CN111763281A - Equipment and method for preparing acrylic resin for powder coating by continuous body process - Google Patents
Equipment and method for preparing acrylic resin for powder coating by continuous body process Download PDFInfo
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- CN111763281A CN111763281A CN202010632903.7A CN202010632903A CN111763281A CN 111763281 A CN111763281 A CN 111763281A CN 202010632903 A CN202010632903 A CN 202010632903A CN 111763281 A CN111763281 A CN 111763281A
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- 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
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- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention provides equipment and a method for preparing acrylic resin for powder coating by a continuous bulk process, wherein the equipment comprises a batching tank, a reactor, a static mixer, a tubular reactor, a preheater, a devolatilizer, a condenser, a recovery liquid tank, a vacuum pump, a crawler-type material guide machine, a crusher and a charging barrel.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to equipment and a method for preparing acrylic resin for powder coating by a continuous body process.
Background
The powder coating is a novel coating which is coated in a powder form without containing an organic solvent and forms a coating, and generally comprises a resin, a curing agent, a filler, an auxiliary agent and the like. Powder coatings are divided into thermoplastic and thermosetting types, and thermoplastic powder coatings do not require curing agents.
The acrylic resin powder coating has extremely excellent decoration, weather resistance, pollution resistance, corrosion resistance, humidity resistance, hardness and wear resistance, and is widely applied to the fields of automobiles, household appliances and high-grade decoration; especially in the automobile field, has good application prospect. Since the last 70 s, the coating is a hot point of domestic and foreign research, and has become an important variety of domestic and foreign powder coatings. The epoxy type acrylic resin powder paint is an important branch of powder paint, and is prepared with (methyl) acrylic acid glycidyl ester (epoxy type) copolymer resin, dicarboxylic acid, pigment and various functional assistants.
The epoxy-type acrylic resin, which is the most important base material as a powder coating and also the largest content of the components, has a decisive influence on the main properties of the powder coating. The polyacrylate resin containing the epoxy group is applied to the preparation of the powder coating, is matched with a proper auxiliary agent and a curing agent, is widely applied to aluminum alloy automobile hub coatings, outdoor furniture, garden equipment, lamps, automobile finishing paints and the like, and has excellent weather resistance, good coating leveling property, transparency, chemical resistance, high gloss and excellent outdoor durability.
Because the epoxy acrylate has higher requirements on molecular weight and distribution, residual monomers, glass transition temperature, epoxy equivalent and thermal stability in the application of powder coating, no industrial application of epoxy acrylic resin exists in China.
Epoxy acrylates are required to have good leveling during the application of the coating, i.e. the coating assumes a smooth and even state after application. The resin has proper glass transition temperature and narrower molecular weight, and has better synergistic effect with the flatting agent. Increasingly stringent environmental standards place higher demands on the odor of coatings, and there is a need for lower residual monomers in powder coating resins. In addition, to meet the baking temperature requirements of powder coatings during curing, the resins require greater thermal stability while maintaining lower melt viscosities.
Patent 105669962A describes a method for preparing ultraviolet light curing powder resin. Adding a saturated polyester catalyst into a four-neck flask provided with a stirrer, a condenser pipe, an inert gas inlet pipe and a thermometer, melting at 90-120 ℃, starting magnetic stirring, dropwise adding Glycidyl Methacrylate (GMA) dissolved with a polymerization inhibitor and an antioxidant into the four-neck flask for 0.5-1 hr, heating to 100-140 ℃ after dropwise adding is finished, reacting for 1.5-3 hr, stopping reaction when the acid value is not changed, cooling the four-neck flask to room temperature, and discharging to obtain the ultraviolet resin. The molecular weight of the obtained product is 4000-10000, and the glass transition temperature is 55-60 ℃.
Patent CN107699098 discloses a preparation method of epoxy acrylic resin: adding 100g of DMF into a mechanical stirring reactor, and heating to 70 ℃; then uniformly mixing 40g of styrene, 30g of butyl methacrylate, 20g of glycidyl methacrylate, 10g of hydroxyethyl methacrylate, 3g of an initiator and 12 g of alkyl mercaptan, slowly dropwise adding into a mechanical stirring reactor filled with DMF (dropwise adding for 2 hours), after dropwise adding, keeping the temperature at 70 ℃ for reaction for 7 hours under the protection of nitrogen, after the reaction is finished, decompressing and evaporating to remove unreacted organic solvent DMF, cooling and crushing the obtained product, and obtaining the granular or powdery epoxy acrylic resin. The obtained product has an epoxy equivalent of 300-800g/eq, a glass transition temperature of 35-79 ℃ and a weight average molecular weight Mw of 4500-12000.
The substrate properties of epoxy acrylic resins determine the application properties and range of powder coatings. The glass transition temperature is proper (45-50 ℃), the weight average molecular weight is low (5000-10000), the distribution is narrow (PD is less than or equal to 2.0), the VOC residue is low, and the product quality, color and luster are uniform and stable. The above patent reacts at normal pressure and low temperature, so that it is difficult to obtain low molecular weight, and a large amount of mercaptan needs to be added as a molecular weight regulator, and the addition of mercaptan inevitably brings unpleasant odor into the product. The low-temperature reaction is more difficult to solve, narrow molecular weight distribution cannot be obtained, the obtained molecular weight distribution is wide, and the obtained molecular weight distribution means that the content of small molecules is more proportional, so that the product has lower thermal stability and lower thermal decomposition temperature, the application range of the powder coating is limited, and the coating quality is reduced. The technical processes of feeding and volatile removal of products belong to intermittent operation processes, and have a plurality of technical problems to be solved and realized in the aspects of safety, production cost, environmental protection and residual VOC.
In an embodiment, the anderson development co. patent US7737238B2 discloses providing a resin prepared from monomers suitable for use in powder coatings. The specific procedure was to add 1930g xylene to a 2 gallon Parr reactor and stir it at 200 rpm; four consecutive pressurizations to 60psig with dry nitrogen through the reactor to remove air; the mixture was heated to 139 ℃ and a mixture of 450g of styrene, 1020g of methacrylic acid, 675g of butyl acrylate, 855g of glycidyl methacrylate, 3g of n-dodecyl mercaptan and 134.1 g of tert-butyl peroctoate was pumped into the reactor over a period of 5 hours; the feed pump and lines were purged with 100g of xylene and the polymer solution was cooled to 130 ℃ over 15 minutes; with the temperature decreasing from 130 ℃ to 100 ℃ a mixture of 60g of xylene and 15g of tert-butyl peroctoate is added over 2 hours; the pump and the line were purged with 10g of xylene, and the polymer solution was maintained at 100 ℃ for 30 minutes; for discharge, the product solution was further cooled to 70 ℃.
The devolatilization process of the patent comprises the following steps: transferring the product solution to a three-neck round-bottom flask, distilling most of xylene under 1 atmosphere, applying vacuum, heating to 160 ℃, stirring the molten material at 167-. The patent further mentions that the devolatilized resin has a melt viscosity of 230poise @125 ℃ and a melt index of 50g/10min @2.16kg load.
The above patent is carried out in a 7.6L pressure reactor, the reaction temperature is carried out at or above the boiling point of solvent xylene, the evaporation and reflux quantity of the polymerization monomer is reduced, and the direct effects of reducing the small molecular content in the product and reducing the molecular weight distribution are achieved; meanwhile, in order to further reduce the content of the dimer in the product, in the later reaction stage, the reaction temperature is reduced to be below the dissolution boiling point, so that the content of the dimer in the product can be properly reduced.
From the industrial production point of view, the process has the limitations that: 1. the process belongs to intermittent reaction, and equipment and pipelines need to be flushed for multiple times after each charging so as to prevent the monomers mixed with the initiator from polymerizing in the pipelines and the monomers to cause blockage under the condition of long-time retention, and the solvent is used for flushing for multiple times, so that the use amount of the solvent is increased, the total reaction time is prolonged, and the production efficiency is reduced; 2. after the reaction was complete, the batch was transferred to a flask, also a batch operation. Considering the safety problems of leakage, scalding and the like caused by high-temperature materials in the transfer process, the materials are required to be reduced to 70 ℃ by a refrigerant and then transferred into a subsequent container, unreacted monomers and solvents are removed by heating, and large energy consumption is generated by cooling and heating in the process. 3. The devolatilization is carried out under the conditions of stirring and vacuum (4mmHg) and 167-; meanwhile, under the stirring condition, the material decomposition is intensified under the shearing action on the high-temperature material. Bringing problems of yellowing of the material and lowering of the glass transition temperature. 4. The process adds a relatively large amount of solvent xylene, as well as unreacted monomer, and does not involve a solvent monomer recovery process.
In the polymerization and devolatilization process of glycidyl methacrylate resin, the patent US2002/0068777A1 specifically describes a resin devolatilization process after the reaction is finished; under the high vacuum condition of 1-10mmHg, the temperature of the material is maintained at 175 ℃ and the retention time is 1-2 hours. The patent also mentions that the devolatilization process of glycidyl methacrylate resins for powder coatings presents a challenge in that the devolatilization temperature is near the decomposition or depolymerization ceiling temperature of the resin, which is high or low depending on the molecular structure and distribution of the resin itself, and the shear forces to which the resin melt is subjected.
On the basis of researching the polymerization process of the (methyl) glycidyl acrylate resin recovery liquid (a small amount of unreacted monomers and solvents), the invention provides a continuous bulk process for producing the (methyl) glycidyl acrylate resin for powder coating by combining the aspects of safety, environmental protection, large scale, economy, convenience in operation, operational reliability and the like under the urgent safety and environmental protection situation of the current chemical industry. The technological process of the invention has the characteristics of continuous and closed operation, after the solvent and the monomer are prepared at one time, no solvent or a little supplementary solvent is added in the polymerization process, the continuous bulk technological process is realized, and the industrial production can be realized subsequently.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides equipment and a method for preparing acrylic resin for powder coating by using a continuous bulk process, wherein unreacted monomers and solvents are recycled, continuous feeding and discharging are realized, products with the weight average molecular weight of 6000-9000 and the distribution below 2.0 are obtained, the color is uniform, and the thermal stability is higher.
In the polymerization process of the glycidyl methacrylate resin, in order to realize a continuous production process, unreacted monomers and solvents in the reaction process must be recycled. If the polymerization condition is not well controlled, more dimers are easily generated, and the dimers enter a recovery liquid tank along with the monomers and the solvent in the devolatilization process; when the recovered liquid returns to the reactor again for polymerization, new dimer is generated, so that dimer is accumulated continuously, the dimer is in the recovered liquid tank more and more, the polymerization process is influenced, and the small molecular weight in the product is more and more. In the later stage of the reaction, materials pass through the static mixer and the tubular reactor, so that the content of the dimer is effectively reduced under the condition of improving the yield, and the recovered liquid can be recycled for multiple times without adding a solvent additionally.
Another difficulty in achieving a continuous process with glycidyl methacrylate resins for powder coatings is that the residual monomer content of the product needs to be maintained low. The product has low molecular weight, and the polymer is easy to decompose due to long-time retention in a high-temperature devolatilization stage. On one hand, narrow molecular weight distribution is required to be realized in the process of polymerization, and the content of small molecules is reduced; on the other hand, in the preheater, under the condition of low superheating temperature, the material temperature is raised to the required devolatilization temperature in a short time, so that enough monomers and solvents are removed, and the low residual monomer content in the product is maintained. According to the invention, in the design of the preheater, the aluminum block with excellent thermal conductivity is adopted as the heat conduction material between hot oil and materials, and the materials are divided into countless trickle flows through gaps formed by splicing aluminum sheets, so that the heat exchange efficiency is greatly enhanced.
The invention is realized by the following technical scheme: the equipment for preparing the acrylic resin for the powder coating by the continuous body process is characterized by comprising the following steps of: comprises a proportioning tank, a reactor, a static mixer, a tubular reactor, a preheater, a devolatilizer, a condenser, a recovery liquid tank, a vacuum pump, a crawler-type guide machine, a crusher and a charging barrel, wherein the bottom of the proportioning tank is connected with the top of the reactor through a metering pump by a pipeline, the bottom of the reactor is connected with the feed end of the static mixer through a discharge pump by a pipeline, the discharge end of the static mixer is connected with the feed end of the tubular reactor, the discharge end of the tubular reactor is connected with the top of the preheater by a pipeline, multi-channel discharge ports are arranged around the preheater and communicated with the devolatilizer, one side of the devolatilizer is connected with the feed end of the condenser through a pipeline, the condenser is provided with the vacuum pump, the discharge end of the condenser is connected with the recovery liquid tank through a pipeline, the bottom of the devolatilizer is connected with a high-viscosity gear pump connected, the high-viscosity gear pump is connected with the crawler-type material guide machine through a pipeline, a crusher is arranged at the discharge end of the crawler-type material guide machine, and a charging barrel is arranged at the discharge end of the crusher.
Further, the reactor is provided with a jacket and an inner coil, a feed inlet at the top of the reactor is directly connected with the bottom of the recovered liquid through a pipeline, the length-diameter ratio L/D of the cylinder body and the diameter of the reactor is 1-1.6, and the heat exchange area ratio of the inner coil of the reactor to the jacket is 0.3-0.6: 1.
Furthermore, the tubular reactor is provided with a jacket, the mixing components are uniformly distributed in the tubular reactor, and the mixing components are SK mixing components.
Further, the preheater is the stack of multilayer aluminum plate, and the conduction oil heat-transfer pipe has been inserted to the centre, the aluminium pig stacks the number of piles and is 100 ~ 300 layers, multichannel discharge gate effective diameter is 1 ~ 10 mm.
Further, the devolatilizer is provided with a jacket.
A method for preparing acrylic resin for powder coating by a continuous bulk process comprises the following steps:
fully mixing 0-40 wt% of solvent, 1-5 wt% of glycidyl (meth) acrylate, 0-5 wt% of methacrylic monomer, acrylic monomer, 1-5 wt% of ethylene monomer, 80-98 wt% of toluene or xylene, ethylbenzene and alcohol ether solvent to obtain a recycling liquid mixture;
adding 0-1 wt% of molecular weight regulator, 1-4 wt% of initiator, 5-50 wt% of methacrylic acid monomer, acrylic acid monomer, 5-50 wt% of ethylene monomer and 0-50 wt% of other monomers into a mixing tank, and fully mixing to obtain a monomer mixture;
thirdly, completely adding the recovered liquid mixture into the reactor through a centrifugal pump;
step four, accurately metering the monomer mixture by a metering pump, and conveying the monomer mixture into a reactor at the speed of 5 kg-10 kg/hr;
fifthly, stirring speed of the reactor is 40-120 rpm, pressure is 2.5-4 bar, reaction temperature is 100-150 ℃, charging coefficient is 65-85%, monomer conversion rate is 90-95%, and after reaction of the monomer mixture, the monomer mixture enters the tubular reactor through a discharge pump and a static mixer;
sixthly, the tubular reactor is filled with materials at the reaction temperature of 100-130 ℃ and the monomer conversion rate of 92-98%, and then the materials enter an inlet at the upper part of the preheater through a conveying pipeline;
seventhly, a preheater is used, the pressure is 1-20 mmHg, the material temperature is 160-220 ℃, the retention time is 4-6 minutes, and the material enters the devolatilization device through a plurality of layers of channels;
step eight, devolatilizing the materials in a devolatilizer under the pressure of 1-20 mmHg and the temperature of 160-220 ℃, standing for 1-2 hr, and continuously discharging the materials through a high-viscosity gear pump and a die head;
and step nine, converting the unreacted monomer and the solvent into gas phase in a devolatilization device, passing through a condenser, and feeding the condensed material into a recovery liquid tank, wherein the temperature of the condensed material is 0-5 ℃.
The initiator comprises tert-butyl peroxybenzoate, dipentavulcanizing agent, dibenzoyl peroxide, tert-amyl cyclohexane peroxide and azobisisobutyronitrile.
The molecular weight regulator is alpha-styrene linear dimer.
The methacrylic monomer comprises methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate, lauryl methacrylate and ethoxyethyl methacrylate;
the acrylic monomer comprises acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-propyl acrylate, lauryl acrylate and isooctyl acrylate;
the ethylene monomer comprises styrene, acrylonitrile, vinyl acetate and acrylamide;
other monomers include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, and glycidyl acrylate.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention realizes the continuous and closed polymerization process of the glycidyl methacrylate resin, and accords with the development direction of a new process which is safe, environment-friendly and encouraged;
2. the recovery liquid is recycled, so that the production cost is reduced; the feeding and reaction time is shortened in the continuous feeding and discharging process, and the production efficiency is improved;
3. the production process of the invention generates no waste water, the operation process is closed, and only a small amount of waste gas is generated by the breather valve in the charging process;
4. the product produced by the method has the advantages of narrow step by step molecular weight, good product quality, good color consistency and high thermal stability, and has stronger competitiveness in subsequent powder coating application;
5. the product obtained in the invention has low residual monomer, and the formula does not contain mercaptan, so that the product has no unpleasant odor.
Drawings
FIG. 1 is a flow chart of the apparatus of the present invention;
FIG. 2 is a schematic front view of a preheater according to the present invention;
FIG. 3 is a schematic top view of a preheater according to the present invention.
In the drawings: 1. a dosing tank; 2. a reactor; 3. a static mixer; 4. a tubular reactor; 5. a preheater; 51. a multi-channel discharge hole; 6. a devolatilizer; 7. a condenser; 8. a vacuum pump; 9. recovering the liquid tank; 10. a crawler-type material guide machine; 11. a crusher; 12. a charging barrel; 13. high-viscosity gear pump.
Detailed Description
The device for preparing acrylic resin for powder coating by continuous bulk process as shown in figures 1 to 3 in the attached drawings of the specification comprises a proportioning tank 1, a reactor 2, a static mixer 3, a tubular reactor 4, a preheater 5, a devolatilization device 6, a condenser 7, a recovery liquid tank 9, a vacuum pump 8, a crawler-type material guide 10, a crusher 11 and a charging barrel 12, wherein the bottom of the proportioning tank 1 is connected with the top of the reactor 2 through a metering pump by a pipeline, the bottom of the reactor 2 is connected with the feeding end of the static mixer 3 through a discharging pump by a pipeline, the discharging end of the static mixer 3 is connected with the feeding end of the tubular reactor 4, the discharging end of the tubular reactor 4 is connected with the top of the preheater 5 through a pipeline, a multi-channel discharging port 51 is arranged around the preheater 5, the multi-channel discharging port 51 is communicated with the devolatilization device 6, one side of the devolatilization device 6 is connected with the feeding end of, be equipped with vacuum pump 8 on the condenser 7, the discharge end of condenser 7 passes through pipe connection recovery liquid jar 9, and 6 bottoms of devolatilizing device are connected with the hyperviscous gear pump 13 of being connected with the die head, and hyperviscous gear pump 13 passes through pipeline to crawler-type stock guide 10, and the discharge end of crawler-type stock guide 10 is equipped with breaker 11, and the discharge end of breaker 11 is equipped with feed cylinder 12.
Unreacted monomers and solvents after the reaction are directly pumped into a reactor, and mixed monomers are added into a batching tank and continuously added into the reactor for reaction; two reactors are connected in parallel, one reactor is used for reaction, and the other reactor is used for continuous discharging to the devolatilization device, so that the technological process of continuous feeding and discharging is realized; a static mixer is arranged at the outlet of the reactor, the materials in the reactor and a small part of condensed and refluxed monomers and solvents are fully mixed with the materials, and the mixture continues to react in the next stage of tubular reactor, so that the conversion rate is further improved; the tubular reactor reduces the temperature of the materials to be lower than the reaction temperature, so that the conversion rate is improved, and the content of dimer in the product can be reduced; the preheater of the devolatilization device adopts heat-conducting oil to heat the multilayer aluminum blocks, the materials flow out from gaps of the multilayer aluminum blocks, the materials are heated to the problem required by devolatilization in a short time (4-6 minutes), the temperature of hot oil is only 5-10 ℃ higher than the temperature required by the materials, the superheat degree of the wall surfaces of the aluminum blocks is reduced, and the material decomposition is effectively reduced.
The reactor 2 is provided with a jacket and an inner coil, a feed inlet at the top is directly connected with the bottom of the recovery liquid through a pipeline, the length-diameter ratio L/D of the cylinder body and the diameter of the reactor 2 is 1.1, 1.2, 1.4 or 1.5, and the heat exchange area ratio of the inner coil of the reactor to the jacket is 0.35:1, 0.4:1, 0.5:1 or 0.55: 1.
The tubular reactor 4 is provided with a jacket, and the mixing components are uniformly distributed in the tubular reactor and are SK mixing components.
The preheater 5 is a stack of multi-layer aluminum plates, a heat transfer oil pipe is inserted in the middle of the stack of the aluminum plates, the number of the stacked aluminum plates is 120, 140, 190 or 250, and the effective diameter of the multi-channel discharge port 51 is 2, 3, 5 or 8 mm.
The devolatilizer 6 is provided with a jacket.
A method for preparing acrylic resin for powder coating by a continuous bulk process comprises the following steps:
fully mixing 0-40% of solvent, 1-5% of glycidyl methacrylate, 0-5% of methacrylic acid monomer, acrylic acid monomer, 1-5% of ethylene monomer, 80-98% of toluene or xylene, ethylbenzene and alcohol ether solvent in parts by weight into a recycling liquid mixture;
adding 0-1 wt% of molecular weight regulator, 1-4 wt% of initiator, 5-50 wt% of methacrylic acid monomer, acrylic acid monomer, 5-50 wt% of ethylene monomer and 0-50 wt% of other monomers into a mixing tank, and fully mixing to obtain a monomer mixture;
thirdly, completely adding the recovered liquid mixture into the reactor through a centrifugal pump;
step four, accurately metering the monomer mixture by a metering pump, and conveying the monomer mixture into a reactor at the speed of 5 kg-10 kg/hr;
fifthly, stirring speed of the reactor is 40-120 rpm, pressure is 2.5-4 bar, reaction temperature is 100-150 ℃, charging coefficient is 65-85%, monomer conversion rate is 90-95%, and after reaction of the monomer mixture, the monomer mixture enters the tubular reactor through a discharge pump and a static mixer;
sixthly, the tubular reactor is filled with materials at the reaction temperature of 100-130 ℃ and the monomer conversion rate of 92-98%, and then the materials enter an inlet at the upper part of the preheater through a conveying pipeline;
seventhly, a preheater is used, the pressure is 1-20 mmHg, the material temperature is 160-220 ℃, the retention time is 4-6 minutes, and the material enters the devolatilization device through a plurality of layers of channels;
step eight, devolatilizing the materials in a devolatilizer under the pressure of 1-20 mmHg and the temperature of 160-220 ℃, standing for 1-2 hr, and continuously discharging the materials through a high-viscosity gear pump and a die head;
and step nine, converting the unreacted monomer and the solvent into gas phase in a devolatilization device, passing through a condenser, wherein the temperature of the material is 0-5 ℃, and condensing the material and then entering a recovery liquid tank.
The initiator comprises tert-butyl peroxybenzoate, dipentavulcanizing agent, dibenzoyl peroxide, tert-amyl cyclohexane peroxide and azobisisobutyronitrile.
The molecular weight regulator is alpha-styrene linear dimer.
The methacrylic monomer comprises methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate, lauryl methacrylate and ethoxyethyl methacrylate;
the acrylic monomer comprises acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-propyl acrylate, lauryl acrylate and isooctyl acrylate;
the ethylene monomer comprises styrene, acrylonitrile, vinyl acetate and acrylamide;
other monomers include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, and glycidyl acrylate.
Example 1
Adding 0.98kg of methyl methacrylate, 0.5kg of butyl methacrylate, 0.24kg of styrene, 0.31kg of glycidyl methacrylate and 20.2kg of dimethylbenzene into a reactor 2, and heating to 140 ℃;
13.22kg of methyl methacrylate, 5.44kg of butyl methacrylate, 5.7kg of styrene and 6.61kg of glycidyl methacrylate are added into a proportioning tank 1,
the mixed material was fed into the reactor 2 through a metering pump over a period of 4.5 hours, with a stirring speed of 70rpm, and the reactor temperature was controlled at 140. + -. 1 ℃. After the reaction is finished, the materials enter a tubular reactor through a static mixer, and the temperature of the materials in the tubular reactor is controlled to be 132 +/-1 ℃.
Controlling the temperature of the devolatilizer of the preheater at 180 ℃, the pressure at 108Pa, and the retention time of the materials in the devolatilizer at 1.5 hr. The condenser temperature was controlled at-2 ℃.
The product conversion rate is 93.3%, and the color of a die head discharging sample is uniform after sampling and color comparison at certain time intervals.
Example 2
The recovered solution of example 1 was charged into a reactor 2 and the contents of the components were measured, wherein the contents of methyl methacrylate, butyl methacrylate, styrene, glycidyl methacrylate, and xylene were 0.78kg, 0.53kg, 0.14kg, 0.51kg, and 20.2kg, respectively, and the temperature was raised to 140 ℃;
11.22kg of methyl methacrylate, 5.98kg of butyl methacrylate, 5.17kg of styrene and 5.61kg of glycidyl methacrylate are added into a proportioning tank 1,
the mixed material was fed into the reactor 2 through a metering pump over a period of 4.5 hours, with a stirring speed of 70rpm, and the reactor temperature was controlled at 140. + -. 1 ℃. After the reaction is finished, the materials enter a tubular reactor through a static mixer, and the temperature of the materials in the tubular reactor is controlled to be 130 +/-1 ℃.
The temperature of the devolatilizer of the preheater was controlled at 185 deg.C, the pressure at 98Pa, and the residence time of the material in the devolatilizer was 1.3 hr. The condenser temperature was controlled at 3 ℃.
The product conversion rate is 94.2 percent, and the color of a die head discharging sample is uniform after sampling and color comparison at certain intervals.
Example 3
The recovered solution obtained in example 2 was charged into a reactor 2, and the contents of the components were measured, wherein the contents of methyl methacrylate, butyl methacrylate, styrene, glycidyl methacrylate, and xylene were 1.38kg, 0.35kg, 0.34kg, 0.78kg, and 21.4kg, respectively, and the temperature was raised to 142 ℃;
12.39kg of methyl methacrylate, 6.34kg of butyl methacrylate, 5.54kg of styrene and 6.35kg of glycidyl methacrylate are added into a proportioning tank 1,
the mixed material was fed into the reactor 2 through a metering pump over a period of 4.1 hours, with a stirring speed of 70rpm, and the reactor temperature was controlled at 142. + -. 1 ℃. After the reaction is finished, the materials enter a tubular reactor through a static mixer, and the temperature of the materials in the tubular reactor is controlled to be 130 +/-1 ℃.
The temperature of the devolatilizer of the preheater was controlled at 185 deg.C, the pressure at 98Pa, and the residence time of the material in the devolatilizer was 1.5 hr. The condenser temperature was controlled at 3 ℃.
The product conversion rate is 91.6 percent, and the color of a die head discharging sample is uniform after sampling and color comparison at certain intervals.
Example 4
The recovered solution obtained in example 3 was charged into a reactor 2 and the contents of the components were measured, wherein the contents of methyl methacrylate, butyl methacrylate, styrene, glycidyl methacrylate, and xylene were 2.18kg, 0.55kg, 0.37kg, 0.48kg, and 20.43kg, respectively, and the temperature was raised to 139 ℃;
12.39kg of methyl methacrylate, 6.34kg of butyl methacrylate, 5.54kg of styrene and 6.35kg of glycidyl methacrylate are added into a proportioning tank 1,
the mixed material was fed into the reactor 2 through a metering pump over a period of 5 hours, with a stirring speed of 70rpm, and the reactor temperature was controlled at 139. + -. 1 ℃. After the reaction is finished, the materials enter a tubular reactor through a static mixer, and the temperature of the materials in the tubular reactor is controlled to be 130 +/-1 ℃.
The temperature of the devolatilizer of the preheater was controlled at 185 ℃, the pressure at 102Pa, and the residence time of the material in the devolatilizer was 1.5 hr. The condenser temperature was controlled at-2 ℃.
The product conversion rate is 93.5 percent, and the color of a die head discharging sample is uniform after sampling and color comparison at certain intervals.
Example 5
Adding the recovered liquid obtained in the example 4 into a reactor 2, testing the content of components of the recovered liquid, wherein the recovered liquid contains 2.38kg of methyl methacrylate, 0.35kg of butyl methacrylate, 0.34kg of styrene, 0.78kg of glycidyl methacrylate and 21.4kg of dimethylbenzene, and simultaneously supplementing 0.54kg of dimethylbenzene, and heating to 140 ℃;
12.39kg of methyl methacrylate, 6.34kg of butyl methacrylate, 5.54kg of styrene and 6.35kg of glycidyl methacrylate are added into a proportioning tank 1,
the mixed material is added into the reactor 2 through a metering pump within 5 hours, the stirring speed is 70rpm, and the temperature of the reactor is controlled at 140 +/-1 ℃. After the reaction is finished, the materials enter a tubular reactor through a static mixer, and the temperature of the materials in the tubular reactor is controlled to be 130 +/-1 ℃.
The temperature of the devolatilizer of the preheater was controlled at 185 ℃, the pressure at 102Pa, and the residence time of the material in the devolatilizer was 1.5 hr. The condenser temperature was controlled at-2 ℃.
The product conversion rate is 95.2 percent, and the color of a die head discharging sample is uniform after sampling and color comparison at certain intervals.
The results of the examples are summarized in the following table:
| example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Molecular weight Mwg/mol | 6250 | 6337 | 6340 | 8525 | 6884 |
| Molecular weight distribution PDI | 1.92 | 1.84 | 1.89 | 2.07 | 1.92 |
| Monomer conversion% | 93.3 | 94.2 | 91.6 | 93.5 | 95.2 |
| Glass transition temperature of | 46.8 | 47.2 | 46.3 | 54.3 | 47.7 |
| Residual monomer% | 0.32 | 0.19 | 0.25 | 0.37 | 0.25 |
In summary, the present invention is only a preferred embodiment, and not intended to limit the scope of the invention, and all equivalent changes and modifications in the shape, structure, characteristics and spirit of the present invention described in the claims should be included in the scope of the present invention.
Claims (10)
1. The equipment for preparing the acrylic resin for the powder coating by the continuous body process is characterized by comprising the following steps of: comprises a proportioning tank (1), a reactor (2), a static mixer (3), a tubular reactor (4), a preheater (5), a devolatilizer (6), a condenser (7), a recycling liquid tank (9), a vacuum pump (8), a crawler-type guide machine (10), a crusher (11) and a charging barrel (12), wherein the bottom of the proportioning tank (1) is connected with the top of the reactor (2) through a metering pump by a pipeline, the bottom of the reactor (2) is connected with the feed end of the static mixer (3) through a discharge pump by a pipeline, the discharge end of the static mixer (3) is connected with the feed end of the tubular reactor (4), the discharge end of the tubular reactor (4) is connected with the top of the preheater (5) by a pipeline, multi-channel discharge ports (51) are arranged around the preheater (5), and the multi-channel discharge ports (51) are communicated with the devolatilizer (6), the utility model discloses a take off and wave device, including devolatilizer (6), vacuum pump (8) are equipped with behind condenser (7), the discharge end of condenser (7) passes through pipe connection recovery liquid jar (9), devolatilizer (6) bottom is connected with hyperviscosity gear pump (13) of being connected with the die head, hyperviscosity gear pump (13) are through pipeline to crawler-type guide machine (10), the discharge end of crawler-type guide machine (10) is equipped with breaker (11), the discharge end of breaker (11) is equipped with feed cylinder (12).
2. The apparatus for preparing acrylic resin for powder coating according to the continuous bulk process of claim 1, wherein: the reactor (2) is provided with a jacket and an inner coil, a feed inlet at the top is directly connected with the bottom of the recovered liquid through a pipeline, the length-diameter ratio L/D of the cylinder body and the diameter of the reactor (2) is 1-1.6, and the heat exchange area ratio of the inner coil of the reactor to the jacket is 0.3-0.6: 1.
3. The apparatus for preparing acrylic resin for powder coating according to the continuous bulk process of claim 1, wherein: the tubular reactor (4) is provided with a jacket, mixing components are uniformly distributed in the tubular reactor, and the mixing components are SK mixing components.
4. The apparatus for preparing acrylic resin for powder coating according to the continuous bulk process of claim 1, wherein: the preheater (5) is a stack of multiple layers of aluminum plates, a heat transfer oil pipe is inserted in the middle of the stack, the number of stacked aluminum blocks is 100-300, and the effective diameter of the multi-channel discharge port (51) is 1-10 mm.
5. The apparatus for preparing acrylic resin for powder coating according to the continuous bulk process of claim 1, wherein: the devolatilization device (6) is provided with a jacket.
6. A method for preparing an acrylic resin for powder coating by using the continuous bulk process of any one of claims 1 to 5, comprising the steps of:
fully mixing 0-40% of solvent, 1-5% of glycidyl methacrylate, 0-5% of methacrylic acid monomer, acrylic acid monomer, 1-5% of ethylene monomer, 80-98% of toluene or xylene, ethylbenzene and alcohol ether solvent in parts by weight into a recycling liquid mixture;
adding 0-1 wt% of molecular weight regulator, 1-4 wt% of initiator, 5-50 wt% of methacrylic acid monomer, acrylic acid monomer, 5-50 wt% of ethylene monomer and 0-50 wt% of other monomers into a mixing tank, and fully mixing to obtain a monomer mixture;
thirdly, completely adding the recovered liquid mixture into the reactor through a centrifugal pump;
step four, accurately metering the monomer mixture by a metering pump, and conveying the monomer mixture into a reactor at the speed of 5 kg-10 kg/hr;
fifthly, stirring speed of the reactor is 40-120 rpm, pressure is 2.5-4 bar, reaction temperature is 100-150 ℃, charging coefficient is 65-85%, monomer conversion rate is 90-95%, and after reaction of the monomer mixture, the monomer mixture enters the tubular reactor through a discharge pump and a static mixer;
sixthly, the tubular reactor is filled with materials at the reaction temperature of 100-130 ℃ and the monomer conversion rate of 92-98%, and then the materials enter an inlet at the upper part of the preheater through a conveying pipeline;
and seventhly, using a preheater, wherein the pressure is 1-20 mmHg, the material temperature is 160-220 ℃, the retention time is 4-6 minutes, and the material enters the devolatilization device through a multilayer channel.
And step eight, performing devolatilization in a devolatilizer under the pressure of 1-20 mmHg, at the material temperature of 160-220 ℃, standing for 1-2 hr, and continuously discharging through a high-viscosity gear pump and a die head.
And step nine, converting the unreacted monomer and the solvent into gas phase in a devolatilization device, passing through a condenser, wherein the temperature of the material is 0-5 ℃, and condensing the material and then entering a recovery liquid tank.
7. The continuous bulk process for preparing acrylic resin for powder coating according to claim 6, wherein: the initiator comprises tert-butyl peroxybenzoate, a dipentavulcanizing agent, dibenzoyl peroxide, tert-amyl cyclohexane peroxide and azobisisobutyronitrile.
8. The continuous bulk process for preparing acrylic resin for powder coating according to claim 6, wherein: the molecular weight regulator is alpha-styrene linear dimer.
9. The continuous bulk process for preparing acrylic resin for powder coating according to claim 6, wherein: the methacrylic monomer comprises methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate, lauryl methacrylate and ethoxyethyl methacrylate.
10. The continuous bulk process for preparing acrylic resin for powder coating according to claim 6, wherein: the acrylic monomer comprises acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, n-propyl acrylate, lauryl acrylate and isooctyl acrylate; the ethylene monomer comprises styrene, acrylonitrile, vinyl acetate and acrylamide; the other monomers include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate and glycidyl acrylate.
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| CN112694554A (en) * | 2021-01-11 | 2021-04-23 | 浙江阿尔法化工科技有限公司 | Synthesis method and production equipment of SMA resin |
| CN112724309A (en) * | 2020-12-21 | 2021-04-30 | 山东友泉新材料有限公司 | Continuous production method of hydroxy acrylic resin aqueous dispersion |
| CN113105576A (en) * | 2021-04-14 | 2021-07-13 | 英德市捷成化工有限公司 | Resin modified acrylic emulsion with core-shell structure and preparation method and application thereof |
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