CN119060227A - Acrylate polymer microspheres, preparation method and application thereof, and system for preparing acrylate polymer microspheres - Google Patents

Acrylate polymer microspheres, preparation method and application thereof, and system for preparing acrylate polymer microspheres Download PDF

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Publication number
CN119060227A
CN119060227A CN202310623413.4A CN202310623413A CN119060227A CN 119060227 A CN119060227 A CN 119060227A CN 202310623413 A CN202310623413 A CN 202310623413A CN 119060227 A CN119060227 A CN 119060227A
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mixture
reactor
monomer
polymer microspheres
acrylate polymer
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刘振杰
张洁
张晓尘
斯维
张嘉桐
代增悦
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Priority to CN202310623413.4A priority Critical patent/CN119060227A/en
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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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00867—Microreactors placed in series, on the same or on different supports
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00873—Heat exchange
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00889—Mixing
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00905—Separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2433/12—Homopolymers or copolymers of methyl methacrylate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to the field of polymer synthesis, and relates to an acrylic ester polymer microsphere, a preparation method and application thereof, and a system for preparing the acrylic ester polymer microsphere. The method comprises the steps of S1, uniformly mixing a dispersion medium, a stabilizer, an initiator and a monomer to obtain a first mixture, S2, carrying out step-by-step polymerization on the first mixture to obtain a second mixture, S3, separating the second mixture to obtain acrylate polymer microspheres, wherein the dispersion medium and the monomer are mutually insoluble, the step-by-step polymerization is N-step polymerization, N is more than or equal to 2, the monomer conversion rate of the N-step polymerization is 1-5 times of the monomer conversion rate of the N-step polymerization in the step-1, and the method carries out the polymerization step by step, so that the heat transfer of a polymerization reaction system is easier to control, further reaction heat is removed, and the uniformity of the polymer microspheres is improved. Meanwhile, the dispersion medium is not mutually compatible with the monomer, and the prepared polymer microsphere has the characteristics of proper particle size, small dispersion coefficient and narrow molecular weight distribution index.

Description

Acrylate polymer microsphere, preparation method and application thereof, and system for preparing acrylate polymer microsphere
Technical Field
The invention relates to the field of polymer synthesis, in particular to an acrylic ester polymer microsphere, a preparation method and application thereof, and a system for preparing the acrylic ester polymer microsphere.
Background
The dispersion polymerization of acrylate monomers is usually carried out in a kettle-type reactor, while under laboratory conditions, a common glass bottle is a common reaction vessel, such as Yu Xianglin, etc., and the alcohol water dispersion polymerization method is used for preparing monodisperse micron-sized crosslinked polymethyl methacrylate microspheres, which are prepared by a Hubei university journal (Nature science edition) 2003,25 (2): 137-140. Shumei et al, preparation of monodisperse polymethyl methacrylate microspheres, liaoning chemical industry, 2012,41 (12): 1242-1244. Jiang Xueliang et al, producer of monodisperse narrow-distribution PMMA microspheres, hubei university journal (Nature science edition) 2014,36 (2): 138-142, the polymer microspheres obtained above are on the order of microns, but the molecular weight distribution is generally broad.
Recently, a process for preparing polymethyl methacrylate microspheres by a non-conventional process has also appeared. The oil phase fluid forms jet flow through the nozzle, the oil phase jet flow disperses in the water phase under vibration to form uniform liquid drops, the uniform liquid drops enter a fluidization reactor to be polymerized to obtain the monodisperse polymethyl methacrylate microsphere, the microsphere has larger particle size and average particle size of about 350 microns, such as Wang, and the like, and the preparation and performance of the monodisperse polymethyl methacrylate magnetic microsphere, chemical engineering and 2015,43 (9): 40-44.
In the traditional reaction process, the heat transfer of a reaction system is not easy to control, so that the final quality of a polymer product is slightly influenced, for example, the polymer has larger particle size, uneven particle size dispersion, wider polymer molecular weight distribution and the like.
Disclosure of Invention
The invention aims to solve the problems of difficult control of heat transfer of a reaction system, complicated preparation method, larger particle size of polymer microspheres and uneven particle size part in the prior art, and provides an acrylic ester polymer microsphere, a preparation method and application thereof, and a system for preparing the acrylic ester polymer microsphere. Meanwhile, the dispersion medium and the monomer are mutually insoluble, and the prepared polymer microsphere has the characteristics of proper particle size, small dispersion coefficient and narrow molecular weight distribution index.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing acrylate polymer microspheres, comprising the steps of:
s1, uniformly mixing a dispersion medium, a stabilizer, an initiator and a monomer to obtain a first mixture;
s2, carrying out step-by-step polymerization on the first mixture to obtain a second mixture;
s3, separating the second mixture to obtain acrylate polymer microspheres;
the dispersion medium is not compatible with the monomer;
wherein the step polymerization is N-step polymerization, and N is more than or equal to 2;
the monomer conversion rate of the N step is 1-5 times of that of the N-1 step.
The second aspect of the invention provides an acrylic polymer microsphere prepared by the preparation method of the first aspect of the invention.
In a third aspect, the present invention provides an application of the acrylate polymer microsphere according to the second aspect of the present invention as a modifier in a polyolefin film.
According to a fourth aspect of the present invention, there is provided a system for preparing the acrylic polymer microspheres according to the second aspect of the present invention, characterized in that the system comprises a raw material tank (1), a reactor (3), a collection tank (4), a separation device (5) and a heater (6);
the outlet of the raw material tank (1) is communicated with the inlet of the reactor (3) and is used for mixing raw materials to obtain a first mixture;
The inlet of the reactor (3) is communicated with the outlet of the raw material tank (1), and a heater (6) is arranged outside the reactor (3) and is used for carrying out polymerization reaction on the first mixture to obtain a second mixture;
The inlet of the collection tank (4) is communicated with the outlet of the reactor (3) and is used for collecting the second mixture;
The inlet of the separation device (5) is communicated with the outlet of the collection tank (4) and is used for separating the collected second mixture to obtain acrylate polymer microspheres;
wherein the number of the reactors 3 is M, the number of the heaters 6 is P, M is more than or equal to 2, and P is more than or equal to 2.
According to the technical scheme, the acrylate polymer microsphere, the preparation method and application thereof and the system for preparing the acrylate polymer microsphere have the advantages that in the method, polymerization is carried out step by step, so that the heat transfer of a polymerization reaction system is easier to control, the reaction heat in the reaction process is further easy to remove, and the uniformity of the prepared polymer microsphere is improved. Meanwhile, the dispersion medium is not mutually compatible with the monomer, and the polymer microsphere prepared by the preparation method has the characteristics of proper particle size, small dispersion coefficient and narrow molecular weight distribution index.
Drawings
FIG. 1 is a scanning electron microscope image of the acrylate polymer microspheres prepared in example 1 of the present invention;
FIG. 2 is a schematic diagram of a system for preparing acrylate polymer microspheres according to example 1 of the present invention.
Description of the reference numerals
1A raw material tank, 2-1 a first chromatographic pump, 2-2 a second chromatographic pump, 2-3 a third chromatographic pump, 3-1 a first reactor, 3-2 a second reactor, 3-3 a third reactor, 4a collecting tank, 5 a separating device, 6-1 a first heater, 6-2 a second heater, 6-3 a third heater, 7a drying device, 8 a condenser and 9a recovery tank.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a preparation method of acrylate polymer microspheres, which is characterized by comprising the following steps:
s1, uniformly mixing a dispersion medium, a stabilizer, an initiator and a monomer to obtain a first mixture;
s2, carrying out step-by-step polymerization on the first mixture to obtain a second mixture;
s3, separating the second mixture to obtain acrylate polymer microspheres;
the dispersion medium is not compatible with the monomer;
wherein the step polymerization is N-step polymerization, and N is more than or equal to 2;
the monomer conversion rate of the N step is 1-5 times of that of the N-1 step.
In the invention, the inventor researches and discovers that the reaction for preparing the acrylic polymer microsphere is easier to control by carrying out the polymerization step by step and controlling the conversion rate relation of the monomers in each polymerization step to meet the range, so that the reaction heat in the reaction process is easy to remove, and the uniformity of the polymer microsphere is improved.
Further, the dispersion medium and the monomer are mutually insoluble, and the prepared polymer microsphere has the characteristics of proper particle size, small dispersion coefficient and narrow molecular weight distribution index.
In the invention, the method further comprises fully purging the system before starting the system. The purge is performed by a protective gas purge as is conventional in the art, such as nitrogen or an inert gas purge. The purging time is not particularly limited and may be, for example, 20 to 40 minutes.
In the invention, the monomer conversion rate of the N step is 1 to 2.5 times of that of the N-1 step.
According to the invention, in step S1, the mixing comprises stirring and nitrogen bubbling.
In the invention, the stabilizer, the initiator and the monomer can be mixed more uniformly by mixing in a mode of combining stirring and bubbling.
According to the invention, the stirring speed of the stirring is 5-200r/min, preferably 50-200r/min, and the stirring time is 5-40min, preferably 10-40min.
According to the invention, the nitrogen bubbling time is 10-40min, preferably 10-30min.
According to the invention, in step S2, the step polymerization comprises heating the first mixture through a plurality of temperature zones.
According to the invention, the heating conditions of each of the plurality of temperature zones independently comprise a temperature of 45-95 ℃ for 60-400min.
In the invention, the inventor researches and discovers that the temperature and time in each temperature zone are controlled to meet the above range, so that the monomer conversion rate in each polymerization step can be controlled, the reaction heat of a reaction system is easier to control, and the polymer microsphere with proper particle size, small dispersion coefficient and narrow molecular weight distribution index is prepared.
According to the invention, the first mixture is heated through 3-5 temperature zones.
According to the invention, the method further comprises drying the acrylate polymer microspheres obtained after separation.
According to the invention, the drying conditions include a drying temperature of 50-120 ℃, a drying pressure of-0.95 to 0MPaG, and a drying time of 300-720min.
According to the present invention, the dispersion medium is selected from at least one of methanol, ethanol, and propanol.
In the invention, the dispersion medium is selected from the above types, and the prepared polymer microsphere has smaller dispersion coefficient and narrower molecular weight distribution index.
According to the invention, the weight average molecular weight of the stabilizer is from 10,000 to 600,000g/mol.
In the present invention, the weight average molecular weight of the stabilizer satisfies the above range, and the formation of a stable polymer colloidal dispersion can be ensured.
Further, the weight average molecular weight of the stabilizer is 10,000-300,000g/mol.
According to the invention, the stabilizer is selected from polyvinylpyrrolidone and/or polyacrylic acid.
According to the invention, the initiator is selected from azo-type initiators and/or peroxy-type initiators.
According to the present invention, the initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptonitrile and dibenzoyl peroxide.
According to the invention, the monomer is selected from methyl methacrylate and/or methyl acrylate.
According to the invention, the concentration of the monomers in the first mixture is 1-10wt%.
According to the invention, the content of the stabilizer is 3-10wt% of the mass of the monomer.
According to the invention, the initiator is present in an amount of 0.2 to 2% by weight based on the mass of the monomers.
In the invention, when any one of the concentration of the monomer, the amount of the stabilizer and the amount of the initiator satisfies the above range, the stable progress of the polymerization reaction can be ensured, thereby improving the reaction efficiency of the polymerization reaction.
Further, the concentration of the monomer in the first mixture is 2 to 10wt%.
Further, the stabilizer is used in an amount of 4 to 10wt% based on the mass of the monomer.
Further, the initiator is used in an amount of 0.5 to 2wt% based on the mass of the monomer.
The second aspect of the invention provides an acrylic polymer microsphere prepared by the preparation method of the first aspect of the invention.
According to the invention, the dispersion coefficient of the acrylate polymer microsphere is 1.008-1.1, preferably 1.008-1.09.
According to the invention, the number average particle size of the acrylate polymer microspheres is 0.5-1.4. Mu.m, preferably 0.8-1.4. Mu.m.
According to the invention, the weight average particle size of the acrylate polymer microspheres is 0.5-1.5. Mu.m, preferably 0.8-1.5. Mu.m.
According to the invention, the number average molecular weight of the acrylate polymer microspheres is 15000-50000, preferably 20000-40000.
According to the present invention, the molecular weight distribution index of the acrylate polymer microspheres is 1.5 to 2.2, preferably 1.5 to 2.
In a third aspect, the present invention provides an application of the acrylate polymer microsphere according to the second aspect of the present invention as a modifier in a polyolefin film.
In the invention, the inventor discovers that the acrylic polymer microsphere is applied to a polyolefin film as a modifier, and can obtain higher haze.
In the invention, when the acrylate polymer microsphere is used as a modifier in a polyolefin film, the acrylate polymer microsphere is used in an amount of 5-35wt%, preferably 15-25wt%.
According to a preferred embodiment of the invention, the polyolefin is polyethylene.
According to a fourth aspect of the present invention, there is provided a system for preparing the acrylic polymer microspheres according to the second aspect of the present invention, characterized in that the system comprises a raw material tank (1), a reactor (3), a collection tank (4), a separation device (5) and a heater (6);
the outlet of the raw material tank (1) is communicated with the inlet of the reactor (3) and is used for mixing raw materials to obtain a first mixture;
The inlet of the reactor (3) is communicated with the outlet of the raw material tank (1), and a heater (6) is arranged outside the reactor (3) and is used for carrying out polymerization reaction on the first mixture to obtain a second mixture;
The inlet of the collection tank (4) is communicated with the outlet of the reactor (3) and is used for collecting the second mixture;
The inlet of the separation device (5) is communicated with the outlet of the collection tank (4) and is used for separating the collected second mixture to obtain acrylate polymer microspheres;
wherein the number of the reactors 3 is M, the number of the heaters 6 is P, M is more than or equal to 2, and P is more than or equal to 2;
the length of the tubes of each reactor 3 decreases in the direction of flow of the reaction mass.
In the present invention, the separation device may be a separation device commonly used in the art, such as a centrifuge or a filtration device with a filter material having a pore size of 3 μm or less.
According to an implementation method of the invention, the rotating speed of the centrifugal machine ranges from 2000 r/min to 10000r/min.
In the invention, the heater can be a water bath device or an oil bath device, and the control precision is +/-1 ℃.
In the invention, the raw material tank (1) and the collecting tank (4) are internally provided with stirring devices for uniformly mixing materials.
According to the invention, the system further comprises a pump (2), a drying device (7), a condenser (8) and a recovery tank (9);
The pump (2) is arranged before the reactor (3) and is used for pumping the first mixture into the reactor (3);
The separation device (5) comprises a liquid phase outlet and a solid phase outlet;
The inlet of the drying device (7) is communicated with the solid phase outlet of the separation device (5) and is used for drying the solid phase material obtained after the second mixture is separated;
The inlet of the condenser (8) is communicated with the outlet of the drying device (7) and is used for condensing the liquid phase in the drying device (7) to obtain condensate;
The recovery tank (9) is communicated with an outlet of the condenser (8) and is used for recovering the condensate;
The recovery tank (9) is communicated with a liquid phase outlet of the separation device (5) and is used for recovering liquid phase materials obtained after the second mixture is separated.
In the invention, after the solid phase material is dried, the volatilized solvent is condensed by the condenser (8) and then enters the recovery tank (9), so that the solvent is prevented from leaking to the environment to cause pollution.
According to the invention, the reactor 3 is a tubular microreactor.
According to the invention, the inner diameter of the pipeline of the reactor 3 is 0.1-5mm, and the length is 0.2-5m.
In the present invention, the inner diameter and the length of the pipe of the reactor 3 satisfy the above ranges, and the reaction can be smoothly performed while ensuring heat transfer of the reaction.
Further, the inner diameter of the pipeline of the reactor 3 is 0.1-1mm, and the length is 0.4-5m.
According to a preferred embodiment of the invention, the inner diameter of the tubes of each reactor 3 increases progressively in the direction of the flow of the reaction mass.
According to the invention, the inner diameter of the tube of the Mth reactor 3 is 1 to 2 times, preferably 1 to 1.5 times, the inner diameter of the tube of the M-1 th reactor 3 in the direction of the flow direction of the reaction mass.
According to the invention, the length of the tubes of the Mth reactor 3 in the direction of flow of the reaction mass is 5 to 1 times, preferably 2.5 to 1 times, the length of the tubes of the Mth reactor 3.
In the invention, the inner diameter and the length of the pipeline of the reactor meet the requirements, so that the material reaction is complete, the preferable range is further met, the material reaction is more thorough, the reaction is smooth, and the condition of equipment stalling or pipeline blockage is avoided.
In the present invention, the pump (2) may be of a type conventional in the art, for example, a chromatographic pump.
According to the invention, the rated output pressure of the pump (2) is 0.3-3MPa, preferably 1-2.5MPa.
According to the invention, the flow rate of the reaction mass in the system is between 0.1 and 10mL/min.
In the invention, the flow rate of the reaction materials in the system meets the range, and the reaction can be stably operated.
Further, the flow rate of the reaction mass in the system is 0.1-8mL/min.
The method and system of the present invention will be further described with reference to fig. 2:
And fully purging the system by nitrogen for 20-40min. Adding dispersion medium, stabilizer (weight average molecular weight 10000-600000 g/mol), initiator and monomer into raw material tank (1), stirring at 5-200r/min for 5-40min. And (3) introducing nitrogen into the raw material tank (1) for bubbling in the stirring process for 10-40min, so that the raw materials are fully dissolved to obtain a first mixture. Wherein the mass concentration of the monomer is 1-10wt% based on the total mass of the first mixture, the content of the stabilizer is 3-10wt% of the mass of the monomer, and the content of the initiator is 0.2-2wt% of the mass of the monomer.
The first chromatographic pump (2-1), the second chromatographic pump (2-2) and the third chromatographic pump (2-3) are sequentially started. Feeding the first mixture into a first reactor (3-1) through a first chromatographic pump (2-1), wherein a first heater (6-1) is arranged outside the first reactor (3-1), the control precision is +/-1 ℃, the first mixture is used for heating the first mixture, and a first polymerization reaction is carried out in the first reactor (3-1) to obtain a second mixture I, the rated output pressure of the first chromatographic pump (2-1) is 0.3-3MPa, the inner diameter of a pipeline of the first reactor (3-1) is 0.1-5mm, the length of the pipeline is 0.2-5m, and the first polymerization reaction conditions comprise the temperature of 45-95 ℃, the time of 60-400min and the material flow rate of 0.1-10mL/min;
Feeding the second mixture I into a second reactor (3-2) through a second chromatographic pump (2-2), wherein a second heater (6-2) is arranged outside the second reactor (3-2), the control precision is +/-1 ℃, the second mixture I is heated and subjected to a second polymerization reaction in the second reactor (3-2) to obtain a second mixture II, the rated output pressure of the second chromatographic pump (2-2) is 0.3-3MPa, the inner diameter of a pipeline of the second reactor (3-2) is 0.1-5mm, the length of the pipeline is 0.2-5m, and the second polymerization reaction conditions comprise the temperature of 45-95 ℃ for 60-400min and the material flow rate of 0.1-10mL/min;
Feeding the second mixture II into a third reactor (3-3) through a third chromatographic pump (2-3), wherein a third heater (6-3) is arranged outside the third reactor (3-3), the control precision is +/-1 ℃, the second mixture II is heated, and a third polymerization reaction is carried out in the third reactor (3-3) to obtain a second mixture III, the rated output pressure of the third chromatographic pump (2-3) is 0.3-3MPa, the inner diameter of a pipeline of the third reactor (3-3) is 0.1-5mm, the length of the pipeline is 0.2-5m, and the third polymerization reaction conditions comprise the temperature of 45-95 ℃, the time of 60-400min and the material flow rate of 0.1-10mL/min;
The inlet of the collecting tank (4) is communicated with the outlet of the third reactor (3-3) and is used for collecting the second mixture III and uniformly mixing the second mixture III at the stirring speed of 5-200 r/min;
The inlet of the separation device (5) is communicated with the outlet of the collection tank (4) and is used for separating the collected second mixture III to obtain a solid-phase material and a liquid-phase material;
The separation device (5) comprises a liquid phase outlet and a solid phase outlet, wherein the inlet of the drying device (7) is communicated with the solid phase outlet of the separation device (5) and is used for drying a solid phase material obtained after the second mixture is separated to obtain acrylate polymer microspheres and a volatilized liquid phase, and the drying conditions comprise a drying temperature of 50-120 ℃, a drying pressure of-0.95-0 MPaG and a drying time of 300-720min;
the inlet of the condenser (8) is communicated with the outlet of the drying device (7) and is used for condensing the volatilized liquid phase in the drying device (7) to obtain condensate;
The recovery tank (9) is communicated with an outlet of the condenser (8) and is used for recovering the condensate;
The recovery tank (9) is communicated with a liquid phase outlet of the separation device (5) and is used for recovering liquid phase materials obtained after the separation of the second mixture III.
The present invention will be described in detail by examples. In the following examples of the present invention,
The morphology of the polymer was observed by means of a scanning electron microscope Hitachi S-4800.
The particle size of the polymer is measured by scanning electron microscope graphics software;
the number average molecular weight of the polymer is determined by gel permeation chromatography;
the weight average molecular weight of the stabilizer is determined by gel permeation chromatography;
The molecular weight distribution index of the polymer was measured by gel permeation chromatography;
the monomer conversion was calculated by the following formula:
Wherein m1 is the mass of the polymer obtained and m0 is the mass of the monomer added.
Number average particle diameter ofWherein n is the number of particles, di is the particle size of the ith particle;
Weight average particle diameter of Wherein n is the number of particles, di is the particle size of the ith particle;
The dispersion coefficient was p=dw/Dn.
The starting materials referred to in the examples and comparative examples are commercially available products which are conventional in the art.
Example 1
The system was purged thoroughly with nitrogen for 20min. The dispersion medium ethanol 888.5g, the stabilizer polyvinylpyrrolidone 10g (weight average molecular weight is 100000 g/mol), the initiator azodiisobutyronitrile 1.5g and the monomer methyl methacrylate 100g are added into a raw material tank (1), and stirring is started, the rotating speed is 150r/min, and the time is 20min. And (3) introducing nitrogen into the raw material tank (1) for bubbling in the stirring process for 30min, so that the raw materials are fully dissolved to obtain a first mixture. Wherein the mass concentration of the methyl methacrylate is 10wt%, the content of the polyvinylpyrrolidone is 10wt% of the mass of the methyl methacrylate, and the content of the azobisisobutyronitrile is 1.5wt% of the mass of the methyl methacrylate, based on the total mass of the first mixture.
The first chromatographic pump (2-1), the second chromatographic pump (2-2) and the third chromatographic pump (2-3) are sequentially started. Feeding the first mixture into a first reactor (3-1) through a first chromatographic pump (2-1), wherein a first heater (6-1) (water bath) is arranged outside the first reactor (3-1), the precision is +/-1 ℃, the first heater is used for heating the first mixture, and a first polymerization reaction is carried out in the first reactor (3-1) to obtain a second mixture I, the methyl methacrylate conversion rate is 36.7%, the rated output pressure of the first chromatographic pump (2-1) is 2.5MPa, the inner diameter of a pipeline of the first reactor (3-1) is 0.1mm, the length is 5m, and the first polymerization reaction conditions comprise a temperature of 75 ℃, the time is 392.5min and the material flow rate is 0.1mL/min;
Feeding the second mixture I into a second reactor (3-2) through a second chromatographic pump (2-2), wherein a second heater (6-2) (water bath) is arranged outside the second reactor (3-2), the control precision is +/-1 ℃, the second mixture I is heated, and a second polymerization reaction is carried out in the second reactor (3-2) to obtain a second mixture II, wherein the methyl methacrylate conversion rate is 66%, the rated output pressure of the second chromatographic pump (2-2) is 2.5MPa, the inner diameter of a pipeline of the second reactor (3-2) is 0.1mm, the length is 4m, and the second polymerization reaction conditions comprise a temperature of 75 ℃, the time is 314min and the material flow rate is 0.1mL/min;
Feeding the second mixture II into a third reactor (3-3) through a third chromatographic pump (2-3), wherein a third heater (6-3) (water bath) is arranged outside the third reactor (3-3), the control precision is +/-1 ℃, the second mixture II is heated, and a third polymerization reaction is carried out in the third reactor (3-3) to obtain a second mixture III, the conversion rate of methyl methacrylate is 88%, the rated output pressure of the third chromatographic pump (2-3) is 2.5MPa, the inner diameter of a pipeline of the third reactor (3-3) is 0.1mm, the length is 3m, and the third polymerization reaction conditions comprise the temperature of 80 ℃, the time of 235.5min and the material flow rate of 0.1mL/min;
the inlet of the collecting tank (4) is communicated with the outlet of the third reactor (3-3) and is used for collecting the second mixture III and uniformly mixing the second mixture III at the rotating speed of 150 r/min;
The inlet of the separation device (5) (a centrifugal machine) is communicated with the outlet of the collection tank (4) and is used for separating the collected second mixture III to obtain a solid-phase material and a liquid-phase material, wherein the rotating speed range of the centrifugal machine is 6000r/min;
The separation device (5) comprises a liquid phase outlet and a solid phase outlet, wherein the inlet of the drying device (7) is communicated with the solid phase outlet of the separation device (5) and is used for drying a solid phase material obtained after the second mixture is separated to obtain acrylate polymer microspheres A1 and a volatilized liquid phase, and the drying condition comprises that the drying temperature is 80 ℃, the drying pressure is-0.8 MPaG and the drying time is 720min;
the inlet of the condenser (8) is communicated with the outlet of the drying device (7) and is used for condensing the volatilized liquid phase in the drying device (7) to obtain condensate;
The recovery tank (9) is communicated with an outlet of the condenser (8) and is used for recovering the condensate;
The recovery tank (9) is communicated with a liquid phase outlet of the separation device (5) and is used for recovering liquid phase materials obtained after the separation of the second mixture III.
The morphology of the polymer microsphere A1 product is shown in FIG. 1. It can be seen from FIG. 1 that the resulting polymer microsphere A1 is a monodisperse microsphere with a smooth surface. The number average molecular weight of the polymer microsphere A1 was 40,000g/mol and the molecular weight distribution was 1.62. The weight average particle diameter was 1.265. Mu.m, the number average particle diameter was 1.25. Mu.m, and the dispersion coefficient was 1.012.
Example 2
According to the method of example 1, except that the concentration of methyl methacrylate by mass based on the total mass of the first mixture was 10% by weight, the amount of polyvinylpyrrolidone used was 8% by weight based on the mass of methyl methacrylate used, and the amount of azobisisobutyronitrile was 2% by weight based on the mass of methyl methacrylate;
the inner diameter of a pipeline of the first reactor (3-1) is 0.5mm, the length is 5m, the material flow rate is 5mL/min, and the methyl methacrylate conversion rate is 36.3%;
the inner diameter of a pipeline of the second reactor (3-2) is 0.5mm, the length is 4m, the material flow rate is 5mL/min, and the methyl methacrylate conversion rate is 65.3%;
the inner diameter of a pipeline of the third reactor (3-3) is 0.5mm, the length is 3m, the material flow rate is 5mL/min, and the methyl methacrylate conversion rate is 87%;
the rotational speed range of the centrifuge is 5000r/min.
Finally, polymer microsphere A2 is obtained, the number average molecular weight of the polymer microsphere A2 is 37,000g/mol, and the molecular weight distribution is 1.73. The weight average particle diameter was 1.102. Mu.m, the number average particle diameter was 1.014. Mu.m, and the dispersion coefficient was 1.087.
Example 3
The procedure of example 2 was followed except that the inner diameter of the tube of the first reactor (3-1) was 1mm and the conversion of methyl methacrylate was 65.7%;
The inner diameter of a pipeline of the second reactor (3-2) is 1mm, the length is 1m, and the conversion rate of methyl methacrylate is 78.9%;
The inner diameter of the pipeline of the third reactor (3-3) is 1mm, the length is 1m, and the conversion rate of methyl methacrylate is 92%.
Finally, polymer microsphere A3 is obtained, the number average molecular weight of the polymer microsphere A3 is 35,000g/mol, and the molecular weight distribution is 1.76. The weight average particle diameter was 1.002. Mu.m, the number average particle diameter was 0.98. Mu.m, and the dispersion coefficient was 1.022.
Example 4
According to the method of example 1, except that the mass concentration of methyl methacrylate based on the total mass of the first mixture was 5% by weight, the amount of polyvinylpyrrolidone (weight average molecular weight: 50000 g/mol) was 6% by weight based on the mass of methyl methacrylate used, the initiator was azobisisoheptonitrile, and the amount was 2% by weight based on the mass of methyl methacrylate;
The inner diameter of the pipeline of the first reactor (3-1) is 0.5mm, and the length is 5m;
the first polymerization reaction condition comprises that the temperature is 50 ℃, the material flow rate is 5mL/min, and the methyl methacrylate conversion rate is 71.3%;
The second polymerization reaction condition comprises that the temperature is 55 ℃, the material flow rate is 5mL/min, and the methyl methacrylate conversion rate is 85.6%;
The third polymerization reaction condition comprises that the temperature is 60 ℃, the material flow rate is 5mL/min, and the methyl methacrylate conversion rate is 86%;
the rotational speed of the centrifuge is 8000r/min.
Finally, polymer microsphere A4 is obtained, the number average molecular weight of the polymer microsphere A4 is 34,000g/mol, and the molecular weight distribution is 1.78. The weight average particle diameter was 0.956. Mu.m, the number average particle diameter was 0.933. Mu.m, and the dispersion coefficient was 1.025.
Example 5
The procedure of example 1 was followed except that the dispersion medium was replaced with propanol and the polyvinylpyrrolidone had a weight average molecular weight of 10000g/mol and the initiator was replaced with dibenzoyl peroxide.
The mass concentration of methyl methacrylate is 8wt% based on the total mass of the first mixture, the amount of polyvinylpyrrolidone is 8wt% based on the mass of methyl methacrylate used, and the amount of initiator is 2wt% based on the mass of methyl methacrylate.
The inner diameter of a pipeline of the first reactor (3-1) is 4mm, the length is 0.4m, the material flow rate is 10mL/min, and the methyl methacrylate conversion rate is 38.7%;
The inner diameter of a pipeline of the second reactor (3-2) is 4mm, the length is 0.3m, the material flow rate is 10mL/min, and the methyl methacrylate conversion rate is 67.7%;
the inner diameter of the pipeline of the third reactor (3-3) is 4mm, the length is 0.2m, the material flow rate is 10mL/min, and the conversion rate of methyl methacrylate is 87%.
The first polymerization conditions include a temperature of 80 ℃;
The second polymerization conditions include a temperature of 85 ℃;
The third polymerization conditions include a temperature of 90 ℃.
Finally, the polymer microsphere A5 is obtained, the number average molecular weight of the polymer microsphere A5 is 32,000g/mol, and the molecular weight distribution is 1.88. The weight average particle diameter was 0.938. Mu.m, the number average particle diameter was 0.905. Mu.m, and the dispersion coefficient was 1.036.
Example 6
The procedure of example 1 was followed, except that the flow rate was 10.5mL/min;
the first reactor (3-1) had a methyl methacrylate conversion of 3.67%;
The second reactor (3-2) had a methyl methacrylate conversion of 6.6%;
the methyl methacrylate conversion of the third reactor (3-3) was 8.5%;
the rotational speed range of the centrifuge is 5000r/min.
Finally, polymer microsphere A6 is obtained, the number average molecular weight of the polymer microsphere A6 is 45000g/mol, and the molecular weight distribution is 1.61. The weight average particle diameter was 0.512. Mu.m, the number average particle diameter was 0.507. Mu.m, and the dispersion coefficient was 1.01.
Example 7
The procedure of example 1 was followed except that bubbling was not performed.
Finally, polymer microsphere A7 is obtained, the number average molecular weight of the polymer microsphere A7 is 42000g/mol, and the molecular weight distribution is 1.63. The weight average particle diameter was 1.21. Mu.m, the number average particle diameter was 1.194. Mu.m, and the dispersion coefficient was 1.013.
Example 8
The procedure of example 1 was followed, except that:
The material flow rate of the first reactor (3-1) is 0.5mL/min, and the methyl methacrylate conversion rate is 7.17%;
The flow rate of the material in the second reactor (3-2) is 0.2mL/min, and the conversion rate of methyl methacrylate is 21.5%;
the material flow rate of the third reactor (3-3) is 0.1mL/min, and the methyl methacrylate conversion rate is 43%;
Finally, the polymer microsphere A8 is obtained, the number average molecular weight of the polymer microsphere A8 is 38000g/mol, and the molecular weight distribution is 1.64. The weight average particle diameter was 0.871. Mu.m, the number average particle diameter was 0.835. Mu.m, and the dispersion coefficient was 1.043.
Comparative example 1
The same and equal amount of raw materials as in example 1 were added to a kettle-type vessel, stirring was started at a stirring speed of 200r/min, and the added raw materials were thoroughly mixed and dissolved. And (3) introducing nitrogen into the kettle-type container during stirring to bubble the liquid system for 30min. The reaction was carried out at 75℃for 10h. Polymer D1 was isolated, at which point the conversion of methyl methacrylate was 85%. Polymer D1 had a number average molecular weight of 25000g/mol, a molecular weight distribution of 2.8, a weight average particle diameter of 1.41. Mu.m, a number average particle diameter of 1.12. Mu.m, and a dispersion coefficient of 1.259.
Comparative example 2
The procedure of example 1 was followed except that the dispersion medium was replaced with an equal amount of ethyl acetate. The pipe was clogged, and a spherical polymer dispersion was not obtained.
Comparative example 3
According to the method of example 1, except that the inner diameter of the pipe of the first reactor (3-1) was 0.1mm, the length was 0.5m, the flow rate of the material was 2mL/min, and the conversion of methyl methacrylate was 0.26%;
The inner diameter of a pipeline of the second reactor (3-2) is 0.1mm, the length is 1m, the material flow rate is 0.5mL/min, and the methyl methacrylate conversion rate is 2.09%;
The inner diameter of the pipeline of the third reactor (3-3) is 0.1mm, the length is 8m, the material flow rate is 0.1mL/min, the operation of the third pump is stopped by the overpressure, and the reaction flow cannot be carried out stably.
Comparative example 4
The procedure of example 1 was followed except that there was only one chromatographic pump, one reactor of 0.1mm diameter and 5m length and one heater, which was in direct communication with the collection tank. The conversion of methyl methacrylate was 35%, and polymer microsphere D4 was obtained with a number average molecular weight of 45000g/mol and a molecular weight distribution of 1.59. The weight average particle diameter was 0.48. Mu.m, the number average particle diameter was 0.475. Mu.m, and the dispersion coefficient was 1.011.
TABLE 1
In order to further illustrate that the polymer microspheres prepared by the invention can be well applied to polyethylene films, the polymer microspheres prepared by the examples and the comparative examples are added to the polyethylene films without adding any additional additives. The haze effect of the resulting films was tested according to GB/T2410-2008 and the results are shown in Table 2.
TABLE 2
* No additive is added
From the contents of Table 2, it can be seen that the polymer microspheres prepared in examples 1 to 8 of the present invention can provide a haze of at least 87% of the polyethylene film when applied to polyethylene.
Further satisfying preferred embodiments 1 to 4 of the present invention, it is possible to make the haze of the polyethylene film not less than 94%.
Wherein, under the condition of not adding any additive, the polyethylene film added with calcium carbonate or silicon dioxide has obvious crystal points (fish eyes) and under the condition of not adding any additive, the polyethylene film added with the microsphere of the invention has no fish eyes.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (12)

1. A method for preparing acrylate polymer microspheres, comprising the steps of:
s1, uniformly mixing a dispersion medium, a stabilizer, an initiator and a monomer to obtain a first mixture;
s2, carrying out step-by-step polymerization on the first mixture to obtain a second mixture;
s3, separating the second mixture to obtain acrylate polymer microspheres;
the dispersion medium is not compatible with the monomer;
wherein the step polymerization is N-step polymerization, and N is more than or equal to 2;
the monomer conversion rate of the N step is 1-5 times of that of the N-1 step.
2. The production method according to claim 1, wherein the monomer conversion in the nth step is 1 to 2.5 times the monomer conversion in the N-1 th step;
preferably, in step S1, the mixing includes stirring and nitrogen bubbling;
Preferably, the stirring speed of the stirring is 5-200r/min, preferably 50-200r/min, and the stirring time is 5-40min, preferably 10-40min;
Preferably, the nitrogen bubbling time is 10-40min, preferably 10-30min.
3. The production method according to claim 1 or 2, wherein in step S2, the step polymerization comprises heating the first mixture through a plurality of temperature zones;
Preferably, the heating conditions of each of the plurality of temperature zones independently comprise a temperature of 45-95 ℃ for 60-400min;
preferably, the first mixture is heated through 3-5 temperature zones.
4. The method according to any one of claims 1 to 3, wherein the method further comprises drying the separated acrylic acid ester polymer microspheres;
Preferably, the drying conditions include a drying temperature of 50-120 ℃, a drying pressure of-0.95 to 0MPaG, and a drying time of 300-720min.
5. The production method according to any one of claims 1 to 4, wherein the dispersion medium is selected from at least one of methanol, ethanol, and propanol;
Preferably, the weight average molecular weight of the stabilizer is from 10,000 to 600,000g/mol, preferably from 10,000 to 300,000g/mol;
preferably, the stabilizer is selected from polyvinylpyrrolidone and/or polyacrylic acid;
Preferably, the initiator is selected from azo-type initiators and/or peroxy-type initiators;
Preferably, the initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptonitrile and dibenzoyl peroxide;
preferably, the monomer is selected from methyl methacrylate and/or methyl acrylate.
6. The preparation method according to any one of claims 1 to 5, wherein the concentration of the monomer in the first mixture is 1 to 10wt%, preferably 2 to 10wt%;
preferably, the stabilizer is used in an amount of 3 to 10wt%, preferably 4 to 10wt% based on the mass of the monomer;
preferably, the initiator is used in an amount of 0.2 to 2wt%, preferably 0.5 to 2wt% based on the mass of the monomer.
7. An acrylic polymer microsphere prepared by the preparation method of any one of claims 1 to 6.
8. The polymeric microspheres according to claim 7, wherein the acrylate polymeric microspheres have a dispersion coefficient of 1.008-1.1, preferably 1.008-1.09;
preferably, the number average particle size of the acrylate polymer microspheres is 0.5-1.4 μm, preferably 0.8-1.4 μm;
Preferably, the weight average particle size of the acrylate polymer microspheres is 0.5-1.5 μm, preferably 0.8-1.5 μm;
Preferably, the acrylate polymer microspheres have a number average molecular weight of 15,000 to 50,000g/mol, preferably 20,000 to 40,000g/mol;
Preferably, the molecular weight distribution index of the acrylate polymer microspheres is 1.5-2.2, preferably 1.5-2.
9. Use of the acrylate polymer microspheres of claim 7 or 8 as a modifier in polyolefin films.
10. A system for preparing the acrylic polymer microsphere according to claim 7 or 8, characterized in that the system comprises a raw material tank 1, a reactor 3, a collection tank 4, a separation device 5 and a heater 6;
the outlet of the raw material tank 1 is communicated with the inlet of the reactor 3 and is used for mixing raw materials to obtain a first mixture;
the inlet of the reactor 3 is communicated with the outlet of the raw material tank 1, and a heater 6 is arranged outside the reactor 3 and is used for carrying out polymerization reaction on the first mixture to obtain a second mixture;
The inlet of the collection tank 4 is communicated with the outlet of the reactor 3 for collecting the second mixture;
The inlet of the separation device 5 is communicated with the outlet of the collection tank 4 and is used for separating the collected second mixture to obtain acrylate polymer microspheres;
Wherein the number of the reactors 3 is M, the number of the heaters 6 is P, M is more than or equal to 2, and P is more than or equal to 2;
the length of the tubes of each reactor 3 decreases in the direction of flow of the reaction mass.
11. The system of claim 10, wherein the system further comprises a pump 2, a drying device 7, a condenser 8, and a recovery tank 9;
Said pump 2 is arranged before said reactor 3 for pumping the first mixture into the reactor 3;
the separation device 5 comprises a liquid phase outlet and a solid phase outlet;
the inlet of the drying device 7 is communicated with the solid phase outlet of the separation device 5 and is used for drying the solid phase material obtained after the second mixture is separated;
the inlet of the condenser 8 is communicated with the outlet of the drying device 7 and is used for condensing the liquid phase in the drying device 7 to obtain condensate;
The recovery tank 9 is communicated with the outlet of the condenser 8 and is used for recovering the condensate;
The recovery tank 9 is communicated with a liquid phase outlet of the separation device 5 and is used for recovering liquid phase materials obtained after the second mixture is separated.
12. The system according to claim 10 or 11, wherein the reactor 3 is a tubular microreactor;
preferably, the reactor 3 has a pipe inner diameter of 0.1-5mm, preferably 0.1-1mm, and a length of 0.2-5m, preferably 0.4-5m;
Preferably, the inner diameter of the tube of each reactor 3 increases in the direction of the flow of the reaction mass;
Preferably, the inner diameter of the pipe of the Mth reactor 3 is 1 to 2 times, preferably 1 to 1.5 times, the inner diameter of the pipe of the M-1 st reactor 3 in the direction of the flow direction of the reaction mass;
preferably, the length of the pipe of the M-1 th reactor 3 is 1 to 2 times, preferably 1 to 1.5 times, the length of the pipe of the M-1 th reactor 3 in the flow direction of the reaction mass;
Preferably, the rated output pressure of the pump 2 is 0.3-3MPa, preferably 1-2.5MPa;
Preferably, the flow rate of the reaction mass in the system is from 0.1 to 10mL/min, preferably from 0.1 to 8mL/min.
CN202310623413.4A 2023-05-30 2023-05-30 Acrylate polymer microspheres, preparation method and application thereof, and system for preparing acrylate polymer microspheres Pending CN119060227A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10310603A (en) * 1997-05-09 1998-11-24 Maruzen Petrochem Co Ltd Method for producing fine spherical copolymer with narrow particle size distribution
CN101054427A (en) * 2007-06-21 2007-10-17 北京舟鼎国生物技术有限责任公司 Method of synthesizing monodisperse micron-level poly(methyl methacrylate) micro-sphere
CN101928368A (en) * 2009-06-19 2010-12-29 北京化工大学 Polymerization method and polymerization device for polyacrylonitrile spinning dope
CN105001367A (en) * 2015-07-10 2015-10-28 中科院广州化学有限公司南雄材料生产基地 Crosslinked monodispersed polymer functional microspheres and preparation method thereof
CN110054727A (en) * 2019-04-25 2019-07-26 西安万德能源化学股份有限公司 A kind of preparation method and device of polyacrylamide nano microballoon

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10310603A (en) * 1997-05-09 1998-11-24 Maruzen Petrochem Co Ltd Method for producing fine spherical copolymer with narrow particle size distribution
CN101054427A (en) * 2007-06-21 2007-10-17 北京舟鼎国生物技术有限责任公司 Method of synthesizing monodisperse micron-level poly(methyl methacrylate) micro-sphere
CN101928368A (en) * 2009-06-19 2010-12-29 北京化工大学 Polymerization method and polymerization device for polyacrylonitrile spinning dope
CN105001367A (en) * 2015-07-10 2015-10-28 中科院广州化学有限公司南雄材料生产基地 Crosslinked monodispersed polymer functional microspheres and preparation method thereof
CN110054727A (en) * 2019-04-25 2019-07-26 西安万德能源化学股份有限公司 A kind of preparation method and device of polyacrylamide nano microballoon

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