CN113617307B - Continuous production system and production method - Google Patents
Continuous production system and production method Download PDFInfo
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- CN113617307B CN113617307B CN202010374620.7A CN202010374620A CN113617307B CN 113617307 B CN113617307 B CN 113617307B CN 202010374620 A CN202010374620 A CN 202010374620A CN 113617307 B CN113617307 B CN 113617307B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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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
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
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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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00103—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor in a heat exchanger separate from the reactor
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Abstract
The invention relates to a continuous production system and a production method. The production system comprises a continuous reaction unit and a comprehensive heat exchange system, the continuous reaction unit is connected with the comprehensive heat exchange system, the continuous reaction unit is used for receiving mixed material liquid and enabling the mixed material liquid to react to form reaction liquid, the comprehensive heat exchange system comprises at least one first heat exchanger, the first heat exchanger comprises two heat exchange strokes, the two heat exchange strokes are used for respectively supplying the mixed material liquid and the reaction liquid to flow, and heat exchange is carried out between the mixed material liquid and the reaction liquid when the mixed material liquid and the reaction liquid flow in the heat exchange strokes. The acrylic resin product obtained by the invention has high solid content (70-90%) and low viscosity (1500-6000 cp). The acrylic resin product does not need to add extra solvent, so that the use and waste of the solvent are reduced while the post-treatment process is avoided, and the environmental pollution and the harm to human bodies caused by excessive solvent volatilization during the use of the product are avoided, thereby being more environment-friendly.
Description
Technical Field
The invention relates to the technical field of resin production, in particular to a production system and a production method for continuously producing high-solid acrylic resin.
Background
High-solid acrylic resin generally refers to acrylic resin with a solid content of 70-80%, and the viscosity of the acrylic resin is generally low and can reach a viscosity range of 1500-6000 cp. The high-solid acrylic resin includes polyester-modified hydroxyacrylic resin, thermosetting acrylic resin, polyester-modified thermosetting acrylic resin, and the like. The high-solid acrylic resin paint is a protective and decorative paint with excellent performance and wide application, and is an important variety of automobile paint.
At present, the production of acrylic resin generally adopts a batch production method, and the production process generally comprises the following steps: adding a solvent into the reaction kettle, and then adding part of monomer and an initiator to carry out prepolymerization for about 1h; meanwhile, the temperature of the kettle is kept at about 140 ℃; a condensation reflux device is arranged at the top of the kettle, and the solvent is subjected to condensation reflux; adding the rest monomers and the initiator into the kettle in a dropwise manner for reaction, wherein the dropwise adding process is about 2-3 h; after the dropwise addition is finished, the kettle is kept at the constant temperature of 140 ℃ for 6 hours to ensure that the polymerization is finished. The acrylic resin produced by the intermittent batch production method has low solid content which is generally not more than 60 percent and high viscosity which is generally more than 10000cp, and when the acrylic resin is used, a solvent is required to be added for blending and dilution, so that the prepared coating has poor application property, the fullness of a paint film is not ideal, and a large amount of organic volatile matters cause serious pollution to the environment. China restricts the emission of VOC in the coating industry, and in order to reduce the emission of VOC, the Ministry of industry and belief imposes a consumption tax on the production and emission of VOC (> 420 g/L) solvent-based coatings. If the resin viscosity is too high (> 10000 cp), the solvent is required to be diluted too much, when the paint is sprayed, the solvent is volatilized in a large amount, the environmental protection requirement cannot be met, a tail gas treatment system needs to be additionally added, the paint spraying cost is improved, and a large amount of solvent is wasted.
Generally, the higher the reaction temperature, the faster the polymerization reaction, the lower the relative molecular mass of the polymer, the lower the viscosity of the polymer, the too high reaction temperature (e.g. above 200 ℃), the increase in viscosity due to branching and the interaction between molecular chains, and in addition, the batch tank process is difficult to control, considering that the temperature used during polymerization matches the half-life of the initiator, the reaction process is safe and controllable, and the reaction temperature for the tank batch production is not too high, so the corresponding reaction time is longer, resulting in lower production efficiency. The volume of the reaction kettle adopted for intermittent batch production is generally large and is 5-50 cubic meters, and the reaction kettle needs to be heated and cooled for each batch of intermittent production, so that energy is wasted. Because the reaction kettle has a large volume, the production process has strict operation requirements on each link, the operation is improper and easy to be out of control, potential safety hazards exist, and time and labor are consumed for cleaning waste materials. Therefore, the batch production method has the defects of high energy consumption, large pollution, incapability of stably and directly obtaining the acrylic resin with high solid content and low viscosity, and the like.
Meanwhile, the conventional formula and the conventional method are adopted to produce the acrylic resin, the viscosity is correspondingly increased along with the increase of the solid content of the resin, so that the acrylic resin with high solid content and low viscosity cannot be directly obtained by batch kettle type production, and in order to improve the solid content of the resin and simultaneously reduce the viscosity of the resin, the common measures are as follows: adding more molecular weight regulator (mass fraction is more than or equal to 2%), adding functional monomer or increasing the using amount of the functional monomer (more than or equal to 10%), strictly controlling the dropping speed of materials and the reaction temperature, or adopting a mode of adding excessive solvent first and then evaporating part of the solvent after polymerization is finished to achieve the effects of improving solid content and reducing viscosity, but the measures have certain limitations, and the too high using amount of the molecular weight regulator can complicate the polymerization reaction, can also influence the performance of a polymer coating film, such as gloss and durability, and can hardly eliminate unpleasant odor caused by the performance; increasing the amount of functional monomer increases the cost of the raw materials; the operation difficulty in the production process is increased by strictly controlling the dropping speed of the materials and the reaction temperature, and the production efficiency is reduced if the dropping speed is too slow; the method of adding excessive solvent for polymerization and then evaporating part of the solvent has the defects of complex operation and high energy consumption.
Therefore, the development of new production technology for producing environment-friendly high-solid acrylic resin is the development direction in the future.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to overcome the defects of high energy consumption, large pollution, incapability of stably and directly obtaining acrylic resin with high solid content and low viscosity and the like in an acrylic resin kettle type synthesis process, and provides a production method and a production system thereof, which are energy-saving and environment-friendly and can directly obtain acrylic resin with high solid content and low viscosity without subsequent processes.
Means for solving the problems
[1] The continuous production system comprises a continuous reaction unit and a comprehensive heat exchange system, wherein the continuous reaction unit is connected with the comprehensive heat exchange system, the continuous reaction unit is used for receiving mixed material liquid and enabling the mixed material liquid to react to form reaction liquid, the comprehensive heat exchange system comprises at least one first heat exchanger E1, the first heat exchanger E1 comprises two heat exchange strokes, the two heat exchange strokes are used for enabling the mixed material liquid and the reaction liquid to flow respectively, and the mixed material liquid and the reaction liquid exchange heat when flowing in the heat exchange strokes;
preferably, the continuous reaction unit comprises at least one microchannel reactor and at least one tubular reactor; more preferably, the tubular reactor is selected from at least one of a dynamic tubular reactor and a static tubular reactor.
[2] The production system according to the item [1], wherein the comprehensive heat exchange system comprises at least one second heat exchanger E2, the second heat exchanger E2 is connected with the first heat exchanger E1 in series, the mixed material liquid and the reaction liquid respectively flow through the first heat exchanger E1 in sequence, and the reaction liquid flows through the second heat exchanger E2.
[3] The production system according to [1] or [2], wherein the production system further comprises at least one third heat exchanger E3, at least one fourth heat exchanger E4; the third heat exchanger E3 and the fourth heat exchanger E4 are respectively connected with the microchannel reactor and the tubular reactor so as to enable the microchannel reactor and the tubular reactor to be at preset temperatures and control the temperature of reaction liquid in the continuous reaction unit in the continuous production process.
[4] The production system according to the item [1] or the item [2], wherein the production system further comprises a continuous conveying unit and at least one receiving tank J1, the continuous conveying unit is connected with the comprehensive heat exchange system, and the mixed feed liquid is conveyed to the continuous reaction unit through the comprehensive heat exchange system; the receiving tank J1 is connected with the comprehensive heat exchange system;
preferably, at least one first continuous conveying unit B1 in the continuous conveying unit is connected with a shell side inlet of at least one first heat exchanger E1 in the integrated heat exchange system, a shell side outlet of the at least one first heat exchanger E1 is connected with a tube side inlet of at least one second heat exchanger E2 in the integrated heat exchange system, a tube side outlet of the at least one second heat exchanger E2 is connected with the at least one microchannel reactor W1, the at least one microchannel reactor W1 is connected with at least one tube reactor G1, the at least one tube reactor G1 is connected with a shell side inlet of the at least one second heat exchanger E2, a shell side outlet of the at least one second heat exchanger E2 is connected with a tube side inlet of the at least one first heat exchanger E1, a tube side outlet of the at least one first heat exchanger E1 is connected with an inlet of the at least one receiving tank J1, and at least one second continuous conveying unit B2 in the continuous conveying unit is connected with the at least one microchannel reactor W1;
or, at least one first continuous conveying unit B1 in the continuous conveying units is connected with the shell side inlet of at least one first heat exchanger E1 in the integrated heat exchange system, the shell side outlet of the at least one first heat exchanger E1 is connected with the at least one microchannel reactor W1, the at least one microchannel reactor W1 is connected with at least one tubular reactor G1, the at least one tubular reactor G1 is connected with the inlet of the at least one second heat exchanger E2, the outlet of the at least one second heat exchanger E2 is connected with the tube side inlet of the at least one first heat exchanger E1, the tube side outlet of the at least one first heat exchanger E1 is connected with the inlet of the at least one receiving tank J1, and at least one second continuous conveying unit B2 in the continuous conveying units is connected with the at least one microchannel reactor W1;
or, at least one first continuous conveying unit B1 in the continuous conveying units is connected with a shell side inlet of at least one first heat exchanger E1 in the integrated heat exchange system, a shell side outlet of the at least one first heat exchanger E1 is connected with the at least one microchannel reactor W1, the at least one microchannel reactor W1 is connected with at least one tubular reactor G1, the at least one tubular reactor G1 is connected with a tube side inlet of the at least one first heat exchanger E1, a tube side outlet of the at least one first heat exchanger E1 is connected with an inlet of at least one second heat exchanger E2, an outlet of the at least one second heat exchanger E2 is connected with an inlet of the at least one receiving tank J1, and at least one second continuous conveying unit B2 in the continuous conveying units is connected with the at least one microchannel reactor W1.
[5] The continuous production system according to [1] or [2], wherein the continuous reaction unit comprises a first feed inlet and a second feed inlet, the first feed inlet is used for conveying the continuous reaction unit to pass through the mixed feed liquid of the comprehensive heat exchange system, and the second feed inlet is used for conveying the continuous reaction unit to pass through the mixed feed liquid of the comprehensive heat exchange system.
[6] And a production method for continuously producing resin, which adopts the production system according to any one of the items [1] to [5] to produce resin, preferably, a first mixed material liquid and a second mixed material liquid respectively enter the continuous reaction unit for reaction, and the comprehensive heat exchange system controls the temperature of the production system.
[7] The production method according to [6], wherein the first mixed feed liquid enters at least one first heat exchanger E1 in the integrated heat exchange system through at least one first continuous conveying unit B1 in the continuous conveying units, enters at least one second heat exchanger E2 in the integrated heat exchange system through the at least one first heat exchanger E1, and enters a microchannel reactor W1 through the at least one second heat exchanger E2 for reaction, and the reaction time is t1;
or the first mixed feed liquid enters at least one first heat exchanger E1 in the integrated heat exchange system through at least one first continuous conveying unit B1 in the continuous conveying units, and enters the microchannel reactor W1 through the at least one first heat exchanger E1 for reaction, wherein the reaction time is t1;
after the reaction time t1, the second mixed feed liquid enters the at least one microchannel reactor W1 through at least one second continuous conveying unit B2 in the continuous conveying units to be mixed with the first mixed feed liquid for continuous reaction, wherein the reaction time is t2;
then the reaction liquid enters a tubular reactor G1 for reaction, and the reaction time is t3;
preferably, the reaction time t1 is 30 to 150s, the reaction time t2 is 30 to 150s, and the reaction time t3 is 1 to 30min; more preferably, the reaction time t1 is 30 to 120s, the reaction time t2 is 30 to 120s, and the reaction time t3 is 5 to 30min.
[8] The production method according to [7], wherein the first mixed feed liquid enters a shell side inlet of at least one first heat exchanger E1 in the integrated heat exchange system through at least one first continuous conveying unit B1 in the continuous conveying units, enters a tube side inlet of at least one second heat exchanger E2 in the integrated heat exchange system from a shell side outlet of the first heat exchanger E1 through the at least one first heat exchanger E1, enters a channel inlet of a microchannel reactor W1 from a tube side outlet of the second heat exchanger E2 through the at least one second heat exchanger E2, and reacts for t1;
or the first mixed feed liquid enters a shell-side inlet of at least one first heat exchanger E1 in the integrated heat exchange system through at least one first continuous conveying unit B1 in the continuous conveying units, and enters a channel inlet of the microchannel reactor W1 from a shell-side outlet of the first heat exchanger E1 through the at least one first heat exchanger E1 for reaction, wherein the reaction time is t1;
after the reaction time t1, the second mixed feed liquid enters at least one middle inlet of the at least one microchannel reactor W1 through at least one second continuous conveying unit B2 in the continuous conveying units to be mixed with the first mixed feed liquid for continuous reaction, and the reaction time is t2;
then, the reaction liquid enters a tubular reactor G1 from a channel outlet of the micro-channel reactor W1 for reaction, and the reaction time is t3;
wherein the channel inlet of the microchannel reactor W1 is located at one side of the microchannel reactor W1, which is different from the position of the middle inlet of the microchannel reactor W1.
[9] The production method according to [7] or [8], wherein the pressure control range of the production system is 1 to 4MPa, preferably 1.5 to 3MPa;
preferably, said at least one microchannel reactor W1 is connected to said at least one third heat exchanger E3;
preferably, said at least one tubular reactor G1 is connected to said at least one fourth heat exchanger E4;
preferably, the first mixed feed liquid is preheated to 90-130 ℃ through the comprehensive heat exchange system; preferably, the at least one microchannel reactor W1 is preheated to 170-220 ℃ by the at least one third heat exchanger E3; preferably, the at least one tubular reactor G1 is preheated to 170 to 220 ℃ by means of at least one fourth heat exchanger E4; preferably, the reaction liquid after the reaction in the tubular reactor G1 is discharged from the tubular reactor G1, and then cooled to 20-90 ℃, preferably to 30-80 ℃ through the comprehensive heat exchange system.
[10] The production method according to any one of [6] to [8], wherein the first and second mixed liquids contain a raw material, a solvent, and an auxiliary agent;
preferably, the mass ratio of the raw materials to the solvent to the auxiliary agent in the first mixed feed liquid is 70-90, and is as follows, the ratio is from 5 to 30, preferably from 70 to 90, from 1 to 4;
preferably, the raw material is a mixture of (meth) acrylic monomers and styrene, or a mixture of resin with (meth) acrylic monomers and styrene,
preferably, the resin is at least one of alkyd resin, thermosetting polyester and hydroxyl polyester,
preferably, the solvent is at least one of an ester solvent, a benzene solvent, an alcohol solvent, and an ether solvent.
ADVANTAGEOUS EFFECTS OF INVENTION
In the actual industrial production, for a 5000t product production line, the production system and the production method for continuously producing the high-solid acrylic resin have the energy saving of up to 60 percent compared with an intermittent batch kettle type production device and the intermittent batch kettle type production method.
The production method for continuously producing the high-solid acrylic resin has the advantages that the raw material conversion rate is more than or equal to 98%, the obtained product has high solid content (70-90%) and low viscosity (1500-6000 cp), and the method can be used for preparing varnish which can reach the spraying viscosity and the VOC emission standard and can also increase the fullness of an acrylic resin paint film. The product obtained by adopting the same raw material mixed liquor to carry out batch production process has low solid content (less than or equal to 60%) and high viscosity (more than 10000 cp), and needs to be added with solvent to be blended and diluted to reduce the viscosity when in use. The product obtained by the production method for continuously producing the high-solid acrylic resin does not need to be additionally added with the solvent when used, so that the use and waste of the solvent are reduced while the post-treatment process is avoided, and the environmental pollution and the harm to the human body caused by the volatilization of the excessive solvent when the product is used are avoided, so that the product with high solid content and low viscosity is more environment-friendly while the product with high solid content and low viscosity is directly obtained.
Drawings
Fig. 1 to 3 are process flow diagrams of the production method of the present invention.
Description of the reference numerals
V1, V2 mixing kettle
B1, B2 metering pump
E1, E2, E3 and E4 heat exchanger
W1 micro-channel reactor
G1 Tubular reactor
J1 Receiving tank
Detailed Description
< production System >
The invention relates to a continuous production system, which comprises a continuous reaction unit and a comprehensive heat exchange system, wherein the continuous reaction unit is connected with the comprehensive heat exchange system, the continuous reaction unit is used for receiving mixed material liquid and enabling the mixed material liquid to react to form reaction liquid, the comprehensive heat exchange system comprises at least one first heat exchanger E1, the first heat exchanger E1 comprises two heat exchange strokes, the two heat exchange strokes are respectively used for enabling the mixed material liquid and the reaction liquid to flow, and the mixed material liquid and the reaction liquid exchange heat when flowing in the heat exchange strokes.
In the present invention, the mixed feed liquid and the reaction liquid naturally perform heat exchange while flowing in different heat exchange strokes of the heat exchanger due to their own temperature difference.
The continuous reaction unit includes at least one microchannel reactor and at least one tubular reactor. Preferably, the tubular reactor is selected from at least one of a dynamic tubular reactor and a static tubular reactor. The dynamic tube reactor includes, for example, a tube reactor with a dynamic stirring structure. The static tubular reactor includes, for example, a straight tube, a coil or a tube bundle reactor with or without mixing structures in the tube.
In the invention, the microchannel reactor is provided with at least one reaction unit; preferably from 1 to 15 reaction units; more preferably from 1 to 10 reaction units.
The comprehensive heat exchange system can comprise at least one second heat exchanger E2, the second heat exchanger E2 is connected with the first heat exchanger E1 in series, the mixed material liquid and the reaction liquid respectively flow through the first heat exchanger E1 in sequence, and the reaction liquid flows through the second heat exchanger E2.
In the present invention, the production system may comprise at least one third heat exchanger E3, at least one fourth heat exchanger E4; the third heat exchanger E3 and the fourth heat exchanger E4 are respectively connected with the microchannel reactor and the tubular reactor so as to enable the microchannel reactor and the tubular reactor to be at preset temperatures and control the temperature of reaction liquid in the continuous reaction unit in the continuous production process.
In the invention, the production system can comprise a continuous conveying unit and at least one receiving tank J1, wherein the continuous conveying unit is connected with the comprehensive heat exchange system and conveys the mixed feed liquid to the continuous reaction unit through the comprehensive heat exchange system; and the receiving tank J1 is connected with the comprehensive heat exchange system.
The continuous conveying unit comprises at least one of a diaphragm pump, a plunger pump, a screw pump and a gear pump, and the tolerance pressure of the continuous conveying unit is 0-8 MPa.
In the invention, the continuous reaction unit may include a first feed inlet and a second feed inlet, the first feed inlet is used for conveying the mixed material liquid passing through the comprehensive heat exchange system to the continuous reaction unit, and the second feed inlet is used for conveying the mixed material liquid not passing through the comprehensive heat exchange system to the continuous reaction unit.
The production system of the present invention is explained in more detail below with reference to fig. 1 to 3, and those skilled in the art will understand that fig. 1 to 3 of the present invention do not constitute a limitation of the production system of the present invention.
As shown in fig. 1, at least one first continuous conveying unit B1 of the continuous conveying units is connected with at least one first heat exchanger E1 of an integrated heat exchange system, the at least one first heat exchanger E1 is connected with at least one second heat exchanger E2 of the integrated heat exchange system, the at least one second heat exchanger E2 is connected with a microchannel reactor W1, the at least one microchannel reactor W1 is connected with at least one tubular reactor G1, and at least one second continuous conveying unit B2 of the continuous conveying units is connected with the at least one microchannel reactor W1.
It should be noted that fig. 1 is only an example, and in practical applications, the second continuous conveying unit B2 may also be connected to the at least one tubular reactor G1, that is, the connection position of the second continuous conveying unit B2 is not particularly limited.
In more detail, as shown in fig. 1, at least one first continuous conveying unit B1 in the continuous conveying units is connected with a shell-side inlet of at least one first heat exchanger E1 in an integrated heat exchange system, a shell-side outlet of the at least one first heat exchanger E1 is connected with a tube-side inlet of at least one second heat exchanger E2 in the integrated heat exchange system, a tube-side outlet of the at least one second heat exchanger E2 is connected with the at least one microchannel reactor W1, the at least one microchannel reactor W1 is connected with at least one tube reactor G1, the at least one tube reactor G1 is connected with a shell-side inlet of the at least one second heat exchanger E2, a shell-side outlet of the at least one second heat exchanger E2 is connected with a tube-side inlet of the at least one first heat exchanger E1, and at least one second continuous conveying unit B2 in the continuous conveying units is connected with the at least one microchannel reactor W1.
As shown in fig. 1, the production system of the present invention may further include at least one third heat exchanger E3, at least one fourth heat exchanger E4, and at least one receiver tank J1; preferably, said at least one microchannel reactor W1 is connected to said at least one third heat exchanger E3; preferably, said at least one tubular reactor G1 is connected to said at least one fourth heat exchanger E4; preferably, the at least one first heat exchanger E1 is connected to the at least one receiver tank J1; more preferably, the tube side outlet of the at least one first heat exchanger E1 is connected to the inlet of the at least one receiver tank J1.
Preferably, in the present invention, the connection position of the at least one second heat exchanger E2 to the microchannel reactor W1 and the connection position of the at least one second continuous conveying unit B2 to the microchannel reactor W1 are different; preferably, the tube-side outlet of the at least one second heat exchanger E2 is connected to a channel inlet of the microchannel reactor W1, and the at least one second continuous conveying unit (B2) is connected to at least one intermediate inlet of the microchannel reactor W1, wherein the channel inlet of the microchannel reactor W1 is located on one side of the microchannel reactor W1, and may be on one radial side or one transverse side. In practical applications, the position of the channel inlet of the microchannel reactor W1 can be set according to production requirements, and is not particularly limited as long as channel communication can be achieved.
In the present invention, the intermediate inlet of the microchannel reactor W1 is not particularly limited, and it may mean an inlet on the same or different side as or from the inlet side of the channels of the microchannel reactor W1. For example, as shown in fig. 1, the channel inlet of the microchannel reactor W1 is located at one side in the radial direction, and the middle inlet of the microchannel reactor W1 may be set at one side in the lateral direction. The intermediate inlet does not necessarily mean an inlet at an intermediate position of the microchannel reactor W1 in a strict sense, and the position thereof can be determined by the number of reaction units of the microchannel reactor W1. For example, the intermediate inlet may be located at the 2 nd, 3 rd, 4 th, 5 …, 10 th, etc. reaction unit inlet of the microchannel reactor W1. The intermediate inlet may also be provided on the tube reactor G1, which is arranged identically to the arrangement on the microchannel reactor W1.
As shown in fig. 2, at least one first continuous conveying unit B1 in the continuous conveying unit is connected with a shell-side inlet of at least one first heat exchanger E1 in the integrated heat exchange system, a shell-side outlet of the at least one first heat exchanger E1 is connected with the at least one microchannel reactor W1, the at least one microchannel reactor W1 is connected with at least one tubular reactor G1, the at least one tubular reactor G1 is connected with an inlet of the at least one second heat exchanger E2, an outlet of the at least one second heat exchanger E2 is connected with a tube-side inlet of the at least one first heat exchanger E1, a tube-side outlet of the at least one first heat exchanger E1 is connected with an inlet of the at least one receiving tank J1, and at least one second continuous conveying unit B2 in the continuous conveying unit is connected with the at least one microchannel reactor W1.
As shown in fig. 3, at least one first continuous conveying unit B1 in the continuous conveying unit is connected with a shell-side inlet of at least one first heat exchanger E1 in the integrated heat exchange system, a shell-side outlet of the at least one first heat exchanger E1 is connected with the at least one microchannel reactor W1, the at least one microchannel reactor W1 is connected with at least one tubular reactor G1, the at least one tubular reactor G1 is connected with a tube-side inlet of the at least one first heat exchanger E1, a tube-side outlet of the at least one first heat exchanger E1 is connected with an inlet of the at least one second heat exchanger E2, an outlet of the at least one second heat exchanger E2 is connected with an inlet of the at least one receiving tank J1, and at least one second continuous conveying unit B2 in the continuous conveying unit is connected with the at least one microchannel reactor W1.
In fig. 2 and 3, the arrangement and connection of other components are the same as those described in fig. 1.
The various components of the production system of the present invention, such as the heat exchanger, microchannel reactor, tubular reactor, continuous feed unit, receiving tank, etc., are commercially available, but the entire production system is not commercially available, nor is it known to those skilled in the art.
< production method >
Further, the present invention relates to a production method for continuously producing a resin, which uses the production system according to the present invention to produce a resin. Preferably, the first mixed feed liquid and the second mixed feed liquid respectively enter the continuous reaction unit for reaction, and the comprehensive heat exchange system controls the temperature of the production system. Preferably, the first mixed feed liquid and the second mixed feed liquid enter the continuous reaction unit through the first continuous conveying unit and the second continuous conveying unit respectively to react.
The first mixed feed liquid and the second mixed feed liquid comprise raw materials, solvents and auxiliaries; preferably, the mass ratio of the raw material to the solvent to the auxiliary in the first mixed feed liquid is 70 to 90 (hereinafter, sometimes referred to as "mass ratio r 1"), and preferably 70 to 90. (hereinafter sometimes referred to as "mass ratio r 2")
Preferably, the raw material is a mixture of a (meth) acrylic monomer and styrene, or a mixture of a resin and a (meth) acrylic monomer and styrene. The ratio of the components in the raw materials is well known to those skilled in the art, and is not particularly limited, and those skilled in the art can adjust and apply the raw materials according to actual production needs.
As a non-limiting example, the (meth) acrylic monomer includes at least one of (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, isooctyl (meth) acrylate, isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate.
By way of non-limiting example, the resin includes at least one of an alkyd, a thermosetting polyester, and a hydroxy polyester.
As a non-limiting example, the solvent is at least one of an ester solvent, a benzene solvent, an alcohol solvent, and an ether solvent.
The ester solvent is at least one of ethyl acetate, butyl acetate, isobutyl acetate, propylene glycol butyl ether acetate, and propylene glycol methyl ether acetate.
The benzene-based solvent is, for example, at least one of benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene.
The alcohol solvent is, for example, at least one of isopropyl alcohol, isobutyl alcohol, and n-butyl alcohol.
The ether solvent is at least one of propylene glycol butyl ether, propylene glycol methyl ether and propylene glycol ethyl ether.
By way of non-limiting example, adjuvants include initiators, molecular weight regulators, and the like. Generally, the amount of initiator used is within the ranges known in the art.
The molecular weight regulator regulates the molecular weight by transferring chain free radicals and makes the molecular weight distribution narrow. For a high-solid acrylic resin which requires both a reduction in molecular weight and a narrow molecular weight distribution, the proper application of a molecular weight modifier can exert a good effect. The viscosity of the polymer in the reaction system decreases with the increase in the concentration of the molecular weight regulator, but the chain transfer complicates the polymerization reaction, and also affects the properties of the polymer coating film such as gloss and durability and its accompanying unpleasant odor is hardly eliminated. Therefore, in order to achieve a reduction in viscosity and a reduction in side effects, the amount of the molecular weight regulator of the invention is less than two thousandths of the total mass of the starting materials. However, this does not constitute a limitation on the amount of molecular weight regulator used, and it will be understood by those skilled in the art that the range of amounts of molecular weight regulators commonly used may be applied to the present invention.
The initiator is at least one of t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, t-amyl hydroperoxide, di-t-amyl peroxide, dibenzoyl peroxide and tert-butyl peroxybenzoate.
The molecular weight regulator is at least one of n-dodecyl mercaptan, sec-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptoethanol, thioglycolic acid and isooctyl mercaptoacrylate.
The production method of the present invention is explained in more detail below with reference to fig. 1 to 3, and it will be understood by those skilled in the art that fig. 1 to 3 of the present invention do not constitute a limitation of the production method of the present invention.
After the first mixed feed liquid is mixed in a mixing kettle V1, the first mixed feed liquid enters at least one first heat exchanger E1 in the integrated heat exchange system through at least one first continuous conveying unit B1 in the continuous conveying units, enters at least one second heat exchanger E2 in the integrated heat exchange system through the at least one first heat exchanger E1, and enters a microchannel reactor W1 through the at least one second heat exchanger E2 for reaction, wherein the reaction time is t1;
or the first mixed feed liquid enters at least one first heat exchanger E1 in the integrated heat exchange system through at least one first continuous conveying unit B1 in the continuous conveying units, and enters the microchannel reactor W1 through the at least one first heat exchanger E1 for reaction, wherein the reaction time is t1;
after the reaction time t1, the second mixed feed liquid premixed in the mixing kettle V2 enters the at least one microchannel reactor W1 through at least one second continuous conveying unit B2 in the continuous conveying units to be mixed with the first mixed feed liquid for reaction, and the reaction time is t2;
then the reaction liquid enters a tubular reactor G1 for reaction, and the reaction time is t3;
preferably, the reaction time t1 is 30 to 150s, the reaction time t2 is 30 to 150s, and the reaction time t3 is 1 to 30min. More preferably, the reaction time t1 is 30 to 120s, the reaction time t2 is 30 to 120s, and the reaction time t3 is 5 to 30min.
More specifically, after being mixed in the mixing kettle V1, the first mixed feed liquid enters a shell-side inlet of at least one first heat exchanger E1 in the integrated heat exchange system through at least one first continuous conveying unit B1 in the continuous conveying units, enters a tube-side inlet of at least one second heat exchanger E2 in the integrated heat exchange system from a shell-side outlet thereof through the at least one first heat exchanger E1, enters a channel inlet of the microchannel reactor W1 from a tube-side outlet thereof through the at least one second heat exchanger E2, and reacts in the microchannel reactor W1 for t1;
or the first mixed feed liquid enters a shell side inlet of at least one first heat exchanger E1 in the integrated heat exchange system through at least one first continuous conveying unit B1 in the continuous conveying units, and enters a channel inlet of a microchannel reactor W1 from a shell side outlet of the first heat exchanger E1 through the at least one first heat exchanger E1 to react, wherein the reaction time is t1;
after the reaction time t1, the second mixed feed liquid premixed in the mixing kettle V2 enters the middle inlet of the at least one microchannel reactor W1 through at least one second continuous conveying unit B2 in the continuous conveying units to be mixed with the first mixed feed liquid for continuous reaction, and the reaction time is t2;
and then the reaction liquid enters the tubular reactor G1 from the channel outlet of the microchannel reactor W1 for reaction, and the reaction time is t3. Wherein the channel inlet of the microchannel reactor W1 is located at one side of the microchannel reactor W1, which is different from the position of the middle inlet of the microchannel reactor W1. The description of the positions of the channel inlet and the intermediate inlet of the microchannel reactor W1 is the same as above.
Then, the reaction liquid flows out of the tubular reactor, enters a shell-side inlet of at least one second heat exchanger E2 in the integrated heat exchange system, passes through the at least one second heat exchanger E2, enters a tube-side inlet of at least one first heat exchanger E1 in the integrated heat exchange system from a shell-side outlet thereof, passes through the at least one first heat exchanger E1, flows out of a tube-side outlet thereof, and enters a receiving tank J1.
In the invention, the production system is provided with an automatic control and temperature-pressure-flow linkage system, and the pressure of the production system is controlled by a back pressure system and the temperature-pressure-flow linkage system. The pressure control range of the production system is 1-4 MPa, and preferably 1.5-3 MPa.
Preferably, said at least one microchannel reactor W1 is connected to said at least one third heat exchanger E3; preferably, the at least one tubular reactor G1 is connected to the at least one fourth heat exchanger E4.
Preferably, the first mixed feed liquid is preheated to 90-130 ℃ through the at least one comprehensive heat exchange system; preferably, the at least one microchannel reactor W1 is preheated to 170-220 ℃ by the at least one third heat exchanger E3; preferably, the at least one tubular reactor G1 is preheated to 170-220 ℃ by means of at least one fourth heat exchanger E4. Preferably, the reaction liquid after the reaction in the tubular reactor G1 is discharged from the tubular reactor G1, and then cooled to 20-90 ℃, preferably to 30-80 ℃ through the comprehensive heat exchange system.
According to the free radical polymerization rule, the increase of the reaction temperature can reduce the molecular weight of the resin, namely, the apparent viscosity of the acrylic resin liquid can be reduced, and the distribution width of the molecular weight of the resin can be reduced, so that the solid content of the resin can be improved, and the high-solid acrylic resin can be obtained. The production system and the production method can control higher reaction temperature and shorter reaction time, achieve the effects of improving solid content and reducing viscosity, and improve production efficiency, and compared with the batch production process of the reaction kettle, the production system and the production method provided by the invention have the advantage that the production efficiency is improved by at least two times.
Compared with the device and the method for producing acrylic resin in batch, the production system and the production method have the advantages of energy conservation and mainly comprise the following three points. The environment where the mixed material liquid reacts maintains a constant temperature area, the temperature is raised to a certain range only before starting, and the repeated temperature reduction and rise process is not needed in the production process, so that the waste of energy is reduced, and the method is one of energy-saving points. The reaction liquid flowing out of the reactor is subjected to heat exchange with the mixed material liquid through the heat exchanger to achieve the effect of temperature reduction, so that the cold quantity required by the temperature reduction of the reaction liquid is saved, and the energy-saving point is two. The mixed material liquid is subjected to heat exchange with the reaction liquid through the heat exchanger to achieve the preheating effect, and the heat required by preheating the mixed material liquid is saved, which is the third energy-saving point. For a production line producing 5000t products every year, compared with an intermittent batch kettle type production device and method, the production system and the production method for continuously producing the high-solid acrylic resin can save energy by 60 percent.
Examples
The invention is further illustrated by the following examples, but it will be understood by those skilled in the art that these examples are not to be construed as limiting the invention.
The individual components used in the examples, such as heat exchangers, microchannel reactors, tube reactors, continuous feed units, receiving tanks, etc., are commercially available. The structure, reaction principles and effects of use of these components are known to those skilled in the art, but the entire production system is not commercially available from the market nor known to those skilled in the art.
The viscosity and solid content of the prepared product are detected by adopting a conventional detection method.
Example 1
The outlet of a B1 diaphragm metering pump of the continuous conveying unit is connected with a shell pass inlet of an E2 heat exchanger in the comprehensive heat exchange system, a shell pass outlet of the E2 heat exchanger is connected with a tube pass inlet of the E1 heat exchanger, a tube pass outlet of the E1 heat exchanger is connected with a channel inlet of a W1 micro-channel reactor with 4 reaction units, a channel outlet of the W1 micro-channel reactor is connected with a tube pass inlet of a G1 dynamic tube reactor, a tube pass outlet of the G1 dynamic tube reactor is connected with a shell pass inlet of the E1 heat exchanger, a shell pass outlet of the E1 heat exchanger is connected with a tube pass inlet of the E2 heat exchanger, and a tube pass outlet of the E2 heat exchanger is connected with a J1 receiving tank inlet. And a B2 plunger metering pump of the continuous conveying unit is connected with an inlet of a third reaction unit of the W1 micro-channel reactor, a heat exchange channel of the W1 micro-channel reactor is connected with an E3 heat exchanger, and a heat exchange channel of the G1 dynamic tubular reactor is connected with an E4 heat exchanger. And a temperature-pressure-flow linkage system is arranged at each connecting point through which the raw material mixed liquid flows, and a back pressure system is connected between the E2 heat exchanger and the J1 receiving tank.
In this embodiment, the method for producing the high-solid acrylic resin by using the production system includes the following steps:
raw materials, a solvent and an auxiliary agent are mixed according to a mass ratio of r1: 76.2.
Raw materials, a solvent and an auxiliary agent are mixed according to a mass ratio of r2:7.6, 2.1, 0.5, and the preparation of the second raw material mixture (hereinafter referred to as "Y2 raw material mixture") is completed in the V2 mixing kettle under normal temperature and pressure, and the mixing kettle is a common kettle with a stirring function on the market.
The raw materials are thermosetting polyester, methyl acrylate, styrene, hydroxypropyl methacrylate, hydroxyethyl acrylate, butyl methacrylate and acrylic acid, and the mass ratio is as follows: 14:12.3:36.1:11.8:10.7:14.5:0.6.
The solvent is selected from dimethylbenzene and butyl acetate, and the mass ratio of the dimethylbenzene to the butyl acetate is as follows: 1:1.
The auxiliary agent is an initiator and a molecular weight regulator, the initiator is selected from di-tert-amyl peroxide and tert-butyl hydroperoxide, the mass ratio of the di-tert-amyl peroxide to the tert-butyl hydroperoxide is 2:1, the molecular weight regulator is selected from n-dodecyl mercaptan, and the mass ratio of the initiator to the molecular weight regulator is 13.
Pumping the prepared Y1 raw material mixed liquor into the shell side of an E2 heat exchanger through a B1 diaphragm metering pump, preheating the mixed liquor to 100 ℃ through the tube side of the E1 heat exchanger, and then entering a W1 micro-channel reactor preheated to 180 ℃ through an E3 heat exchanger for rapid reaction for 60s. And at the middle feed inlet of the W1 micro-channel reactor (the inlet of the third reaction unit), the raw material is contacted and mixed with the raw material mixed liquor pumped into the Y2 micro-channel reactor by the B2 plunger metering pump, and the reaction is continued for 60s. Then the mixture enters a G1 dynamic tubular reactor preheated to 180 ℃ by an E4 heat exchanger for continuous reaction for 10min. The reaction liquid flowing out of the G1 dynamic tubular reactor flows through the shell side of the E1 heat exchanger, then flows through the tube side of the E2 heat exchanger, is cooled to 50 ℃, and then flows into the J1 receiving tank. The production system is provided with an automatic control and temperature-pressure-flow linkage system, the pressure of the production system is controlled by a back pressure system and the temperature-pressure-flow linkage system, and the pressure of the production system is controlled at 1.9MPa.
And (3) detection results: the conversion rate of the raw material is 98%, the solid content of the product is 75%, and the viscosity of the product is 3500cp at 30 ℃.
Example 2
The outlet of a B1 diaphragm metering pump of the continuous conveying unit is connected with a shell side inlet of an E1 heat exchanger in the comprehensive heat exchange system, a shell side outlet of the E1 heat exchanger is connected with a channel inlet of a W1 micro-channel reactor with 4 reaction units, a channel outlet of the W1 micro-channel reactor is connected with a tube side inlet of a G1 coil type reactor, a tube side outlet of the G1 coil type reactor is connected with a tube side inlet of an E2 heat exchanger, a tube side outlet of the E2 heat exchanger is connected with a tube side inlet of the E1 heat exchanger, and a tube side outlet of the E1 heat exchanger is connected with a J1 receiving tank inlet. And a B2 plunger metering pump of the continuous conveying unit is connected with an inlet of a third reaction unit of the W1 micro-channel reactor, a heat exchange channel of the W1 micro-channel reactor is connected with an E3 heat exchanger, and a heat exchange channel of the G1 coil type reactor is connected with an E4 heat exchanger. And a temperature-pressure-flow linkage system is arranged at each connecting point through which the raw material mixed liquid flows, and a back pressure system is connected between the E2 heat exchanger and the J1 receiving tank. In this embodiment, the method for producing the high solid content acrylic resin by using the production system includes the following steps:
raw materials, a solvent and an auxiliary agent are mixed according to a mass ratio of r1: 76.2, 2.8, the first raw material mixture (hereinafter referred to as "Y1 raw material mixture") was prepared in the V1 mixing tank under normal temperature and pressure, and the mixing tank was a commercially available tank with a stirring function.
Raw materials, a solvent and an auxiliary agent are mixed according to a mass ratio of r2:7.6, 2.1, 0.5, and the preparation of the second raw material mixture (hereinafter referred to as "Y2 raw material mixture") is completed in the V2 mixing kettle under normal temperature and pressure, and the mixing kettle is a common kettle with a stirring function on the market.
The raw materials are selected from hydroxyl polyester, styrene, butyl acrylate, isooctyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate and acrylic acid, and the mass ratio is as follows: 20:18:21.5:13:9.4:16.7:0.5.
The solvent is xylene.
The auxiliary agent is an initiator and a molecular weight regulator, the initiator is selected from di-tert-amyl peroxide and tert-butyl hydroperoxide, the mass ratio of the di-tert-amyl peroxide to the tert-butyl hydroperoxide is 2:1, the molecular weight regulator is selected from isooctyl thioglycolate, and the mass ratio of the initiator to the molecular weight regulator is 10. Pumping the prepared Y1 raw material mixed liquor into the shell side of an E2 heat exchanger through a B1 diaphragm metering pump, preheating the mixed liquor to 100 ℃ through the tube side of the E1 heat exchanger, and then entering a W1 micro-channel reactor preheated to 180 ℃ through an E3 heat exchanger for rapid reaction for 60s. And at the middle feed inlet of the W1 micro-channel reactor (the inlet of the third reaction unit), the raw material is contacted and mixed with the raw material mixed liquor pumped into the Y2 micro-channel reactor by the B2 plunger metering pump, and the reaction is continued for 60s. Then the mixture enters a G1 coil type reactor preheated to 180 ℃ by an E4 heat exchanger for continuous reaction for 10min. The reaction liquid flowing out of the G1 coil type reactor flows through the shell side of the E1 heat exchanger, then flows through the tube side of the E2 heat exchanger, is cooled to 50 ℃, and then flows into the J1 receiving tank. The production system is provided with an automatic control and temperature-pressure-flow linkage system, the pressure of the production system is controlled by a back pressure system and the temperature-pressure-flow linkage system, and the pressure of the production system is controlled at 1.9MPa.
And (3) detection results: the conversion rate of the raw materials is 98%, the solid content of the product is 75%, and the viscosity of the product is 2600cp at 30 ℃.
Example 3
The outlet of a B1 diaphragm metering pump of the continuous conveying unit is connected with the shell side inlet of an E1 heat exchanger in the comprehensive heat exchange system, the shell side outlet of the E1 heat exchanger is connected with the channel inlet of a W1 micro-channel reactor with 4 reaction units, the channel outlet of the W1 micro-channel reactor is connected with the channel inlet of a G1 tube bundle reactor, the channel outlet of the G1 tube bundle reactor is connected with the tube side inlet of the E1 heat exchanger, the tube side outlet of the E1 heat exchanger is connected with the tube side inlet of an E2 heat exchanger, and the tube side outlet of the E2 heat exchanger is connected with a J1 receiving tank inlet. And a B2 plunger metering pump of the continuous conveying unit is connected with an inlet of a third reaction unit of the W1 micro-channel reactor, a heat exchange channel of the W1 micro-channel reactor is connected with an E3 heat exchanger, and a heat exchange channel of the G1 tube bundle reactor is connected with an E4 heat exchanger. And a temperature-pressure-flow linkage system is arranged at each connecting point through which the raw material mixed liquid flows, and a back pressure system is connected between the E2 heat exchanger and the J1 receiving tank. In this embodiment, the method for producing the high-solid acrylic resin by using the production system includes the following steps:
raw materials, a solvent and an auxiliary agent are mixed according to a mass ratio of r1: 76.2, 2.8, the first raw material mixture (hereinafter referred to as "Y1 raw material mixture") was prepared in the V1 mixing tank under normal temperature and pressure, and the mixing tank was a commercially available tank with a stirring function.
Raw materials, a solvent and an auxiliary agent are mixed according to a mass ratio of r2:7.6, 2.1, 0.5, and the preparation of the second raw material mixture (hereinafter referred to as "Y2 raw material mixture") is completed in the V2 mixing kettle under normal temperature and pressure, and the mixing kettle is a common kettle with a stirring function on the market.
The raw materials are styrene, methyl acrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, isooctyl acrylate, acrylic acid and methyl acrylate, and the mass ratio is 16.7.
The solvent is selected from dimethylbenzene and butyl acetate, and the mass ratio of the dimethylbenzene to the butyl acetate is 2:1.
The auxiliary agent is an initiator and a molecular weight regulator, the initiator is selected from di-tert-butyl peroxide, the molecular weight regulator is selected from tert-dodecyl mercaptan, and the mass ratio of the initiator to the molecular weight regulator is 15.
Pumping the prepared Y1 raw material mixed liquor into the shell side of an E2 heat exchanger through a B1 diaphragm metering pump, preheating the mixed liquor to 100 ℃ through the tube side of the E1 heat exchanger, and then entering a W1 micro-channel reactor preheated to 180 ℃ through an E3 heat exchanger for rapid reaction for 60s. And at the middle feed inlet of the W1 micro-channel reactor (the inlet of the third reaction unit), the raw material is contacted and mixed with the raw material mixed liquor pumped into the Y2 micro-channel reactor by the B2 plunger metering pump, and the reaction is continued for 60s. Then the mixture enters a G1 winding tube type reactor preheated to 180 ℃ by an E4 heat exchanger for continuous reaction for 10min. The reaction liquid flowing out of the G1 winding tube type reactor flows through the shell side of the E1 heat exchanger, then flows through the tube side of the E2 heat exchanger, is cooled to 50 ℃, and then flows into the J1 receiving tank. The production system is provided with an automatic control and temperature-pressure-flow linkage system, the pressure of the production system is controlled by a backpressure system and the temperature-pressure-flow linkage system, and the pressure of the production system is controlled at 2.3MPa.
And (3) detection results: the conversion rate of the raw material is 98%, the solid content of the product is 75%, and the viscosity of the product is 2900cp at 30 ℃.
Example 4
The outlet of a B1 metering pump of the continuous conveying unit is connected with a shell side inlet of an E2 heat exchanger in the comprehensive heat exchange system, a shell side outlet of the E2 heat exchanger is connected with a tube side inlet of the E1 heat exchanger, a tube side outlet of the E1 heat exchanger is connected with a channel inlet of a W1 micro-channel reactor, a channel outlet of the W1 micro-channel reactor is connected with a tube side inlet of a G1 coil reactor, a tube side outlet of the G1 coil reactor is connected with a shell side inlet of the E1 heat exchanger, a shell side outlet of the E1 heat exchanger is connected with a tube side inlet of the E2 heat exchanger, and a tube side outlet of the E2 heat exchanger is connected with a J1 receiving tank inlet. The B2 metering pump of the continuous conveying unit is connected with a middle feeding port (an inlet of the reaction unit) of the W1 micro-channel reactor, a heat exchange channel of the W1 micro-channel reactor is connected with an E3 heat exchanger, and a heat exchange channel of the G1 coil type reactor is connected with an E4 heat exchanger. And a temperature-pressure-flow linkage system is arranged at each connecting point through which the raw material mixed liquid flows, and a back pressure system is connected between the E2 heat exchanger and the J1 receiving tank.
In this embodiment, the method for producing the high-solid acrylic resin by using the production system includes the following steps:
the raw materials, the solvent and the auxiliary agent are put into a V1 mixing kettle according to the mass ratio r1, the preparation of a first raw material mixed solution (hereinafter referred to as a Y1 raw material mixed solution) is completed in the V1 mixing kettle, the preparation environment is normal temperature and normal pressure, and the mixing kettle is a common kettle with a stirring function in the market.
The raw materials, the solvent and the auxiliary agent are put into a V2 mixing kettle according to the mass ratio r2, the preparation of a second raw material mixed solution (hereinafter referred to as a Y2 raw material mixed solution) is completed in the V2 mixing kettle, the preparation environment is normal temperature and normal pressure, and the mixing kettle is a common kettle with a stirring function in the market.
The raw materials are styrene, methyl acrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, isooctyl acrylate, acrylic acid and methyl acrylate, and the mass ratio is 16.7.
The solvent is selected from dimethylbenzene and butyl acetate, and the mass ratio of the dimethylbenzene to the butyl acetate is 2:1.
The auxiliary agent is an initiator and a molecular weight regulator, the initiator is selected from di-tert-amyl peroxide and tert-butyl hydroperoxide, the mass ratio of the di-tert-amyl peroxide to the tert-butyl hydroperoxide is 2:1, the molecular weight regulator is selected from isooctyl thioglycolate, and the mass ratio of the initiator to the molecular weight regulator is 15.
Pumping the prepared Y1 raw material mixed liquor into a shell side of an E2 heat exchanger through a B1 metering pump, preheating the mixed liquor to T1 through a tube side of the E1 heat exchanger, and then entering a W1 micro-channel reactor preheated to T2 through an E3 heat exchanger for rapid reaction for T1. And at the middle feed inlet (reaction unit inlet) of the W1 micro-channel reactor, the raw material is contacted and mixed with the raw material mixed liquor pumped into the Y2 micro-channel reactor by the B2 metering pump, and the reaction is continued for reaction time t2. Then enters a G1 coil type reactor preheated to T3 by an E4 heat exchanger for continuing the reaction for a reaction time T3. And the reaction liquid flowing out of the G1 coil type reactor flows through the shell side of the E1 heat exchanger, then flows through the tube side of the E2 heat exchanger, is cooled to T4, and then flows into the J1 receiving tank. The production system is provided with an automatic control and temperature-pressure-flow linkage system, the pressure of the production system is controlled by a back pressure system and the temperature-pressure-flow linkage system, and the pressure of the production system is controlled at P1.
In this embodiment, the number of reaction units of the W1 microchannel reactor is changed, the reaction times t1 and t2 of the raw material mixed solution in the W1 microchannel reactor are changed accordingly, and the reaction parameters and the product detection results related to the production method are shown in table 1 below.
TABLE 1
Example 5
In this example, the production system and the production method are the same as those in example 4, the number of reaction units of the W1 microchannel reactor is 6, the position of the middle feed port (inlet of the reaction unit) of the W1 microchannel reactor is changed, that is, the feed position of the Y2 mixed feed liquid is changed, the reaction times t1 and t2 of the mixed feed liquid in the W1 microchannel reactor are changed accordingly, and the reaction parameters and the product detection results involved in the production method are shown in table 2 below.
TABLE 2
Example 6
In this example, the production system and the production method were the same as in example 4, the volume of the coil reactor was changed, that is, the reaction time t3 of the reaction solution in the G1 coil reactor was changed, and the reaction parameters and the product test results involved in the production method are shown in table 3 below.
TABLE 3
Example 7
In this example, the production system and the production method were the same as those in example 4, the temperature T2 of the W1 microchannel reactor was controlled by changing the E3 heat exchanger, and the reaction parameters and the product detection results involved in the production method are shown in table 4 below.
TABLE 4
Example 8
In this example, the production system and the production method were the same as those in example 4, the temperature T3 of the G1 coil reactor was controlled by changing the E4 heat exchanger, and the reaction parameters and the product detection results involved in the production method are shown in table 5 below.
TABLE 5
Example 9
In this example, the production system and the production method were the same as those in example 4, and the temperature T2 of the microchannel reactor controlled by the E3 heat exchanger and the temperature T3 of the coil reactor G1 controlled by the E4 heat exchanger were changed at the same time, and the reaction parameters and the product detection results involved in the production method are shown in table 6 below.
TABLE 6
Example 10
In this example, the production system and the production method were the same as those in example 4, while the mass ratios r1 and r2 of the raw materials, the solvent, and the auxiliary were changed, and the reaction parameters and the product detection results involved in the production method are shown in table 7 below.
TABLE 7
Comparative example 1
In this comparative example, the production system and production method were the same as in example 4, while changing the temperature T2 of the W1 microchannel reactor controlled by the E3 heat exchanger and the temperature T3 of the G1 coil reactor controlled by the E4 heat exchanger, and the reaction parameters and product detection results involved in the production method are shown in table 8 below.
TABLE 8
As shown in Table 8 above, when T2 and T3 are lower than 170 ℃, the reaction time is shorter, so that the conversion rate of raw materials is low, the solid content of products is low, and the similar reaction effect can be realized by prolonging the reaction time, but the production efficiency is reduced and is less than one fourth of the production efficiency when T2 and T3 are both 180 ℃. When T2 and T3 are higher than 220 ℃, the initiator is instantaneously decomposed due to very high reaction temperature, instantaneous violent reaction is not easy to control, the overhigh temperature exceeds the tolerance temperature of the continuous reaction unit, the pressure of a reaction system is increased along with the increase of the reaction temperature, and the service life of the continuous reaction unit is shortened by one third of the normal service life when the continuous reaction unit is operated at high temperature and high pressure for a long time.
Comparative example 2
In this comparative example, the production system and the production method were the same as in example 4, the reaction times t1, t2, and t3 of the materials in the W1 microchannel reactor and the G1 coil reactor were changed, and the reaction parameters and the product test results involved in the production method are shown in table 9 below.
TABLE 9
As shown in Table 9 above, at 180 ℃ for both T2 and T3, the shorter reaction time resulted in low conversion of the starting materials and low solids content of the product. Although increasing the reaction time of the feed in the G1 coil reactor increases the solids content, there is a corresponding increase in the viscosity. On the other hand, the reaction time of the materials in the W1 microchannel reactor is prolonged, and the reaction time of the materials in the G1 tubular reactor is shortened, so that the materials only react in the W1 microchannel reactor, and although the similar reaction effect can be obtained, the production capacity of the production system is low, and the production capacity is less than 50% of the production capacity when only the continuous reaction unit is that the W1 microchannel reactor is connected with the G1 coil tubular reactor in series.
Based on the above, the production system and the production method of the invention can control higher reaction temperature and shorter reaction time, achieve the effects of improving solid content and reducing viscosity, improve production efficiency and obtain excellent technical effects.
Claims (28)
1. A continuous production system is characterized by comprising a continuous reaction unit and a comprehensive heat exchange system, wherein the continuous reaction unit is connected with the comprehensive heat exchange system, the continuous reaction unit is used for receiving mixed feed liquid and reacting the mixed feed liquid to form reaction liquid, the comprehensive heat exchange system comprises at least one first heat exchanger (E1), the first heat exchanger (E1) comprises two heat exchange strokes, the two heat exchange strokes are used for allowing the mixed feed liquid and the reaction liquid to flow respectively, and the mixed feed liquid and the reaction liquid exchange heat when flowing in the heat exchange strokes;
the comprehensive heat exchange system comprises at least one second heat exchanger (E2), the second heat exchanger (E2) is connected with the first heat exchanger (E1) in series, the mixed feed liquid and the reaction liquid respectively flow through the first heat exchanger (E1) in sequence, the reaction liquid flows through the second heat exchanger (E2),
the production system also comprises a continuous conveying unit and at least one receiving tank (J1), wherein the continuous conveying unit is connected with the comprehensive heat exchange system and conveys the mixed feed liquid to the continuous reaction unit through the comprehensive heat exchange system; the receiving tank (J1) is connected with the comprehensive heat exchange system,
at least one first continuous conveying unit (B1) in the continuous conveying unit is connected with a shell side inlet of at least one first heat exchanger (E1) in the integrated heat exchange system, a shell side outlet of the at least one first heat exchanger (E1) is connected with a tube side inlet of at least one second heat exchanger (E2) in the integrated heat exchange system, a tube side outlet of the at least one second heat exchanger (E2) is connected with at least one microchannel reactor (W1), the at least one microchannel reactor (W1) is connected with at least one tube reactor (G1), the at least one tube reactor (G1) is connected with a shell side inlet of the at least one second heat exchanger (E2), a shell side outlet of the at least one second heat exchanger (E2) is connected with a tube side inlet of the at least one first heat exchanger (E1), a tube side outlet of the at least one first heat exchanger (E1) is connected with an inlet of the at least one receiving tank (J1), and at least one continuous conveying unit (B2) in the continuous conveying unit is connected with the at least one second heat exchanger (W2);
or at least one first continuous conveying unit (B1) in the continuous conveying units is connected with the shell side inlet of at least one first heat exchanger (E1) in the integrated heat exchange system, the shell side outlet of the at least one first heat exchanger (E1) is connected with the at least one microchannel reactor (W1), the at least one microchannel reactor (W1) is connected with at least one tubular reactor (G1), the at least one tubular reactor (G1) is connected with the inlet of at least one second heat exchanger (E2), the outlet of the at least one second heat exchanger (E2) is connected with the tube side inlet of the at least one first heat exchanger (E1), the tube side outlet of the at least one first heat exchanger (E1) is connected with the inlet of the at least one receiving tank (J1), and at least one second continuous conveying unit (B2) in the continuous conveying units is connected with the at least one microchannel reactor (W1);
or at least one first continuous conveying unit (B1) in the continuous conveying units is connected with the shell side inlet of at least one first heat exchanger (E1) in the integrated heat exchange system, the shell side outlet of the at least one first heat exchanger (E1) is connected with the at least one microchannel reactor (W1), the at least one microchannel reactor (W1) is connected with at least one tubular reactor (G1), the at least one tubular reactor (G1) is connected with the shell side inlet of the at least one first heat exchanger (E1), the shell side outlet of the at least one first heat exchanger (E1) is connected with the inlet of the at least one second heat exchanger (E2), the outlet of the at least one second heat exchanger (E2) is connected with the inlet of the at least one receiving tank (J1), and the at least one second continuous conveying unit (B2) in the continuous conveying units is connected with the at least one microchannel reactor (W1).
2. The production system of claim 1, wherein the continuous reaction unit comprises at least one microchannel reactor and at least one tubular reactor.
3. The production system according to claim 1 or 2, wherein the pipe reactor is selected from at least one of a dynamic pipe reactor and a static pipe reactor.
4. The production system according to claim 1 or 2, further comprising at least one third heat exchanger (E3), at least one fourth heat exchanger (E4); the third heat exchanger (E3) and the fourth heat exchanger (E4) are respectively connected with the microchannel reactor and the tubular reactor so as to enable the microchannel reactor and the tubular reactor to be at preset temperatures and control the temperature of the reaction liquid in the continuous reaction unit in the continuous production process.
5. The production system of claim 1 or 2, wherein the continuous reaction unit comprises a first feed inlet and a second feed inlet, the first feed inlet is used for conveying the mixed material liquid which passes through the comprehensive heat exchange system to the continuous reaction unit, and the second feed inlet is used for conveying the mixed material liquid which does not pass through the comprehensive heat exchange system to the continuous reaction unit.
6. A production method for continuously producing a resin, characterized in that the resin is produced using the production system according to any one of claims 1 to 5.
7. The production method according to claim 6, wherein the first mixed feed liquid and the second mixed feed liquid are respectively fed into the continuous reaction unit for reaction, and the temperature of the production system is controlled by the integrated heat exchange system.
8. The production method according to claim 7, wherein the first mixed feed liquid enters at least one first heat exchanger (E1) in the integrated heat exchange system through at least one first continuous conveying unit (B1) in the continuous conveying units, enters at least one second heat exchanger (E2) in the integrated heat exchange system through the at least one first heat exchanger (E1), enters the microchannel reactor (W1) through the at least one second heat exchanger (E2) for reaction, and has the reaction time of t1;
or the first mixed feed liquid enters at least one first heat exchanger (E1) in the integrated heat exchange system through at least one first continuous conveying unit (B1) in the continuous conveying units, and enters a microchannel reactor (W1) through the at least one first heat exchanger (E1) for reaction, wherein the reaction time is t1;
after the reaction time t1, the second mixed feed liquid enters the at least one microchannel reactor (W1) through at least one second continuous conveying unit (B2) in the continuous conveying units to be mixed with the first mixed feed liquid for continuous reaction, and the reaction time is t2;
then the reaction liquid enters a tubular reactor (G1) for reaction, and the reaction time is t3.
9. The production process according to claim 8, wherein the reaction time t1 is 30 to 150s, the reaction time t2 is 30 to 150s, and the reaction time t3 is 1 to 30min.
10. The production process according to claim 9, wherein the reaction time t1 is 30 to 120s, the reaction time t2 is 30 to 120s, and the reaction time t3 is 5 to 30min.
11. The production process according to claim 8, wherein the first mixed liquor enters the shell-side inlet of at least one first heat exchanger (E1) in the integrated heat exchange system through at least one first continuous conveying unit (B1) in the continuous conveying units, enters the tube-side inlet of at least one second heat exchanger (E2) in the integrated heat exchange system from the shell-side outlet thereof through the at least one first heat exchanger (E1), enters the channel inlet of the microchannel reactor (W1) from the tube-side outlet thereof through the at least one second heat exchanger (E2) for reaction, and has a reaction time t1;
or the first mixed feed liquid enters a shell side inlet of at least one first heat exchanger (E1) in the integrated heat exchange system through at least one first continuous conveying unit (B1) in the continuous conveying units, passes through the at least one first heat exchanger (E1) and enters a channel inlet of the microchannel reactor (W1) from a shell side outlet thereof for reaction, and the reaction time is t1;
after the reaction time t1, the second mixed feed liquid enters at least one middle inlet of the at least one microchannel reactor (W1) through at least one second continuous conveying unit (B2) in the continuous conveying units to be mixed with the first mixed feed liquid for continuous reaction, and the reaction time is t2;
then, the reaction liquid enters the tubular reactor (G1) from the channel outlet of the microchannel reactor (W1) for reaction, and the reaction time is t3;
wherein the channel inlet of the microchannel reactor (W1) is located at one side of the microchannel reactor (W1) at a position different from the position of the middle inlet of the microchannel reactor (W1).
12. The production process according to claim 11, wherein the reaction time t1 is 30 to 150s, the reaction time t2 is 30 to 150s, and the reaction time t3 is 1 to 30min.
13. The production process according to claim 12, wherein the reaction time t1 is 30 to 120s, the reaction time t2 is 30 to 120s, and the reaction time t3 is 5 to 30min.
14. The production method according to any one of claims 8 to 13, wherein the pressure control range of the production system is 1 to 4MPa.
15. The production method according to claim 14, wherein the pressure control range of the production system is 1.5 to 3MPa.
16. The production process according to any one of claims 8 to 13, wherein the at least one microchannel reactor (W1) is connected to the at least one third heat exchanger (E3).
17. The production process according to any one of claims 8 to 13, wherein the at least one tubular reactor (G1) is connected to the at least one fourth heat exchanger (E4).
18. The production method according to any one of claims 8 to 13, wherein the first mixed liquor is preheated to 90 to 130 ℃ by the integrated heat exchange system.
19. The production process according to any one of claims 8 to 13, wherein the at least one microchannel reactor (W1) is preheated to 170 to 220 ℃ by at least one third heat exchanger (E3).
20. The production process according to any one of claims 8 to 13, wherein the at least one tubular reactor (G1) is preheated to 170 to 220 ℃ by means of at least one fourth heat exchanger (E4).
21. The production process according to any one of claims 8 to 13, wherein the reaction liquid after the reaction in the tubular reactor (G1) is discharged from the tubular reactor (G1) and then cooled to 20 to 90 ℃.
22. The method of claim 21, wherein the temperature is subsequently reduced to 30-80 ℃.
23. The production method according to any one of claims 7 to 13, wherein the first and second mixed liquors comprise a raw material, a solvent and an auxiliary agent.
24. The production method according to claim 23, wherein the mass ratio of the raw material to the solvent to the auxiliary in the first mixed feed liquid is 70-90.
25. The production method according to claim 24, wherein the mass ratio of the raw material to the solvent to the auxiliary agent in the first mixed feed liquid is 70-90.
26. The production method according to claim 24, wherein the raw material is a mixture of a (meth) acrylic monomer and styrene, or a mixture of a resin and a (meth) acrylic monomer and styrene.
27. The method of claim 26, wherein the resin is at least one of an alkyd, a thermosetting polyester, and a hydroxy polyester.
28. The production method according to claim 24, wherein the solvent is at least one of an ester solvent, a benzene solvent, an alcohol solvent, and an ether solvent.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1144810A (en) * | 1995-07-03 | 1997-03-12 | Basf公司 | Continuous preparation of polymers and apparatus therefor |
JP2001040366A (en) * | 1999-05-27 | 2001-02-13 | Mitsubishi Chemicals Corp | Cooling method for mixed gas |
CN108514855A (en) * | 2018-06-04 | 2018-09-11 | 山东豪迈机械制造有限公司 | A kind of reaction unit |
CN109966995A (en) * | 2019-04-26 | 2019-07-05 | 山东豪迈化工技术有限公司 | A kind of continuous flow Comprehensive Experiment skid-mounted device and method |
CN110982004A (en) * | 2019-12-24 | 2020-04-10 | 万华化学集团股份有限公司 | Preparation method of styrene-acrylonitrile copolymer |
-
2020
- 2020-05-06 CN CN202010374620.7A patent/CN113617307B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1144810A (en) * | 1995-07-03 | 1997-03-12 | Basf公司 | Continuous preparation of polymers and apparatus therefor |
JP2001040366A (en) * | 1999-05-27 | 2001-02-13 | Mitsubishi Chemicals Corp | Cooling method for mixed gas |
CN108514855A (en) * | 2018-06-04 | 2018-09-11 | 山东豪迈机械制造有限公司 | A kind of reaction unit |
CN109966995A (en) * | 2019-04-26 | 2019-07-05 | 山东豪迈化工技术有限公司 | A kind of continuous flow Comprehensive Experiment skid-mounted device and method |
CN110982004A (en) * | 2019-12-24 | 2020-04-10 | 万华化学集团股份有限公司 | Preparation method of styrene-acrylonitrile copolymer |
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