CN111100240B - System and method for preparing maleic anhydride copolymer microspheres - Google Patents

System and method for preparing maleic anhydride copolymer microspheres Download PDF

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CN111100240B
CN111100240B CN201811249795.4A CN201811249795A CN111100240B CN 111100240 B CN111100240 B CN 111100240B CN 201811249795 A CN201811249795 A CN 201811249795A CN 111100240 B CN111100240 B CN 111100240B
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alcohol
liquid
separation
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washing
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宋文波
袁浩
胡慧杰
刘振杰
毕福勇
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene

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Abstract

The invention relates to the field of continuous production of maleic anhydride copolymer microspheres, and discloses a system and a method for preparing maleic anhydride copolymer microspheres. The system comprises: a copolymerization unit, a washing unit, a drying unit and a solvent recovery unit which are communicated in sequence; the copolymerization unit is used for carrying out copolymerization reaction on a comonomer, and the obtained polymer mother liquor containing the maleic anhydride copolymer microspheres is continuously subjected to first separation to obtain a separated solid-containing phase and a separation liquid; the washing unit is used for carrying out alcohol washing and continuous second separation on the separated solid-containing phase to obtain a slag phase and a washing clear liquid; the drying unit is used for drying the slag phase to obtain maleic anhydride copolymer microspheres; the solvent recovery unit is used for removing impurities from the separation liquid and the washing clear liquid and returning the obtained products to the copolymerization unit and the washing unit respectively; the system is used for realizing continuous production of the maleic anhydride copolymer microspheres. Can provide continuous production, washing purification and solid-liquid separation of copolymer microspheres.

Description

System and method for preparing maleic anhydride copolymer microspheres
Technical Field
The invention relates to the field of continuous production of maleic anhydride copolymer microspheres, in particular to a system and a method for preparing maleic anhydride copolymer microspheres.
Background
At present, researches on preparation and application of polymer microspheres are a hotspot in the field of functional polymer materials, and the polymer microspheres from nano-scale to micron-scale have the special properties of large specific surface area, strong adsorbability, large condensation effect and strong surface reaction capability, and can be widely applied to many high and new technical fields.
The self-stabilizing precipitation polymerization technique has the following characteristics: monodisperse polymer microspheres can be prepared without adding any stabilizer in the reaction process, the concentration of the reaction system is higher, a relatively stable milky dispersion system can be formed after polymerization, and the obtained polymer has uniform appearance and size.
CN 101235117A discloses a styrene/maleic anhydride high molecular copolymer microsphere with particle size of about 90-1700 nm and uniform particle size distribution prepared by a self-stabilization precipitation polymerization method. The copolymer microspheres prepared by the method have controllable morphology and particle size.
CN 101338008A discloses a method for preparing crosslinked styrene/maleic anhydride copolymer microspheres in a styrene/maleic anhydride copolymer system by adjusting the addition amount of a crosslinking agent.
Chen Cheng and He Jian, etc. in the research on the preparation of crosslinked (alpha-methylstyrene/maleic anhydride) copolymer particles by a self-stabilizing precipitation polymerization method (Beijing university of chemical industry, Nature's edition, 2014, 41 (5): 70-75), alpha-methylstyrene is used as a polymerization monomer, and crosslinked (alpha-methylstyrene/maleic anhydride) copolymer microspheres are prepared by using different crosslinking agents.
The existing polymer microspheres must be subjected to washing purification and solid-liquid separation of ultrafine particles in industrial production, and the existing common method is a three-leg centrifuge or a plate-and-frame filter, so that the sudden empty operation exists, and the process continuity and safety need to be improved.
Disclosure of Invention
The invention aims to overcome the problems of difficult washing purification and solid-liquid separation of ultrafine particles in industrial production of maleic anhydride copolymer microspheres and provide a system and a method for preparing the maleic anhydride copolymer microspheres.
In order to achieve the above object, a first aspect of the present invention provides a system for preparing maleic anhydride copolymer microspheres, the system comprising:
a copolymerization unit, a washing unit, a drying unit and a solvent recovery unit which are communicated in sequence, wherein,
the copolymerization unit is used for carrying out copolymerization reaction on a comonomer, and the obtained polymer mother liquor containing the maleic anhydride copolymer microspheres is continuously subjected to first separation to obtain a separated solid-containing phase and a separated liquid;
the washing unit is used for carrying out at least one time of alcohol washing and continuous second separation on the separated solid-containing phase to obtain a slag phase and a washing clear liquid;
the drying unit is used for drying the slag phase to obtain the maleic anhydride copolymer microspheres;
the solvent recovery unit is used for removing impurities from the separation liquid and the washing clear liquid, and returning the recovered solvent and the recovered alcohol obtained by separation to the copolymerization unit and the washing unit respectively;
the system is used for realizing continuous production of the maleic anhydride copolymer microspheres.
In a second aspect, the present invention provides a method for preparing maleic anhydride copolymer microspheres using the system of the present invention, comprising:
(1) carrying out copolymerization reaction on maleic anhydride, a monomer B shown in a formula (I), an initiator, a cross-linking agent and a reaction solvent in a copolymerization unit of a system to obtain a polymer mother liquor containing maleic anhydride copolymer microspheres;
(2) continuously carrying out first separation on the polymer mother liquor to obtain a separated solid-containing phase and a separation liquid;
(3) introducing the separated solid-containing phase into a washing unit of a system, and performing at least one alcohol washing and second separation to obtain a slag phase and a washing clear liquid;
(4) sending the slag phase into a drying unit of a system for drying to obtain maleic anhydride copolymer microspheres;
(5) introducing the separation liquid and the clear liquid into a solvent recovery unit of the system, and respectively returning the recovered solvent and the recovered alcohol obtained by recovery to the steps (1) and (3);
Figure BDA0001841384290000031
in the formula (I), R is H or methyl.
Through the technical scheme, the invention provides a system and a method for continuously preparing the maleic anhydride copolymer with the cross-linking and microsphere structures. The technological process of the method can realize continuous solid-liquid centrifugal separation of the superfine copolymerization product microspheres and the solvent, and the used reaction solvent and the washed alcohol solvent can be recycled. The method provided by the invention can save the separation process which is manually operated among the units of the system in the prior art, effectively avoid the sudden empty operation of the solvent, realize the continuous washing and separation process of the prepared copolymer microspheres, effectively stabilize the separation effect and avoid the frequent start-up and shutdown operations of a centrifugal machine. The average particle size of the obtained microspheres can be 600-2000 nm.
Drawings
FIG. 1 is an infrared spectrum of a maleic anhydride copolymer microsphere obtained in example 1;
FIG. 2 is a scanning electron micrograph of maleic anhydride copolymer microspheres obtained in example 1;
FIG. 3 is a schematic flow chart of a system for preparing maleic anhydride copolymer microspheres according to the present invention;
FIG. 4 is a schematic flow chart of a method for preparing maleic anhydride copolymer microspheres according to the present invention.
Description of the reference numerals
V-13 reaction solvent storage tank R-11 reaction liquid mixing kettle R-12 copolymerization reactor
R-22 washing kettle V-27 alcohol storage tank V-25 separation liquid storage tank
V-26 clear liquid storage tank S-21 first disk centrifuge S-22 second disk centrifuge
A-21 first online turbidimeter A-22 second online turbidimeter G-41 dryer
E-41 condenser V-41 drying condensate tank T-51 alcohol rectifying tower
E-51 alcohol heat exchanger E-52 raffinate reboiler V-51 alcohol condensate tank
T-52 reaction solvent rectifying column E-53 solvent heat exchanger E-54 waste liquid reboiler
V-53 solvent condensate tank V-55 feed tank
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a system for preparing maleic anhydride copolymer microspheres, as shown in fig. 3, the system comprising:
a copolymerization unit, a washing unit, a drying unit and a solvent recovery unit which are communicated in sequence, wherein,
the copolymerization unit is used for carrying out copolymerization reaction on a comonomer, and the obtained polymer mother liquor containing the maleic anhydride copolymer microspheres is continuously subjected to first separation to obtain a separated solid-containing phase and a separated liquid;
the washing unit is used for carrying out at least one time of alcohol washing and continuous second separation on the separated solid-containing phase to obtain a slag phase and a washing clear liquid;
the drying unit is used for drying the slag phase to obtain the maleic anhydride copolymer microspheres;
the solvent recovery unit is used for removing impurities from the separation liquid and the washing clear liquid, and returning the recovered solvent and the recovered alcohol obtained by separation to the copolymerization unit and the washing unit respectively;
the system is used for realizing continuous production of the maleic anhydride copolymer microspheres.
According to the present invention, preferably, the copolymerization unit includes: a reaction solvent storage tank V-13, a reaction liquid mixing kettle R-11, a copolymerization reactor R-12, a first disk centrifuge S-21, a first online turbidity meter A-21 and a separation liquid storage tank V-25; wherein the reaction solvent storage tank V-13 is used for storing a reaction solvent; the reaction liquid mixing kettle R-11 is used for mixing the reaction solvent and the reaction raw materials into reaction liquid; the copolymerization reactor R-12 is used for continuously carrying out the copolymerization reaction on the reaction liquid; and continuously flowing the obtained polymer mother liquor into a first disc centrifuge S-21 for continuous first separation, and introducing the obtained separation liquid into a copolymerization reactor R-12 and a separation liquid storage tank V-25 after passing through a first online turbidity meter A-21.
In the invention, the copolymerization reactor can be selected from a tubular reactor, a groove type baffled reactor or two full mixing kettle type reactors connected in parallel.
According to the invention, a first online turbidimeter a-21 is used to monitor the turbidity of the separated liquid obtained by the separation in the first disc centrifuge S-21, in order to control the flow direction of the separated liquid. Preferably, valves are respectively arranged between the first online turbidity meter A-21 and the copolymerization reactor R-12 and between the first online turbidity meter A-21 and the separation liquid storage tank V-25, and are used for introducing the separation liquid into the separation liquid storage tank V-25 when the turbidity of the separation liquid reaches the standard and introducing the separation liquid into the copolymerization reactor R-12 when the turbidity of the separation liquid does not reach the standard. By standard is meant that the turbidity of the separation solution is below a predetermined value, such as 0.1 wt% (turbidity value corresponding to a turbid solution formed by 0.1g of polymeric microspheres dispersed in 100g of solvent).
In the context of the present invention, turbidity is the degree of turbidity of a mixture which appears macroscopically in the homogeneously mixed mixture as a result of absorption, scattering or refraction of light by suspended particles, the value of which is determined using a turbidimeter. The turbidity value is related to the nature and concentration of the particles, and thus can be used as an indicator of the concentration of particles for the same type of particles, and is characterized here by the concentration of particles (mass in g of particles in 100g of solvent, in% by weight).
In the system provided by the invention, the high-concentration reaction liquid discharged from the copolymerization reactor R-12 can avoid the separation process of manual operation in the prior art, and the first disk centrifuge S-21 and the first online turbidity meter A-21 which are arranged between the copolymerization reactor R-12 and the washing kettle R-22 are matched for use, so that the continuous first separation of the reaction liquid can be realized, the exposure of the reaction liquid is reduced, and the violent operation is avoided.
In this context, the high concentration is relative to: the existing disk centrifuge is generally applied to the separation of low-concentration turbid liquid with solid content less than 5 weight percent.
According to the invention, the washing unit comprises: an alcohol tank V-27, a clear liquid tank V-26 and at least one set of washing devices, each set of washing devices comprising: a washing kettle R-22, a second disc centrifuge S-22 and a second online turbidimeter A-22; wherein the alcohol storage tank V-27 is used for storing alcohol solvent; the washing kettle R-22 is used for continuously carrying out alcohol washing on the separated solid-containing phase and the alcohol solvent to obtain dispersed slurry; and continuously introducing the dispersed slurry into a second disc centrifuge S-22 for continuous second separation, and introducing the obtained washing clear liquid into a washing kettle R-22 or a clear liquid storage tank V-26 after passing through a second online turbidity meter A-22.
According to the invention, valves are respectively arranged between the second online turbidity meter A-22 and the washing kettle R-22, and between the second online turbidity meter A-22 and the clear liquid storage tank V-26, and are used for introducing the washing clear liquid into the clear liquid storage tank V-26 when the turbidity of the washing clear liquid reaches the standard, and introducing the washing clear liquid into the washing kettle R-22 when the turbidity does not reach the standard.
In the present invention, the washing unit may include a plurality of groups of the washing devices, for example, the residue phase separated by the second disk centrifuge S-22 in the previous group is continuously sent to the next group of the washing devices, alcohol washing is performed with the alcohol solvent, the same continuous second separation as above is performed, and finally the residue phase satisfying the alcohol washing effect enters the drying unit of the system provided by the present invention.
In the invention, the high-concentration dispersed slurry discharged from the washing kettle R-22 can avoid the separation process of manual operation in the prior art, and the continuous second separation of the dispersed slurry can be realized by using the second disk centrifuge S-22 arranged between the washing kettle R-22 and the dryer G-41 and the matching use of the second online turbidity meter A-22, so that the exposure of the dispersed slurry is reduced, and the operation of sudden emptying is avoided.
According to the invention, the drying unit comprises: a dryer G-41, a condenser E-41 and a drying condensate tank V-41; the drier G-41 is used for drying the slag phase to obtain the maleic anhydride copolymer microspheres; the condenser E-41 is communicated with the drying condensate tank V-41 and is used for condensing the gaseous solvent discharged by the condensing dryer G-41 into liquid and introducing the liquid into the drying condensate tank V-41; the drying condensate tank V-41 is communicated with an alcohol storage tank V-27.
In the present invention, the dryer G-41 may be, for example, a microwave dryer, a microwave vacuum dryer, or a rake vacuum dryer.
To facilitate drying, the drying gel tank V-41 may also be connected to a vacuum device.
According to the invention, the solvent recovery unit comprises: an alcohol solvent recovery device and a reaction solvent recovery device; the alcohol solvent recovery device is communicated with the clear liquid storage tank V-26, the alcohol storage tank V-27 and the reaction solvent recovery device, and is used for recovering the alcohol solvent in the clear liquid from the clear liquid storage tank V-26, returning the alcohol solvent to the alcohol storage tank V-27, and simultaneously introducing residual liquid of the clear liquid into the reaction solvent recovery device; and the reaction solvent recovery device is communicated with the separation liquid storage tank V-25 and the reaction solvent storage tank V-13, is used for recovering the separation liquid from the separation liquid storage tank V-25 and the reaction solvent in the residual liquid, and returns to the reaction solvent storage tank V-13.
According to the present invention, the alcohol solvent recovery apparatus comprises: an alcohol rectifying tower T-51, an alcohol heat exchanger E-51, an alcohol condensate tank V-51 and a raffinate reboiler E-52; wherein the alcohol rectifying tower T-51 is used for distilling clear liquid from the clear liquid storage tank V-26, and alcohol vapor discharged from the top of the alcohol rectifying tower T-51 sequentially passes through the alcohol heat exchanger E-51 and the alcohol condensate tank V-51 to obtain recovered alcohol; one part of the recovered alcohol is returned to the alcohol rectifying tower T-51, and the other part of the recovered alcohol is returned to the alcohol storage tank V-27 to be reused in the washing unit; and discharging raffinate from the bottom of the alcohol rectifying tower T-51, wherein one part of the raffinate passes through a raffinate reboiler E-52 and then returns to the alcohol rectifying tower T-51, and the other part of the raffinate is introduced into the reaction solvent recovery device.
In the present invention, the alcohol rectification column T-51 may be a normal pressure or micro positive pressure column for refining the alcohol in the clear liquid. A metering pump can be arranged between the alcohol condensate tank V-51 and the alcohol rectifying tower T-51.
According to the present invention, the reaction solvent recovery apparatus comprises: a feeding tank V-55, a reaction solvent rectifying tower T-52, a solvent heat exchanger E-53, a solvent condensate tank V-53 and a waste liquid reboiler E-54; wherein the feed tank V-55 is communicated with the bottom of the alcohol rectifying tower T-51 and the separated liquid storage tank V-25 and is used for mixing the residual liquid and the separated liquid from the separated liquid storage tank V-25 to be used as feed; the reaction solvent rectifying tower T-52 is used for fractionating the feed, and the solvent vapor discharged from the top of the reaction solvent rectifying tower T-52 passes through the solvent heat exchanger E-53 and the solvent condensate tank V-53 in sequence to obtain a recovered solvent; one part of the recovered solvent is returned to the reaction solvent rectifying tower T-52, and the other part of the recovered solvent is returned to the reaction solvent storage tank V-13 to be reused in the copolymerization unit; and discharging waste liquid from the bottom of the reaction solvent rectifying tower T-52, wherein one part of the waste liquid returns to the reaction solvent rectifying tower T-52 after passing through a waste liquid reboiler E-54, and the other part of the waste liquid is discharged.
In the present invention, the reaction solvent rectification column T-52 is used to refine the reaction solvent in the feed from the feed tank V-55. A metering pump can be arranged between the solvent condensate tank V-53 and the reaction solvent rectifying tower T-52.
In the invention, the reaction solvent recovery device can also be provided with a communicated vacuum system, which can promote the efficiency of the reaction solvent rectifying tower T-52 and reduce the energy consumption.
In the invention, a discharge pump and an adjusting valve can be arranged between the outlet of the tower top of the alcohol rectifying tower T-51 and the alcohol heat exchanger E-51 for controlling the discharge and reflux ratio. The reaction solvent rectifying column T-52 can be provided with a discharge pump and an adjusting valve between the outlet of the top of the column and the solvent heat exchanger E-53 for controlling the discharge and reflux ratio.
In the invention, the various devices, such as the tank, the tower, the device, the kettle, the centrifuge and the like can be respectively provided with a feed inlet and/or a discharge outlet according to requirements, wherein the feed inlet is used for receiving introduced materials, and the discharge outlet is used for discharging the materials. One or more feed inlets and discharge outlets can be arranged according to actual needs.
In the invention, stirring mechanisms can be arranged in the reaction liquid mixing kettle R-11, the washing kettle R-22 and the copolymerization reactor R-12. The stirring mechanism is used for stirring materials in the kettle or the reactor when needed, so that mass transfer is more sufficient. In addition, jackets can be arranged in the reaction liquid mixing kettle R-11, the washing kettle R-22 and the copolymerization reactor R-12, and the temperature can be regulated and controlled by circulating water.
In the present invention, the system may further include:
and the metering pumps are arranged between the reaction liquid mixing kettle R-11 and the copolymerization reactor R-12, between the copolymerization reactor R-12 and the first disk centrifuge S-21, and between the washing kettle R-22 and the second disk centrifuge S-22.
In the present invention, the first disk centrifuge and the second disk centrifuge included in the above system are preferably selected to have a separation factor greater than 9000, preferably 9000-. Values in the range of 9000, 10000, 20000, 30000, 40000, 50000, or 60000, and any two of the foregoing may be selected. The disc centrifuge within the limited range can better meet the condition that the centrifugal separation of the microsphere-containing material is realized under the condition of high concentration by the system provided by the invention, so that the system provided by the invention can be continuously operated, and the risk of sudden empty operation is reduced.
In the context of the present invention, the separation factor refers to the ratio of the centrifugal force to which the suspension or emulsion in the centrifuge is subjected in the centrifugal force field to its gravitational force, i.e. the ratio of the centrifugal acceleration to the gravitational acceleration. The separation factor is expressed as Fr: wherein R is the radius (meter) of the position of the separated material in the rotary drum; ω is the rotational angular velocity (radians/sec) of the drum; g is the acceleration of gravity (9.81 m/s)2) (ii) a n is the rotating drum rotating speed (revolution/minute); and m is the mass (kg) of the materials in the rotary drum. The separation factor is a primary measure of centrifuge performance. The larger Fr is, the larger driving force of centrifugal separation is, and the better separation performance of the centrifugal machine is
Figure BDA0001841384290000091
In a second aspect, the present invention provides a method for preparing maleic anhydride copolymer microspheres by using the system of the present invention, as shown in fig. 4, comprising:
(1) carrying out copolymerization reaction on maleic anhydride, a monomer B shown in a formula (I), an initiator, a cross-linking agent and a reaction solvent in a copolymerization unit of a system to obtain a polymer mother liquor containing maleic anhydride copolymer microspheres;
(2) continuously carrying out first separation on the polymer mother liquor to obtain a separated solid-containing phase and a separation liquid;
(3) introducing the separated solid-containing phase into a washing unit of a system, and performing at least one alcohol washing and second separation to obtain a slag phase and a washing clear liquid;
(4) sending the slag phase into a drying unit of a system for drying to obtain maleic anhydride copolymer microspheres;
(5) introducing the separation liquid and the washing clear liquid into a solvent recovery unit of the system, and respectively returning the recovered solvent and the recovered alcohol obtained by recovery to the steps (1) and (3);
Figure BDA0001841384290000092
in the formula (I), R is H or methyl.
According to the present invention, the amount of each raw material used in step (1) is not particularly limited, and preferably, the amount of the monomer B is 50 to 150mol, more preferably 75 to 100mol, relative to 100mol of maleic anhydride. Wherein, the monomer B can be alpha-methyl styrene or styrene.
According to the invention, the initiator is preferably used in an amount of 0.05 to 10mol, more preferably 1 to 1.5mol, relative to 100mol of maleic anhydride.
According to the present invention, the crosslinking agent is preferably used in an amount of 1 to 40mol, more preferably 10 to 20mol, and further preferably 15 to 20mol, relative to 100mol of maleic anhydride.
According to the present invention, the reaction solvent is preferably used in an amount of 50 to 150L, more preferably 75 to 100L, relative to 100mol of maleic anhydride.
In the step (1) of the present invention, the conditions of the copolymerization reaction are not particularly limited, but preferably, the conditions of the copolymerization reaction are such that the degree of crosslinking of the copolymer microspheres obtained is 65% or more. More preferably, in step (1), the copolymerization reaction conditions include: under inert atmosphere, the temperature is 50-90 ℃, preferably 60-70 ℃, and the time is 3-15h, preferably 3-12 h. The inert atmosphere may be nitrogen or argon.
In the step (1) of the present invention, the reaction solvent may be any solvent commonly used in solution polymerization, for example, the reaction solvent includes organic acid alkyl ester, that is, organic acid alkyl ester, or a mixture of organic acid alkyl ester and alkane, or a mixture of organic acid alkyl ester and aromatic hydrocarbon. Wherein the organic acid alkyl esters include, but are not limited to: at least one of methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, and ethyl phenylacetate. Such alkanes include, but are not limited to: n-hexane and/or n-heptane. The aromatic hydrocarbons include, but are not limited to: at least one of benzene, toluene and xylene.
In step (1) of the present invention, the initiator may be a reagent commonly used in the art for initiating the polymerization reaction of maleic anhydride and α -methylstyrene (or styrene), and may be a thermal decomposition type initiator. Preferably, the initiator is at least one selected from the group consisting of dibenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile, and azobisisoheptonitrile.
In the step (1), the crosslinking agent is divinylbenzene and/or an acrylate crosslinking agent containing at least two acrylate groups, and the acrylate groups have a structural formula：-O-C(O)-C(R’)＝CH2R' is H or C1-C4Alkyl groups of (a); preferably, the crosslinking agent is selected from divinylbenzene, 1, 3-propanediol dimethacrylate, 1, 2-propanediol dimethacrylate, 1, 3-propanediol diacrylate, 1, 2-propanediol diacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, phthalic acid diethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol, and/acrylate, polyethylene glycol, and/styrene, polyethylene glycol, and/acrylate, polyethylene glycol, and/acrylate, polyethylene glycol, and/styrene, at least one of pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and ethoxylated multifunctional acrylate.
According to the present invention, the washing of step (3) for the separation of the solid-containing phase may remove the residue of the copolymerization reaction in step (1), and preferably, the alcohol washing uses 100-250L of alcohol solvent in total, more preferably 150-200L, relative to 100mol of maleic anhydride. Preferably, the alcohol may be methanol and/or ethanol.
According to the invention, the separation of the microspheres from the resulting material containing microspheres is carried out in both steps (2) and (3). For example, the polymer mother liquor containing the maleic anhydride copolymer microspheres in the step (2) is subjected to first separation; and (4) carrying out continuous second separation on the separated solid-containing phase containing the copolymer microspheres washed by the alcohol in the step (3). The materials containing the microspheres are subjected to solid-liquid separation under the condition of high concentration to obtain the high-purity and superfine microspheres. Preferably, the separation factor of the first separation in step (2) is greater than 9000, preferably 9000-; the separation factor of the second separation in step (3) is greater than 9000, preferably 9000-. Within the above-mentioned range of separation factors, it is possible to achieve the industrial continuous operation of the above-mentioned separations in steps (2) to (3) of the present invention under the condition of high concentration of microspheres.
In the step (4) of the present invention, the drying temperature is 50-150 ℃, and the drying pressure may be 10-1013mbar, preferably 10-200mbar, to further remove the reaction solvent and/or alcohol solvent entrained in the slag phase.
In the present invention, step (5) is used for recovering the solvent and the alcohol, and is performed in the solvent recovery unit of the system provided by the present invention. And the operation and control conditions of each part of devices in the solvent recovery unit meet the requirements of recovering the reaction solvent and the alcohol in the separation liquid and the washing clear liquid. The operating conditions are not described in detail.
In the method provided by the invention, the aim of the invention can be better achieved under the limited conditions, the continuous preparation of the maleic anhydride copolymer with the cross-linking and microsphere structures is realized, the sudden empty operation of a solvent is avoided, and the frequent start-up and shutdown operations of a centrifuge are avoided.
The present invention will be described in detail below by way of examples.
In the following examples, the infrared spectroscopic analysis of the prepared maleic anhydride copolymer microspheres was carried out by a Spectrum Two instrument from PerkinElmer;
conditions of vacuum drying: the vacuum degree is-0.095 MPa at 100 ℃ and the time is 8 h.
The average particle size is determined by selecting 300-500 microspheres from a scanning electron microscope picture, measuring the diameter of the microspheres and calculating the average particle size of the microspheres by a mathematical average method;
scanning Electron microscopy analysis was determined by an XL-30ESEM-FEG instrument from FEI.
The method for measuring the degree of crosslinking comprises the following steps: weighing 2-3g of cross-linked maleic anhydride copolymer microspheres (w1), wrapping with medium-speed qualitative filter paper, placing into a Soxhlet extractor, extracting with tetrahydrofuran for 24h, drying the obtained residue, weighing (w2),
Figure BDA0001841384290000121
turbidity: the turbidity value is characterized by the concentration of particles (mass in g of particles in 100g of solvent, in% by weight) as determined using a turbidimeter.
Example 1
Isoamyl acetate is stored in a reaction solvent storage tank V-13; preparing a reaction solution in a reaction solution mixing kettle R-11: 1014mol of maleic anhydride, 12.2mol of azobisisobutyronitrile, 200mol of divinylbenzene, 1000mol of alpha-methyl styrene and 1000L of isoamyl acetate.
The reaction solution is put into a copolymerization reactor R-12 (two parallel full-mixing kettle type reactors R-12B and R-12A) and copolymerization reaction is carried out for 5 hours at 75 ℃ in the atmosphere of nitrogen. The polymerization mother liquor containing the maleic anhydride copolymer microspheres obtained by the reaction is added into a first disk centrifuge S-21 through a metering pump (the flow rate is 100kg/h) to carry out continuous first separation (separation factor 9000), the separated separation liquor obtained by the separation passes through a first online turbidity meter A-21, when the turbidity is less than 0.1 wt%, the separation liquor is conveyed into a separation liquor storage tank V-25, and when the turbidity is more than 0.1 wt%, the separation liquor is returned to a copolymerization reactor R-12. The separated solid-containing phase obtained by the centrifugal separation is sent to a washing kettle R-22.
Feeding the methanol in the alcohol storage tank V-27 into a washing kettle R-22 by a metering pump, wherein the flow rate is 143kg/h, and carrying out alcohol washing on the separated solid-containing phase for 1 h; the alcohol washing product is sent into a second disk centrifuge S-22 by a metering pump (the flow is 173kg/h) for second separation (the separation factor is 9000), the obtained clear liquid is sent into a clear liquid storage tank V-26 when the turbidity is judged to be less than 0.1 weight percent by a second online turbidity meter A-22, and the clear liquid is returned into a washing kettle R-22 when the turbidity is more than 0.1 weight percent; the obtained slag phase was sent to a dryer G-41.
And conveying the slag phase into a rake vacuum drier G-41(36kg/h) according to the material level, drying the slag phase in the rake vacuum drier at the drying temperature of 140 ℃, the pressure of 80mbar, the retention time of 4h and the condensation temperature of a condenser E-41 of 0 ℃ to obtain the crosslinked alpha-methylstyrene/maleic anhydride copolymer microspheres with the yield of 14.5 kg/h.
Carrying out infrared spectroscopic analysis on the microspheres, as shown in figure 1, displaying a maleic anhydride characteristic peak and an aromatic ring characteristic peak, and proving the structure of a target polymer; scanning electron microscope analysis is carried out on the microspheres, and as shown in figure 2, the microspheres are shown to have a microsphere structure; the average particle size was determined to be 1521 nm. The degree of crosslinking was determined to be 82%.
And the full mixing kettle type reactor R-12B and the full mixing kettle type reactor R-12A are connected in parallel and alternately discharged.
And respectively introducing the separated liquid in the separated liquid storage tank V-25 and the clear liquid in the clear liquid storage tank V-26 into a reaction solvent rectifying tower T-52 in the reaction solvent recovery device and an alcohol rectifying tower T-51 in the alcohol solvent recovery device, and respectively recovering the reaction solvent and the methanol for recycling. The methanol recovery and reaction solvent recovery conditions were as follows:
alcohol rectifying tower T-51 Reaction solvent rectifying tower T-52
Overhead temperature/. degree.C 68.9 74.0
Temperature of the bottom of the column/. degree.C 156.3 173.5
Operating pressure/bar (gauge pressure) 1.4bar -0.9bar
Reflux ratio 0.13 0.3
Example 2
The procedure is as in example 1, except that ethanol is present in the alcohol tank V-27.
Example 3
Isoamyl acetate is stored in a reaction solvent storage tank V-13; preparing a reaction solution in a reaction solution mixing kettle R-11: 1014mol of maleic anhydride, 10.14mol of azobisisobutyronitrile, 150mol of divinylbenzene, 750mol of alpha-methyl styrene and 900L of isoamyl acetate.
The reaction liquid enters a tubular reactor R-12 with the feeding amount of 100kg/h, and the outlet temperature of the tubular reactor R-12 is controlled at 90 ℃ for 3h under the nitrogen atmosphere. Adding the polymerization mother liquor containing the maleic anhydride copolymer microspheres obtained by the reaction from an outlet (the flow rate is 100kg/h) of the reactor R-12 into a first disk centrifuge S-21 for continuous first separation (the separation factor is 12000), conveying the separated liquid into a separated liquid storage tank V-25 when the turbidity is less than 0.1 weight percent through a first online turbidity meter A-21, and returning the separated liquid into the copolymerization reactor R-12 when the turbidity is more than 0.1 weight percent. The separated solid-containing phase obtained by the centrifugal separation is sent to a washing kettle R-22.
Feeding the washing methanol in the alcohol storage tank V-27 into a washing kettle R-22 by a metering pump, wherein the flow rate is 133kg/h, and carrying out alcohol washing on the separated solid-containing phase for 1 h; feeding the alcohol washing product into a second disk centrifuge S-22 by a metering pump (the flow is 162kg/h) for second separation (the separation factor is 12000), feeding the obtained washing clear liquid into a clear liquid storage tank V-26 when the turbidity is judged to be less than 0.1 weight percent by a second online turbidity meter A-22, and returning the washing clear liquid into a washing kettle R-22 when the turbidity is more than 0.1 weight percent; the obtained slag phase was sent to a dryer G-41.
The slag phase is fed into a rake vacuum drier G-41(33kg/h) according to the material level, the slag phase is dried in the rake vacuum drier at the drying temperature of 50 ℃, the pressure of 10mbar, the retention time of 4h, the condensation temperature of a condenser E-41 of 0 ℃ and the yield of 13.3 kg/h.
Carrying out infrared spectrum analysis on the microspheres, displaying a maleic anhydride characteristic peak and an aromatic ring characteristic peak, and proving the structure of the target polymer; carrying out scanning electron microscope analysis on the microspheres to show that the microspheres have a microsphere structure; the average particle size was determined to be 1600 nm. The degree of crosslinking was determined to be 78%.
And respectively introducing the separated liquid in the separated liquid storage tank V-25 and the clear liquid in the clear liquid storage tank V-26 into a reaction solvent rectifying tower T-52 in the reaction solvent recovery device and an alcohol rectifying tower T-51 in the alcohol solvent recovery device, and respectively recovering the reaction solvent and the methanol for recycling. The methanol recovery and reaction solvent recovery conditions were as follows:
alcohol rectifying tower T-51 Reaction solvent rectifying tower T-52
Overhead temperature/. degree.C 68.9 74.0
Temperature of the bottom of the column/. degree.C 156.3 173.5
Operating pressure/bar (gauge pressure) 1.4bar -0.9bar
Reflux ratio 0.13 0.3
Example 4
Isoamyl acetate is stored in a reaction solvent storage tank V-13; preparing a reaction solution in a reaction solution mixing kettle R-11: 1014mol of maleic anhydride, 15mol of azobisisobutyronitrile, 180mol of divinylbenzene, 850mol of alpha-methyl styrene and 850L of isoamyl acetate.
And (3) feeding the reaction liquid into a groove type baffling reactor R-12 with the feeding amount of 100kg/h, and controlling the outlet temperature of the groove type baffling reactor R-12 to be 85 ℃ and the retention time to be 3h under the nitrogen atmosphere.
Adding the polymerization mother liquor containing the maleic anhydride copolymer microspheres obtained by the reaction from an outlet (the flow rate is 100kg/h) of a reactor R-12 into a first disk centrifuge S-21 for continuous first separation (the separation factor is 14000), conveying the separated liquid into a separated liquid storage tank V-25 when the turbidity is less than 0.1 weight percent through a first online turbidity meter A-21, and returning the separated liquid to the copolymerization reactor R-12 when the turbidity is more than 0.1 weight percent. The separated solid-containing phase obtained by the centrifugal separation is sent to a washing kettle R-22.
Feeding the washing methanol in the alcohol storage tank V-27 into a washing kettle R-22 by a metering pump, wherein the flow rate is 170kg/h, and carrying out alcohol washing on the separated solid-containing phase for 1 h; feeding the alcohol washing product into a second disk centrifuge S-22 by a metering pump (the flow is 207kg/h) for second separation (the separation factor is 14000), feeding the obtained clear liquid into a clear liquid storage tank V-26 when the turbidity is judged to be less than 0.1 weight percent by a second online turbidity meter A-22, and returning the clear liquid into a washing kettle R-22 when the turbidity is more than 0.1 weight percent; the obtained slag phase was sent to a dryer G-41.
The slag phase is fed into a rake vacuum drier G-41(43kg/h) according to the material level, and is dried in the rake vacuum drier at the drying temperature of 100 ℃, the pressure of 100mbar, the retention time of 4h, the condensation temperature of a condenser of 0 ℃ and the yield of 17.2 kg/h.
Carrying out infrared spectrum analysis on the microspheres, displaying a maleic anhydride characteristic peak and an aromatic ring characteristic peak, and proving the structure of the target polymer; carrying out scanning electron microscope analysis on the microspheres to show that the microspheres have a microsphere structure; the average particle size was determined to be 2000 nm. The degree of crosslinking was determined to be 80%.
And respectively introducing the separated liquid in the separated liquid storage tank V-25 and the clear liquid in the clear liquid storage tank V-26 into a reaction solvent rectifying tower T-52 in the reaction solvent recovery device and an alcohol rectifying tower T-51 in the alcohol solvent recovery device, and respectively recovering the reaction solvent and the methanol for recycling. The methanol recovery and reaction solvent recovery conditions were as follows:
alcohol rectifying tower T-51 Reaction solvent rectifying tower T-52
Overhead temperature/. degree.C 68.9 74.0
Temperature of the bottom of the column/. degree.C 156.3 173.5
Operating pressure/bar (gauge pressure) 1.4bar -0.9bar
Reflux ratio 0.13 0.3
Comparative example 1
The following reaction liquid is prepared in a polymer reaction kettle: 1014mol of maleic anhydride, 12.2mol of azobisisobutyronitrile, 200mol of divinylbenzene, 1000mol of alpha-methyl styrene and 1000L of isoamyl acetate.
Heating the reaction solution to 75 ℃ (the heating time is 1h), and carrying out copolymerization reaction for 5h at 75 ℃; and (3) carrying out solid-liquid separation on the polymerization mother liquor containing the maleic anhydride copolymer microspheres obtained by the reaction by using a three-leg centrifuge. In order to ensure safety, the reaction solution needs to be cooled to 30 ℃ (the cooling time is 1 h). The separation time was 2 h/batch (number of batches depends on whether the filter was clogged). After separation, the centrifuge was stopped for 1 h. Separating to obtain separated solid-containing phase.
The separated solid-containing phase is manually added into a washing kettle (the time of material transfer and atmosphere replacement is 1 h). The washing methanol was transferred from the alcohol tank by means of a metering pump into the washing vessel and stirred for 1 h. The obtained washing liquid is added into a three-leg centrifuge by a metering pump for separation, the separation time is 2 h/batch (the batch number depends on whether the filter material is blocked), and after separation, the centrifuge is stopped for 1 h. A slag phase is obtained.
The slag phase is manually added into a rake type vacuum drier G-41 (the time for material transfer and atmosphere replacement is 1h), the slag phase is dried in the rake type vacuum drier at the drying temperature of 140 ℃ (the temperature rise time is 1h), the pressure is 80mbar, the retention time is 4h, the condensation temperature of a condenser is 0 ℃, and the yield is 172kg of the crosslinked alpha-methylstyrene/maleic anhydride copolymer microspheres.
The production efficiency of the batch operation was 8.2kg/h (solid-liquid separation of one batch was carried out using a three-leg centrifuge in each stage).
The method provided by the invention eliminates manual operation and reduces the influence of human on the stability of the production process.
It can be seen from the results of the examples, the comparative examples and the table 1 that the continuous preparation of the crosslinked maleic anhydride copolymer having crosslinked and microsphere structures can be realized by using the examples 1 to 4 of the present invention, the separation process of manual operation between the units of the preparation system in the prior art is overcome, the obvious effects of higher production efficiency and stable production process are achieved, the production process does not need manual field operation, no organic solvent explosion operation exists, and the harm to personnel and environment is low.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (14)

1. A system for preparing maleic anhydride copolymer microspheres, the system comprising:
a copolymerization unit, a washing unit, a drying unit and a solvent recovery unit which are communicated in sequence, wherein,
the copolymerization unit is used for carrying out copolymerization reaction on a comonomer, and the obtained polymer mother liquor containing the maleic anhydride copolymer microspheres is continuously subjected to first separation to obtain a separated solid-containing phase and a separated liquid;
the washing unit is used for carrying out at least one time of alcohol washing and continuous second separation on the separated solid-containing phase to obtain a slag phase and a washing clear liquid;
the drying unit is used for drying the slag phase to obtain the maleic anhydride copolymer microspheres;
the solvent recovery unit is used for removing impurities from the separation liquid and the washing clear liquid, and returning the recovered solvent and the recovered alcohol obtained by separation to the copolymerization unit and the washing unit respectively;
the copolymerized units include: a reaction solvent storage tank (V-13), a reaction liquid mixing kettle (R-11), a copolymerization reactor (R-12), a first disk centrifuge (S-21), a first on-line turbidity meter (A-21) and a separation liquid storage tank (V-25); wherein the content of the first and second substances,
the reaction solvent storage tank (V-13) is used for storing the reaction solvent;
the reaction liquid mixing kettle (R-11) is used for mixing the reaction solvent and the reaction raw materials into reaction liquid;
a copolymerization reactor (R-12) for continuously subjecting the reaction liquid to the copolymerization reaction;
the obtained polymer mother liquor continuously flows into a first disc centrifuge (S-21) to carry out continuous first separation, and the obtained separation liquid passes through a first online turbidimeter (A-21) and then is introduced into a copolymerization reactor (R-12) or a separation liquid storage tank (V-25);
the system is used for realizing continuous production of the maleic anhydride copolymer microspheres.
2. The system according to claim 1, wherein valves are provided between the first on-line turbidimeter (a-21) and the copolymerization reactor (R-12), between the first on-line turbidimeter (a-21) and the separation liquid tank (V-25), respectively, for passing the separation liquid to the separation liquid tank (V-25) when the turbidity of the separation liquid is up to standard and to the copolymerization reactor (R-12) when the turbidity is not up to standard.
3. The system of claim 1 or 2, wherein the washing unit comprises: an alcohol tank (V-27), a clear liquid tank (V-26) and at least one set of washing devices, each set of washing devices comprising: a washing kettle (R-22), a second disc centrifuge (S-22) and a second online turbidimeter (A-22); wherein the content of the first and second substances,
an alcohol storage tank (V-27) for storing an alcohol solvent;
a washing tank (R-22) for continuously subjecting the separated solid-containing phase and the alcohol solvent to the alcohol washing to obtain a dispersed slurry;
and continuously introducing the dispersed slurry into a second disc centrifuge (S-22) for continuous second separation, and introducing the obtained clear liquid into a washing kettle (R-22) or a clear liquid storage tank (V-26) after passing through a second online turbidity meter (A-22).
4. The system according to claim 1 or 2, wherein valves are provided between the second on-line turbidimeter (a-22) and the wash tank (R-22), between the second on-line turbidimeter (a-22) and the clear liquid tank (V-26), respectively, for passing the clear liquid to the clear liquid tank (V-26) when the turbidity of the clear liquid is up to standard and to the wash tank (R-22) when the turbidity is not up to standard.
5. The system of claim 1 or 2, wherein the drying unit comprises: a dryer (G-41), a condenser (E-41) and a dry condensate tank (V-41); wherein the content of the first and second substances,
the dryer (G-41) is used for drying the slag phase to obtain the maleic anhydride copolymer microspheres;
the condenser (E-41) is communicated with the drying condensate tank (V-41) and is used for condensing the gaseous solvent discharged by the condensing dryer (G-41) into liquid and introducing the liquid into the drying condensate tank (V-41);
the drying gel tank (V-41) is communicated with the alcohol storage tank (V-27).
6. The system of claim 1 or 2, wherein the solvent recovery unit comprises: an alcohol solvent recovery device and a reaction solvent recovery device; wherein the content of the first and second substances,
the alcohol solvent recovery device is communicated with the clear liquid storage tank (V-26), the alcohol storage tank (V-27) and the reaction solvent recovery device, is used for recovering the alcohol solvent in the clear liquid from the clear liquid storage tank (V-26), returns to the alcohol storage tank (V-27), and simultaneously leads residual liquid of the clear liquid to the reaction solvent recovery device;
and the reaction solvent recovery device is communicated with the separation liquid storage tank (V-25) and the reaction solvent storage tank (V-13) and is used for recovering the separation liquid from the separation liquid storage tank (V-25) and the reaction solvent in the residual liquid and returning the separation liquid and the reaction solvent to the reaction solvent storage tank (V-13).
7. The system of claim 6, wherein the alcohol solvent recovery device comprises: an alcohol rectifying tower (T-51), an alcohol heat exchanger (E-51), an alcohol condensate tank (V-51) and a raffinate reboiler (E-52);
wherein the alcohol rectifying tower (T-51) is used for distilling clear liquid from the clear liquid storage tank (V-26), and alcohol vapor discharged from the top of the alcohol rectifying tower (T-51) passes through the alcohol heat exchanger (E-51) and the alcohol condensate tank (V-51) in turn to obtain recovered alcohol; a part of the recovered alcohol is returned to an alcohol rectification column (T-51), and another part of the recovered alcohol is returned to an alcohol storage tank (V-27) to be reused in the washing unit;
and discharging a raffinate from the bottom of the alcohol rectification column (T-51), wherein a part of the raffinate is returned to the alcohol rectification column (T-51) after passing through a raffinate reboiler (E-52), and the other part of the raffinate is passed to the reaction solvent recovery unit.
8. The system of claim 6, wherein the reaction solvent recovery device comprises: a feeding tank (V-55), a reaction solvent rectifying tower (T-52), a solvent heat exchanger (E-53), a solvent condensate tank (V-53) and a waste liquid reboiler (E-54);
wherein the feed tank (V-55) communicates the bottom of the alcohol rectification column (T-51) and the separated liquid storage tank (V-25) for mixing the residue and the separated liquid from the separated liquid storage tank (V-25) as a feed;
the reaction solvent rectifying tower (T-52) is used for fractionating the feed, and the solvent vapor discharged from the top of the reaction solvent rectifying tower (T-52) sequentially passes through the solvent heat exchanger (E-53) and the solvent condensate tank (V-53) to obtain a condensed solvent; one part of the condensed solvent is returned to the reaction solvent rectifying tower (T-52), and the other part of the condensed solvent is returned to the reaction solvent storage tank (V-13) to be reused in the copolymerization unit;
and discharging waste liquid from the bottom of the reaction solvent rectifying tower (T-52), wherein one part of the waste liquid returns to the reaction solvent rectifying tower (T-52) after passing through a waste liquid reboiler (E-54), and the other part of the waste liquid is discharged.
9. A method of using the system of any one of claims 1-8 for making maleic anhydride copolymer microspheres, comprising:
(1) carrying out copolymerization reaction on maleic anhydride, a monomer B shown in a formula (I), an initiator, a cross-linking agent and a reaction solvent in a copolymerization unit of a system to obtain a polymer mother liquor containing maleic anhydride copolymer microspheres;
(2) continuously carrying out first separation on the polymer mother liquor to obtain a separated solid-containing phase and a separation liquid;
(3) introducing the separated solid-containing phase into a washing unit of a system, and performing at least one alcohol washing and continuous second separation to obtain a slag phase and a washing clear liquid;
(4) sending the slag phase into a drying unit of a system for drying to obtain maleic anhydride copolymer microspheres;
(5) introducing the separation liquid and the washing clear liquid into a solvent recovery unit of the system, and respectively returning the recovered solvent and the recovered alcohol obtained by recovery to the steps (1) and (3);
Figure FDA0003186887420000041
r is H or methyl.
10. The process according to claim 9, wherein in the step (1), the monomer B is used in an amount of 50 to 150mol, the initiator is used in an amount of 0.05 to 10mol, the crosslinking agent is used in an amount of 1 to 40mol, and the reaction solvent is used in an amount of 50 to 150L, relative to 100mol of maleic anhydride.
11. The method of claim 9, wherein in step (1), the copolymerization reaction conditions comprise: under inert atmosphere, the temperature is 50-90 ℃, and the time is 3-15 h.
12. The method as claimed in claim 9, wherein, in the step (3), a total of 100 and 250L of alcoholic solvent is used for the alcohol washing; the alcohol solvent is selected from methanol or ethanol.
13. The method of any of claims 9-12, wherein the separation factor for the first separation in step (2) is greater than 9000 and the separation factor for the second separation in step (3) is greater than 9000.
14. The method as claimed in claim 13, wherein the separation factor for the first separation in step (2) is 9000-.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4420599A (en) * 1981-08-05 1983-12-13 Idemitsu Kosan Company Limited Process of producing copolymers of an aromatic vinyl monomer and maleic anhydride
CN101338008A (en) * 2008-08-19 2009-01-07 北京化工大学 Process for preparing cross-linking maleic anhydride-styrene copolymer
CN105949388A (en) * 2016-05-23 2016-09-21 北京化工大学 Functional copolymer directly prepared from higher olefin mixture and preparation method
CN106477600A (en) * 2016-10-09 2017-03-08 青海盐湖工业股份有限公司 A kind of tail salt removes magnesium apparatus

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4420599A (en) * 1981-08-05 1983-12-13 Idemitsu Kosan Company Limited Process of producing copolymers of an aromatic vinyl monomer and maleic anhydride
CN101338008A (en) * 2008-08-19 2009-01-07 北京化工大学 Process for preparing cross-linking maleic anhydride-styrene copolymer
CN105949388A (en) * 2016-05-23 2016-09-21 北京化工大学 Functional copolymer directly prepared from higher olefin mixture and preparation method
CN106477600A (en) * 2016-10-09 2017-03-08 青海盐湖工业股份有限公司 A kind of tail salt removes magnesium apparatus

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