and the pipeline pressure is adjusted to be 2Mpa by a back pressure valve 7. The polymerization temperature in the tubular reactor 4 was controlled to 200 ℃ by means of an oil bath 5, and the reaction residence time was 328 s. And (3) after the reaction product passes through the cooling coil 6 in ice-water bath, the reaction product flows out of the reactor in a continuous flow state, and the reaction liquid is collected and dried by a product collecting tank 8 to obtain a colorless transparent polymer. The overall yield of the product was found to be about 96.5%, the number average molecular weight was 4746, and the molecular weight distribution PDI was 1.87.
Example 2
The same procedure as in example 1 was used, except that the material feed rate was increased. The materials are sent into a tubular reactor 4 by a raw material pump 2 at the speed of 48mL/min, and the reaction liquid is collected and dried by a product collecting tank 8 to obtain the colorless transparent polymer. The total yield of the product was found to be about 91.2%, the number average molecular weight was 3500, and the molecular weight distribution PDI was 2.66.
Example 3
The same procedure as in example 1 was used, except that the polymerization temperature of the system was lowered. The polymerization temperature in the tubular reactor 4 was 180 ℃ and the reaction solution was collected by the product collection tank 8 and dried to obtain a colorless transparent polymer. The overall yield of the product was found to be about 90.9%, the number average molecular weight was 4200, and the molecular weight distribution PDI was 2.49.
Example 4
The same procedure as in example 1 was used, except that the polymerization temperature of the system was lowered and the feed rate of the material was decreased. The materials are sent into a tubular reactor 4 by a raw material pump 2 at the speed of 11mL/min, the polymerization temperature in the tubular reactor 4 is 180 ℃, and the reaction liquid is collected and dried by a product collecting tank 8 to obtain the colorless transparent polymer. The total yield of the product was found to be about 91.5%, the number average molecular weight was 3200, and the molecular weight distribution PDI was 2.37.
Comparative example 1
The same procedure as in example 1 was used. Except that the tubular reactor was changed to a complete mixing tank reactor with jacket and stirring. Adding 300g of butyl acetate into a reaction kettle, starting nitrogen replacement, starting stirring, heating to 108 ℃, introducing nitrogen, and pressurizing to 0.05 MPa. Heating to 200 ℃, mixing 75g of methyl methacrylate, 98g of hydroxyethyl methacrylate, 3g of acrylic acid and 6g of tert-butyl peroxybenzoate, dropwise adding into the reaction kettle at the speed of 2g/min, keeping the temperature at 200 ℃ for 2h after dropwise adding is finished, cooling to 80 ℃, and discharging. The reaction solution was dried to obtain a colorless transparent polymer, and the total yield of the product was found to be 94.5%, the number average molecular weight was 2650, and the molecular weight distribution PDI was found to be 4.33. In the complete mixing kettle type reactor, the viscosity of the system is obviously increased after 6 hours of polymerization. Analysis suggests that the molecular weight distribution of the resulting polymer is broadened due to local overheating of the system caused by unfavorable heat and mass transfer.
Comparative example 2
The same procedure as in comparative example 1 was used. The difference is that there is no heat preservation stage, after the dripping is finished, the temperature is reduced to 80 ℃ and the material is discharged. The reaction solution was dried to obtain a colorless transparent polymer, and the total yield of the product was found to be 63%, the number average molecular weight was 1900, and the molecular weight distribution PDI was found to be 6.83. In the complete mixing kettle type reactor, the viscosity of the system is not changed greatly after 4 hours of polymerization. Analysis suggests that the tank reactor is inefficient in reaction due to lower mass transfer efficiency and unfavorable in heat transfer causes local overheating of the system, resulting in broadening of the molecular weight distribution of the resulting polymer, as compared to a tubular reactor.
FIG. 2 and FIG. 3 are GPC graphs of acrylic resins of example 1 and comparative example 1, respectively. The following results are shown in FIG. 2 and FIG. 3 in combination with example 1 and comparative example 1: the number average molecular weight Mn of the acrylic resin synthesized by adopting the tubular reactor is 4746, the weight average molecular weight Mw is 8903, and the molecular weight distribution PDI is 1.87; under the same conditions, the number average molecular weight Mn of the acrylic resin synthesized by adopting the kettle reactor is 2650 and 1900, the weight average molecular weight Mw of the acrylic resin synthesized by adopting the kettle reactor is 11486 and 12977, and the molecular weight distribution PDI of the acrylic resin synthesized by adopting the kettle reactor is respectively as high as 4.33 and 6.83.
Therefore, compared with a kettle type reactor, the tubular reactor can be used for synthesizing the acrylic resin with low molecular weight (the number average molecular weight is controlled within the range of 2000-6000) and narrow distribution (PDI is less than 2.70), so that the aim of preparing the high-solid coating is fulfilled, and the technical advancement of the invention is demonstrated.
Claims (5)
1. A method for preparing acrylic resin by adopting a tubular reactor is characterized by comprising the following steps: the method comprises the following steps of (1),
(1) adding an initiator tert-butyl peroxybenzoate and monomers of acrylic acid, isooctyl acrylate and hydroxyethyl methacrylate into a solvent as reaction materials under stirring, and reducing the content of oxygen dissolved in a comonomer and the initiator to below 2ppm through a nitrogen system;
(2) introducing the materials into a pipeline reactor through a metering pump for reaction, controlling the set temperature by an external heat exchanger, using heat transfer oil as a heat exchange medium, and changing the retention time through flow control;
(3) and after the reaction is finished, drying the reaction liquid in the receiving tank to obtain an acrylic resin product, wherein the total yield of the product is 90-96%, the number average molecular weight is controlled within the range of 3000-6000, and the molecular weight distribution is less than 2.70.
2. The method for preparing acrylic resin according to claim 1, wherein: the solvent comprises one or more selected from butyl acetate, ethylene glycol butyl ether acetate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, diethylene glycol ethyl ether acetate and diethylene glycol butyl ether acetate.
3. The method for preparing acrylic resin according to claim 1, wherein: the molar ratio of the initiator to acrylic acid, isooctyl acrylate and hydroxyethyl methacrylate is 1: 1-1.5: 10-15: 20-30, and the mass ratio of the total mass of the acrylic monomers to the mass of the solvent is 1: 1-2.
4. The method for preparing acrylic resin according to claim 1, wherein: the flow rate of the reaction liquid is as follows: 10 mL/min-50 mL/min.
5. The method for preparing acrylic resin according to claim 1, wherein: the reaction residence time of the materials in the tubular reactor is 150-600 s, the reaction temperature is 150-250 ℃, and the pressure is 1-2.5 MPa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115417938A (en) * | 2022-09-06 | 2022-12-02 | 广东省邦得利新材料技术有限公司 | Method for preparing maleic rosin hydroxyethyl methacrylate polymer from rosin |
| CN115746184A (en) * | 2022-06-24 | 2023-03-07 | 华东师范大学 | Preparation method of polymethyl methacrylate with regular structure and narrow molecular weight distribution |
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