CN113501902B - Preparation method of styrene-acrylic acid copolymer type dispersing agent - Google Patents
Preparation method of styrene-acrylic acid copolymer type dispersing agent Download PDFInfo
- Publication number
- CN113501902B CN113501902B CN202110667232.2A CN202110667232A CN113501902B CN 113501902 B CN113501902 B CN 113501902B CN 202110667232 A CN202110667232 A CN 202110667232A CN 113501902 B CN113501902 B CN 113501902B
- Authority
- CN
- China
- Prior art keywords
- acrylic acid
- mass
- mixed solution
- aqueous solution
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/30—Sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of a styrene-acrylic acid copolymer type dispersing agent, which is characterized by comprising the following steps: preparing a sodium styrenesulfonate aqueous solution, an acrylic mixed solution, a persulfate initiator aqueous solution and a sodium bisulfate chain transfer agent aqueous solution, mixing the sodium styrenesulfonate aqueous solution and the acrylic mixed solution by a micromixer, heating, mixing the mixture with the initiator aqueous solution again by the micromixer, initiating polymerization at fixed points, adding the chain transfer agent aqueous solution at fixed points after passing through the micromixer in the later stage of reaction to terminate the reaction, and performing aftertreatment to obtain the styrene-acrylic copolymerization type dispersing agent. The invention adopts the micromixer to react, and immediately terminates the reaction after the reaction is completed in a short time, the reaction process is easy to control, the efficiency is high, the equipment investment is small, the preparation process is simple, the practicability is strong, and the prepared styrene-acrylic acid copolymer dispersing agent has good dispersing effect and is suitable for the fields of pesticides, pigments, dyes and the like.
Description
Technical Field
The invention belongs to the preparation of high molecular organic compounds, and relates to a preparation method of a styrene-acrylic acid copolymer type dispersing agent. The styrene-acrylic acid copolymer dispersing agent prepared by the invention is suitable for the fields of pesticides, pigments, dyes and the like.
Background
The dispersing agent has important application in the fields of pesticides, pigments, dyes and the like. Conventional small molecule dispersants fail by being easily dissociated from the surface of solid particles. The carboxylate copolymer dispersant is one kind of water soluble anionic polymer dispersant, and has stable system dispersion via electrostatic repulsion and steric hindrance, no sensitivity to system temperature, pH value and ionic strength, and capacity of exerting the dispersing capacity to the maximum degree in water system. The electrostatic repulsion stabilizing mechanism is to ionize the polymer dispersant to form an electric double layer on the surface of the nanometer particles, and to make the nanometer particles stably exist in the medium through electrostatic repulsion. The steric stabilization is based on the theory that the polymeric dispersant forms a firm adsorption on the surface of the nanoparticles and has a complete coating layer with sufficient thickness (1-10 nm) of the adsorption layer. Meanwhile, compared with a small molecular dispersing agent with a single anchoring group, the high molecular dispersing agent contains a plurality of anchoring points, can be more effectively adsorbed on the surface of the dispersed particles, and has large adsorption capacity. In general, homopolymers are not good dispersants because they are good solvating chains or good anchor groups, and good repulsion stabilization requires both to be present, as are copolymers such as random, graft or block copolymers which are generally present as aqueous pigment dispersants. Therefore, the polymer type carboxylate copolymer, such as styrene-acrylic copolymer dispersant, can make the dispersion system more stable through charge action and steric hindrance, and thus has better dispersing effect than the small molecular type dispersant.
The traditional copolymer dispersing agent generally adopts an intermittent kettle type synthesis method, styrene, acrylic acid and the like are used as raw material monomers, a water-soluble oxidation-reduction system is used as an initiator, water and the like are used as solvents, all materials are fed in a certain proportion in a dropwise manner at a constant temperature, polymerization is completed through heat preservation reaction and adding a terminator, and then a powdery product is finally obtained through post-treatment processes such as acid-base neutralization, spray drying and the like. The above synthetic route belongs to the free radical polymerization mechanism. The reaction process of free radical polymerization mostly belongs to rapid and strongly exothermic easy-to-run-away reaction, and the commonality is that the reaction cannot be initiated without reaching a certain condition, and the reaction is easy to run away when the reaction is slightly higher than the condition; in the initial stage of free radical polymerization, the initiator is slowly initiated to form primary free radicals, and once the primary free radicals are generated, the monomer is rapidly initiated to carry out polymerization, and the step can be completed in a few seconds or even shorter; the characteristics of slow initiation, rapid growth and rapid termination of free radical polymerization determine that high molecular polymers are generated in extremely short time, most of free radical polymerization reactions are strong exothermic reactions, rapid heat release is easy to further promote the improvement of reaction speed, an automatic acceleration phenomenon occurs, and meanwhile, the viscosity of a reaction system is rapidly increased along with the progress of the reaction, so that the reaction process is uncontrollable. Therefore, the implementation route of the prior art has the problems of easy uncontrolled explosion polymerization, high safety risk, high equipment investment, poor batch stability of products and the like of the traditional batch kettle type reaction of free radical polymerization.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a styrene-acrylic copolymer type dispersing agent. The preparation method of the styrene-acrylic copolymer dispersing agent with excellent dispersing effect is provided by mixing the sodium styrene sulfonate aqueous solution and the acrylic mixed solution through a micromixer, heating, mixing with the initiator aqueous solution again through the micromixer, initiating the mixture at fixed points to polymerize the mixture, adding the chain transfer agent aqueous solution at fixed points to terminate the reaction after passing through the micromixer in the later period of the reaction, and performing aftertreatment.
The invention comprises the following steps: a preparation method of a styrene-acrylic acid copolymer type dispersing agent is characterized by comprising the following steps:
a. preparation of an aqueous sodium styrenesulfonate solution:
adding 100 parts by mass of sodium styrenesulfonate into 150-400 parts by mass of water, stirring and mixing to prepare 40-20% sodium styrenesulfonate aqueous solution, and standing at normal temperature for later use; too low a concentration would result in too slow a subsequent reaction rate and a double extension of the polymerization residence time in step f; if the concentration is too high, the reaction is too fast, and the efficiency of water bath temperature control cannot be matched;
b. Preparing an acrylic mixed solution:
100 to 200 parts by mass of acrylic acid, 25 to 50 parts by mass of methacrylic acid, 25 to 50 parts by mass of methyl methacrylate and 25 to 50 parts by mass of hydroxypropyl acrylate (equal acrylic monomer) are stirred and mixed by a high-speed stirrer to prepare an acrylic mixed solution, and the acrylic mixed solution is placed at normal temperature for standby;
c. preparing an aqueous initiator solution:
adding 15-45 parts by mass of persulfate initiator into 85-250 parts by mass of water, stirring and mixing to prepare an initiator aqueous solution, and standing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 5-15 parts by mass of sodium bisulphite into 300-900 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and standing at normal temperature for later use;
e. micromixing of sodium styrenesulfonate aqueous solution and acrylic mixed solution:
the sodium styrenesulfonate aqueous solution prepared in the step a and the acrylic acid mixed solution prepared in the step b are respectively conveyed by a conveying pump according to the volume flow ratio of 1:0.7 and simultaneously conveyed in a stable continuous flow mode and pass through a micromixer 1, and the temperature is quickly increased to 50-70 ℃ under the temperature control condition of a water bath 1, so that the sodium styrenesulfonate-acrylic acid mixed solution is obtained;
f. Initiating reaction polymerization of sodium styrenesulfonate-acrylic acid mixed solution:
c, the initiator aqueous solution prepared in the step c is pumped by a delivery pump and the mixed solution of sodium styrenesulfonate and acrylic acid obtained in the step e passes through a micromixer 2 in a form of stable continuous flow according to the volume flow ratio of 1:3, and is rapidly heated to 85-90 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize, and the reaction residence time is controlled to be 3-5 min (by adjusting the length of a reaction pipeline in the water bath 2) to obtain the mixed solution still in the polymerization stage;
g. polymerization termination:
the chain transfer agent aqueous solution prepared in the step d and the mixed solution still in the polymerization stage obtained in the step f pass through a micromixer 3 in a form of stable continuous flow according to the volume flow ratio of 1:3, and are rapidly cooled to below 40 ℃ under the temperature control condition of a water bath 3, so that the polymerization reaction is stopped, and the mixed solution is obtained;
h. post-treatment:
and (3) after the mixed solution obtained in the step (g) is discharged out of the micromixer (3), adjusting the pH value to 7-8 by using alkali liquor, and performing spray drying (the obtained powdery particle product) to obtain the styrene-acrylic copolymer type dispersing agent.
In the content of the invention: the persulfate initiator in the step c belongs to a water-soluble free radical polymerization initiator, and can be any one of potassium persulfate, sodium persulfate, ammonium persulfate and the like.
In the content of the invention: the mass dosage of the persulfate initiator in the step c is 5-15% of the total mass (namely the mass sum) of the sodium styrene sulfonate in the step a and the acrylic acid mixed solution in the step b; if the ratio (concentration) is too low, the initiation rate is slow, and the polymerization residence time in the step f is prolonged by times; too high a duty cycle (concentration) would result in too fast a reaction and an unmatched efficiency of the water bath temperature control.
In the content of the invention: the mass dosage of the sodium bisulfite in the step d is 1/3 of that of the persulfate initiator in the step c; the use of sodium bisulphite with a lower proportion cannot realize the effect of rapid fixed-point termination reaction, and other side reactions are caused by a higher proportion, so that the polymerization degree is reduced.
In the content of the invention: the alkali liquor in the step h can be one or a mixture of two of sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
In the content of the invention: the water used in step a, step b and step c may be pure water, distilled water, deionized water, etc. to reduce the influence of excessive ions in water on free radical polymerization and other side reactions.
In the content of the invention: the conveying pump used in the step e, the step f and the step g can be a constant flow pump or a advection pump, the required flow is continuous and stable, and typically an MP2010D medium-pressure constant flow pump of Shanghai three of science and instruments, a TBP2H10S advection pump of Shanghai field same biotechnology Co, and the like are provided.
In the content of the invention: the micromixers used in step e, step f, step g may be static mixers, typically 0.5-2.6ml HP type mixers supplied by Shimadzu corporation, etc.
In the content of the invention: the high-speed mixer in the step b may be FA, FAB, FAS, FM, FMB, an emulsifying machine of FMS series, etc. manufactured by Fluko, germany.
In the content of the invention: the reaction tubes used in step e, step f and step g which are in communication with the micromixers and convey the material are preferablyThe length of each section of reaction pipeline and the flow of the pump are adjusted to freely control the residence reaction time in each section of water bath kettle.
In the content of the invention: the continuous flows in step e, step f and step g must be simultaneously and continuously mixed, initiated, polymerized and terminated by a conveying pump and stably and continuously passing through the mixers in each stage in the form of constant flow rate, so as to ensure the uniformity of the reaction environment and the stability of the final product.
In the content of the invention: the sodium styrenesulfonate in the step a can be of industrial grade, and the product suppliers include Shanghai microphone Biochemical technology Co., ltd.
In the content of the invention: the raw materials in the acrylic acid in the step b are preferably analytically pure, and suppliers include Shanghai microphone Biotechnology Co., ltd, shanghai Baishun Biotechnology Co., ltd, and the like.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) According to the invention, the styrene sodium sulfonate aqueous solution and the acrylic acid mixed solution are mixed by a micromixer and then heated, then mixed with the initiator aqueous solution again by the micromixer, then the mixture is initiated at fixed points to polymerize, the chain transfer agent aqueous solution is added at fixed points to terminate the reaction after passing through the micromixer in the later period of the reaction, and then the reaction is post-treated to obtain the styrene-acrylic acid copolymerization dispersing agent with good dispersing effect;
(2) The invention adopts the micromixer for reaction, the micromixer has small internal size, so that the diffusion path of reactants is very short, the time required for realizing full mixing can be obviously shortened, and the micromixer has good heat transfer performance due to the extremely large specific surface area, and the accurate temperature control can be realized more easily; the micro mixer can control free radical polymerization more conveniently due to good heat and mass transfer characteristics, meanwhile, intermittent reaction can be changed into a continuous flow process, the reaction is initiated at a designated time and position, the reaction is stopped immediately after the reaction is completed in a short time, the reaction process is easy to control, the efficiency is high, and the effect is good;
(3) The invention adopts sectional micro-mixing, prepares the styrene-acrylic acid copolymer dispersing agent in the form of constant flow and continuous flow, realizes fixed-point initiation and fixed-point termination polymerization by optimizing the catalyst and controlling the temperature and the residence time (the length of a reaction pipeline) of each stage, can ensure the uniformity of the reaction environment, and has controllable molecular weight, good batch stability of the obtained product, controllable reaction heat release, small equipment investment and safe operation and use;
(4) The preparation method has the advantages of simple preparation process, simple and convenient working procedures, easy operation and strong practicability.
Drawings
FIG. 1 is a schematic view of a process for preparing a styrene-acrylic copolymer dispersant according to the present invention and examples.
Detailed Description
The following examples are intended to further illustrate the present invention but are not to be construed as limiting its scope, as many insubstantial modifications and adaptations of the invention that are within the scope of the invention as described above would be within the skill of the art.
The following examples and comparative examples of the present invention relate to the test methods:
(1) The number average relative molecular weight was determined using a gel permeation chromatograph with aqueous solution as the mobile phase and sodium polyacrylate as the standard.
(2) Dispersibility test of the dispersant on inorganic minerals:
adding 0.4g of the dispersing agent prepared in the patent and 50ml of water into a 100ml measuring cylinder with a plug, adding 1.00g of solid particles to be dispersed after the dispersing agent is dissolved, adding water to 100ml, and reversing the mixture upside down for 30 times, wherein the mixture is reversed upside down for 180 degrees and returned to the original position for 1 time; vertically placing the measuring cylinder in 25deg.C water bath without vibration, avoiding sunlight irradiation, removing upper layer 90ml suspension with a suction tube after 30min, transferring the rest 10ml suspension and precipitate to the weight of m 1 In a surface dish, and washing the measuring cylinder with distilled water to ensure that all sediment in the measuring cylinder is transferred to the surface dish, placing the surface dish into an oven for drying, and weighing m 2 Calculate mass of insoluble M, m=m 2 -m 1 To determine the suspension rate.
The calculation formula of the suspension rate:
suspension ratio = (1.400-M)/(1.400×10 +.9×100%
Wherein: m is the mass (g) of the dispersant and the solid particles contained in 10ml of the bottom of a 100ml plugged cylinder, and 1.400 is the total mass (g) of the dispersant and the solid particles contained in a 100ml plugged cylinder.
(3) Dispersibility test of the dispersant on water dispersible granule pesticides:
preparing water dispersible granule pesticide by using the dispersing agent, weighing 1.0g of the water dispersible granule pesticide, transferring to a beaker, adding 50ml of distilled water, standing for 30s, stirring for 30s by using a glass rod, transferring the suspension to a 100ml cylinder with a plug by using water, and adding distilled water to enable the suspension to reach 100ml. Plugging the measuring cylinder, and reversing the measuring cylinder with the plug for 30 times within 1 min; the measuring cylinder is immersed in a constant temperature water bath until the scale mark is 100ml and kept stand for 30min, and the temperature in the constant temperature water bath is kept at 30 ℃. After 30min, the upper 90ml of suspension was removed with a pipette without shaking or stirring the sediment in the measuring cylinder, ensuring that the tip was always a few millimeters below the liquid surface. Transferring the remaining 10ml of suspension and precipitate to a weighed mass of m 1 And flushing the measuring cylinder with distilled water to ensure that the sediment in the measuring cylinder is completely transferred into the surface dish, placing the surface dish into an oven for drying, and weighing m 2 Calculation ofMass of insoluble M (M) 2 -m 1 ) The suspension ratio was then calculated.
The calculation formula of the suspension rate:
suspension ratio = (1.00-M)/(1.00×10 +.9×100%
The amounts of the substances used in the examples below were 100% by weight, as described herein.
Examples 1 to 8: see fig. 1:
a preparation method of a styrene-acrylic acid copolymer type dispersing agent comprises the following steps:
a. preparation of an aqueous sodium styrenesulfonate solution:
adding 100 parts by mass of sodium styrenesulfonate into 150-400 parts by mass of water, stirring and mixing for 10min to prepare 40-20% sodium styrenesulfonate aqueous solution, and standing at normal temperature for later use;
b. preparing an acrylic mixed solution:
mixing 100-200 parts by mass of acrylic acid, 25-50 parts by mass of methacrylic acid, 25-50 parts by mass of methyl methacrylate and 25-50 parts by mass of hydroxypropyl acrylate for 1-3 min by a high-speed stirrer to prepare an acrylic acid mixed solution, and standing at normal temperature for later use;
c. preparing an aqueous initiator solution:
adding 15-45 parts by mass of persulfate initiator (slowly) into 85-250 parts by mass of water, stirring and mixing for 10min to prepare an initiator aqueous solution, and standing at normal temperature for later use;
d. Preparation of an aqueous chain transfer agent solution:
adding 5-15 parts by mass of sodium bisulphite into 300-900 parts by mass of water, stirring and mixing for 10min to prepare a chain transfer agent aqueous solution, and standing at normal temperature for later use;
e. micromixing of sodium styrenesulfonate aqueous solution and acrylic mixed solution:
the sodium styrenesulfonate aqueous solution prepared in the step a and the acrylic acid mixed solution prepared in the step b are respectively conveyed by a conveying pump according to the volume flow ratio of 1:0.7 (the flow rate is adjustable within the range of 10-90% of a pump body) and simultaneously conveyed in a stable continuous flow mode and pass through a micromixer 1, and the temperature is quickly increased to 50-70 ℃ under the temperature control condition of a water bath 1 (after the reaction pipeline length in the water bath 1 is adjusted to ensure that the temperature stays for 1-2 min), so as to obtain the sodium styrenesulfonate-acrylic acid mixed solution;
f. initiating reaction polymerization of sodium styrenesulfonate-acrylic acid mixed solution:
c, the initiator aqueous solution prepared in the step c is conveyed by a conveying pump and the mixed solution of sodium styrenesulfonate and acrylic acid obtained in the step e passes through a micromixer 2 according to the volume flow ratio of 1:3 (the flow rate is adjustable within the range of 10-90% of a pump body), and simultaneously the mixed solution is conveyed in a stable continuous flow mode, and is rapidly heated to 85-90 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize, and the reaction residence time is controlled to be 3-5 min by adjusting the length of a reaction pipeline in the water bath 2, so that the mixed solution still in the polymerization stage is obtained;
g. Polymerization termination:
the chain transfer agent aqueous solution prepared in the step d and the mixed solution still in the polymerization stage obtained in the step f are subjected to a micro-mixer 3 according to the volume flow ratio of 1:3 (the flow rate is adjustable within the range of 10-90% of a pump body), and simultaneously the mixed solution is subjected to a stable continuous flow mode, and the reaction residence time is maintained to be less than 40 ℃ under the temperature control condition of a water bath 3 (the reaction pipeline length in the water bath 3 is adjusted to maintain the reaction residence time to be 0.5-1 min, the temperature is adjusted), so that the polymerization reaction is stopped, and the mixed solution is obtained;
h. post-treatment:
and (3) after the mixed solution obtained in the step (g) is discharged out of the micromixer (3), adjusting the PH to 7-8 by using alkali liquor, and performing spray drying (the obtained powdery particle product) to obtain the styrene-acrylic copolymer type dispersing agent.
The specific amounts, process parameters, test results, etc. for each of examples 1-8 are shown in the following table:
table 1: examples 1 to 8 Process parameters for preparing sodium styrene sulfonate aqueous solutions
Table 2: examples 1 to 8 Process parameters for preparing acrylic Mixed solutions
Note that: the high-speed stirring emulsifier used in the examples of the above tables was manufactured by Fluko, germany, model FA25.
Table 3: examples 1 to 8 Process parameters for the preparation of aqueous initiator solutions
And (3) injection: the "initiator accounts for the total mass percent of the monomers" in table 3, i.e., the mass amount of (persulfate) initiator accounts for the total mass (i.e., the mass sum) of the sodium styrenesulfonate in step a and the acrylic mixture in step b.
Table 4: examples 1 to 8 Process parameters for the preparation of aqueous solutions of chain transfer agents
Table 5: examples 1 to 8 micromixing Process parameter Table of aqueous sodium styrene sulfonate solution and acrylic acid Mixed solution
Table 6: examples 1 to 8 polymerization process parameters of sodium styrene sulfonate-acrylic acid mixed solution
Table 7: examples 1 to 8 polymerization termination process parameter tables
Table 8: examples 1 to 8 product test results table
The post-treatment processes of pH adjustment by adding alkali, spray drying and the like for preparing the dispersing agent in the embodiments 1 to 8 of the invention are omitted here, and the operation method is the same as that of the prior art.
Example 9: see fig. 1:
a preparation method of a styrene-acrylic acid copolymer type dispersing agent comprises the following steps:
a. preparation of an aqueous sodium styrenesulfonate solution:
adding 100 parts by mass of sodium styrenesulfonate into 150 parts by mass of water, stirring and mixing to prepare a 40% sodium styrenesulfonate aqueous solution, and standing at normal temperature for later use;
b. preparing an acrylic mixed solution:
100 parts by mass of acrylic acid, 25 parts by mass of methacrylic acid, 25 parts by mass of methyl methacrylate and 25 parts by mass of hydroxypropyl acrylate are stirred and mixed by a high-speed stirrer to prepare an acrylic acid mixed solution, and the acrylic acid mixed solution is placed at normal temperature for standby;
c. preparing an aqueous initiator solution:
adding 15 parts by mass of persulfate initiator into 85 parts by mass of water, stirring and mixing to prepare an initiator aqueous solution, and standing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 5 parts by mass of sodium bisulphite into 300 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and standing at normal temperature for later use;
e. micromixing of sodium styrenesulfonate aqueous solution and acrylic mixed solution:
the sodium styrenesulfonate aqueous solution prepared in the step a and the acrylic acid mixed solution prepared in the step b are respectively conveyed by a conveying pump according to the volume flow ratio of 1:0.7 and simultaneously conveyed in a stable continuous flow mode and pass through a micromixer 1, and the temperature is quickly increased to 50 ℃ under the temperature control condition of a water bath 1, so that the sodium styrenesulfonate-acrylic acid mixed solution is obtained;
f. initiating reaction polymerization of sodium styrenesulfonate-acrylic acid mixed solution:
c, the initiator aqueous solution prepared in the step c is conveyed by a conveying pump and the mixed solution of sodium styrenesulfonate and acrylic acid obtained in the step e passes through a micromixer 2 in a form of stable continuous flow according to the volume flow ratio of 1:3, and the temperature is quickly increased to 85 ℃ under the temperature control condition of a water bath 2 to initiate and (quickly) react and polymerize to obtain the mixed solution still in the polymerization stage;
g. Polymerization termination:
the chain transfer agent aqueous solution prepared in the step d and the mixed solution still in the polymerization stage obtained in the step f pass through a micromixer 3 in a form of stable continuous flow according to the volume flow ratio of 1:3, and are rapidly cooled to below 40 ℃ under the temperature control condition of a water bath 3, so that the polymerization reaction is stopped, and the mixed solution is obtained;
h. post-treatment:
and (3) after the mixed solution obtained in the step (g) is discharged out of the micromixer (3), adjusting the pH value to 7 by using alkali liquor, and performing spray drying (the obtained powdery particle product) to obtain the styrene-acrylic acid copolymer type dispersing agent.
Example 10: see fig. 1:
a preparation method of a styrene-acrylic acid copolymer type dispersing agent comprises the following steps:
a. preparation of an aqueous sodium styrenesulfonate solution:
adding 100 parts by mass of sodium styrenesulfonate into 400 parts by mass of water, stirring and mixing to prepare a sodium styrenesulfonate aqueous solution with the concentration of 20%, and standing at normal temperature for later use;
b. preparing an acrylic mixed solution:
200 parts by mass of acrylic acid, 50 parts by mass of methacrylic acid, 50 parts by mass of methyl methacrylate and 50 parts by mass of hydroxypropyl acrylate are stirred and mixed by a high-speed stirrer to prepare an acrylic acid mixed solution, and the acrylic acid mixed solution is placed at normal temperature for standby;
c. Preparing an aqueous initiator solution:
adding 45 parts by mass of persulfate initiator into 250 parts by mass of water, stirring and mixing to prepare an initiator aqueous solution, and standing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 15 parts by mass of sodium bisulphite into 900 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and standing at normal temperature for later use;
e. micromixing of sodium styrenesulfonate aqueous solution and acrylic mixed solution:
the sodium styrenesulfonate aqueous solution prepared in the step a and the acrylic acid mixed solution prepared in the step b are respectively conveyed by a conveying pump according to the volume flow ratio of 1:0.7 and simultaneously conveyed in a stable continuous flow mode and pass through a micromixer 1, and the temperature is quickly increased to 70 ℃ under the temperature control condition of a water bath 1, so that the sodium styrenesulfonate-acrylic acid mixed solution is obtained;
f. initiating reaction polymerization of sodium styrenesulfonate-acrylic acid mixed solution:
c, the initiator aqueous solution prepared in the step c is conveyed by a conveying pump and the mixed solution of sodium styrenesulfonate and acrylic acid obtained in the step e passes through a micromixer 2 in a form of stable continuous flow according to the volume flow ratio of 1:3, and the temperature is quickly increased to 90 ℃ under the temperature control condition of a water bath 2 to initiate and (quickly) react and polymerize to obtain the mixed solution still in the polymerization stage;
g. Polymerization termination:
the chain transfer agent aqueous solution prepared in the step d and the mixed solution still in the polymerization stage obtained in the step f pass through a micromixer 3 in a form of stable continuous flow according to the volume flow ratio of 1:3, and are rapidly cooled to below 40 ℃ under the temperature control condition of a water bath 3, so that the polymerization reaction is stopped, and the mixed solution is obtained;
h. post-treatment:
and (3) after the mixed solution obtained in the step (g) is discharged out of the micromixer (3), adjusting the PH to 8 by using alkali liquor, and performing spray drying (the obtained powdery particle product) to obtain the styrene-acrylic acid copolymer type dispersing agent.
Example 11: see fig. 1:
a preparation method of a styrene-acrylic acid copolymer type dispersing agent comprises the following steps:
a. preparation of an aqueous sodium styrenesulfonate solution:
adding 100 parts by mass of sodium styrenesulfonate into 235 parts by mass of water, stirring and mixing to prepare a sodium styrenesulfonate aqueous solution, and standing at normal temperature for later use;
b. preparing an acrylic mixed solution:
150 parts by mass of acrylic acid, 38 parts by mass of methacrylic acid, 38 parts by mass of methyl methacrylate and 38 parts by mass of hydroxypropyl acrylate are stirred and mixed by a high-speed stirrer to prepare an acrylic acid mixed solution, and the acrylic acid mixed solution is placed at normal temperature for standby;
c. Preparing an aqueous initiator solution:
adding 30 parts by mass of persulfate initiator into 120 parts by mass of water, stirring and mixing to prepare an initiator aqueous solution, and standing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 10 parts by mass of sodium bisulphite into 450 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and standing at normal temperature for later use;
e. micromixing of sodium styrenesulfonate aqueous solution and acrylic mixed solution:
the sodium styrenesulfonate aqueous solution prepared in the step a and the acrylic acid mixed solution prepared in the step b are respectively conveyed by a conveying pump according to the volume flow ratio of 1:0.7 and simultaneously conveyed in a stable continuous flow mode and pass through a micromixer 1, and the temperature is quickly increased to 60 ℃ under the temperature control condition of a water bath 1, so that the sodium styrenesulfonate-acrylic acid mixed solution is obtained;
f. initiating reaction polymerization of sodium styrenesulfonate-acrylic acid mixed solution:
c, the initiator aqueous solution prepared in the step c is conveyed by a conveying pump and the mixed solution of sodium styrenesulfonate and acrylic acid obtained in the step e passes through a micromixer 2 in a form of stable continuous flow according to the volume flow ratio of 1:3, and is rapidly heated to 88 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize to obtain the mixed solution still in the polymerization stage;
g. Polymerization termination:
the chain transfer agent aqueous solution prepared in the step d and the mixed solution still in the polymerization stage obtained in the step f pass through a micromixer 3 in a form of stable continuous flow according to the volume flow ratio of 1:3, and are rapidly cooled to below 40 ℃ under the temperature control condition of a water bath 3, so that the polymerization reaction is stopped, and the mixed solution is obtained;
h. post-treatment:
and (3) after the mixed solution obtained in the step (g) is discharged out of the micromixer (3), adjusting the PH to 7.5 by using alkali liquor, and performing spray drying (the obtained powdery particle product) to obtain the styrene-acrylic copolymer type dispersing agent.
Example 12: see fig. 1:
a preparation method of a styrene-acrylic acid copolymer type dispersing agent comprises the following steps:
a. preparation of an aqueous sodium styrenesulfonate solution:
adding 100 parts by mass of sodium styrenesulfonate into 265 parts by mass of water, stirring and mixing to prepare a sodium styrenesulfonate aqueous solution, and standing at normal temperature for later use;
b. preparing an acrylic mixed solution:
mixing 150 parts by mass of acrylic acid, 37 parts by mass of methacrylic acid, 37 parts by mass of methyl methacrylate and 37 parts by mass of hydroxypropyl acrylate by stirring with a high-speed stirrer to obtain an acrylic acid mixed solution, and standing at normal temperature for later use;
c. Preparing an aqueous initiator solution:
adding 30 parts by mass of persulfate initiator into 115 parts by mass of water, stirring and mixing to prepare an initiator aqueous solution, and standing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 10 parts by mass of sodium bisulphite into 430 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and standing at normal temperature for later use;
e. micromixing of sodium styrenesulfonate aqueous solution and acrylic mixed solution:
the sodium styrenesulfonate aqueous solution prepared in the step a and the acrylic acid mixed solution prepared in the step b are respectively conveyed by a conveying pump according to the volume flow ratio of 1:0.7 and simultaneously conveyed in a stable continuous flow mode and pass through a micromixer 1, and the temperature is quickly increased to 62 ℃ under the temperature control condition of a water bath 1, so that the sodium styrenesulfonate-acrylic acid mixed solution is obtained;
f. initiating reaction polymerization of sodium styrenesulfonate-acrylic acid mixed solution:
c, the initiator aqueous solution prepared in the step c is pumped by a delivery pump and the mixed solution of sodium styrenesulfonate and acrylic acid obtained in the step e passes through a micromixer 2 in a form of stable continuous flow according to the volume flow ratio of 1:3, and is rapidly heated to 89 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize, and the reaction residence time is controlled to be 3min (by adjusting the length of a reaction pipeline in the water bath 2) to obtain the mixed solution still in the polymerization stage;
g. Polymerization termination:
the chain transfer agent aqueous solution prepared in the step d and the mixed solution still in the polymerization stage obtained in the step f pass through a micromixer 3 in a form of stable continuous flow according to the volume flow ratio of 1:3, and are rapidly cooled to below 40 ℃ under the temperature control condition of a water bath 3, so that the polymerization reaction is stopped, and the mixed solution is obtained;
h. post-treatment:
and (3) after the mixed solution obtained in the step (g) is discharged out of the micromixer (3), adjusting the pH value to 7 by using alkali liquor, and performing spray drying (the obtained powdery particle product) to obtain the styrene-acrylic acid copolymer type dispersing agent.
Example 13: see fig. 1:
a preparation method of a styrene-acrylic acid copolymer type dispersing agent comprises the following steps:
a. preparation of an aqueous sodium styrenesulfonate solution:
adding 100 parts by mass of sodium styrenesulfonate into 280 parts by mass of water, stirring and mixing to prepare a sodium styrenesulfonate aqueous solution, and standing at normal temperature for later use;
b. preparing an acrylic mixed solution:
160 parts by mass of acrylic acid, 38 parts by mass of methacrylic acid, 37 parts by mass of methyl methacrylate and 38 parts by mass of hydroxypropyl acrylate are stirred and mixed by a high-speed stirrer to prepare an acrylic acid mixed solution, and the acrylic acid mixed solution is placed at normal temperature for standby;
c. Preparing an aqueous initiator solution:
adding 30 parts by mass of persulfate initiator into 130 parts by mass of water, stirring and mixing to prepare an initiator aqueous solution, and standing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 10 parts by mass of sodium bisulphite into 400 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and standing at normal temperature for later use;
e. micromixing of sodium styrenesulfonate aqueous solution and acrylic mixed solution:
the sodium styrenesulfonate aqueous solution prepared in the step a and the acrylic acid mixed solution prepared in the step b are respectively conveyed by a conveying pump according to the volume flow ratio of 1:0.7 and simultaneously conveyed in a stable continuous flow mode and pass through a micromixer 1, and the temperature is quickly increased to 58 ℃ under the temperature control condition of a water bath 1, so that the sodium styrenesulfonate-acrylic acid mixed solution is obtained;
f. initiating reaction polymerization of sodium styrenesulfonate-acrylic acid mixed solution:
c, the initiator aqueous solution prepared in the step c is pumped by a delivery pump and the mixed solution of sodium styrenesulfonate and acrylic acid obtained in the step e passes through a micromixer 2 in a form of stable continuous flow according to the volume flow ratio of 1:3, and is rapidly heated to 86 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize, and the reaction residence time is controlled to be 5min (by adjusting the length of a reaction pipeline in the water bath 2), so that the mixed solution still in the polymerization stage is obtained;
g. Polymerization termination:
the chain transfer agent aqueous solution prepared in the step d and the mixed solution still in the polymerization stage obtained in the step f pass through a micromixer 3 in a form of stable continuous flow according to the volume flow ratio of 1:3, and are rapidly cooled to below 40 ℃ under the temperature control condition of a water bath 3, so that the polymerization reaction is stopped, and the mixed solution is obtained;
h. post-treatment:
and (3) after the mixed solution obtained in the step (g) is discharged out of the micromixer (3), adjusting the PH to 8 by using alkali liquor, and performing spray drying (the obtained powdery particle product) to obtain the styrene-acrylic acid copolymer type dispersing agent.
Example 14: see fig. 1:
a preparation method of a styrene-acrylic acid copolymer type dispersing agent comprises the following steps:
a. preparation of an aqueous sodium styrenesulfonate solution:
adding 100 parts by mass of sodium styrenesulfonate into 260 parts by mass of water, stirring and mixing to prepare a sodium styrenesulfonate aqueous solution, and standing at normal temperature for later use;
b. preparing an acrylic mixed solution:
153 parts by mass of acrylic acid, 38 parts by mass of methacrylic acid, 37 parts by mass of methyl methacrylate and 37 parts by mass of hydroxypropyl acrylate are stirred and mixed by a high-speed stirrer to prepare an acrylic acid mixed solution, and the acrylic acid mixed solution is placed at normal temperature for standby;
c. Preparing an aqueous initiator solution:
adding 18.3 parts by mass of persulfate initiator into 175 parts by mass of water, stirring and mixing to prepare an initiator aqueous solution, and standing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 6.1 parts by mass of sodium bisulphite into 500 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and standing at normal temperature for later use;
e. micromixing of sodium styrenesulfonate aqueous solution and acrylic mixed solution:
the sodium styrenesulfonate aqueous solution prepared in the step a and the acrylic acid mixed solution prepared in the step b are respectively conveyed by a conveying pump according to the volume flow ratio of 1:0.7 and simultaneously conveyed in a stable continuous flow mode and pass through a micromixer 1, and the temperature is quickly increased to 59 ℃ under the temperature control condition of a water bath 1, so that the sodium styrenesulfonate-acrylic acid mixed solution is obtained;
f. initiating reaction polymerization of sodium styrenesulfonate-acrylic acid mixed solution:
c, the initiator aqueous solution prepared in the step c is pumped by a delivery pump and the mixed solution of sodium styrenesulfonate and acrylic acid obtained in the step e passes through a micromixer 2 in a form of stable continuous flow according to the volume flow ratio of 1:3, and is rapidly heated to 85-90 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize, and the reaction residence time is controlled to be 5min (by adjusting the length of a reaction pipeline in the water bath 2) to obtain the mixed solution still in the polymerization stage;
g. Polymerization termination:
the chain transfer agent aqueous solution prepared in the step d and the mixed solution still in the polymerization stage obtained in the step f pass through a micromixer 3 in a form of stable continuous flow according to the volume flow ratio of 1:3, and are rapidly cooled to below 40 ℃ under the temperature control condition of a water bath 3, so that the polymerization reaction is stopped, and the mixed solution is obtained;
h. post-treatment:
and (3) after the mixed solution obtained in the step (g) is discharged out of the micromixer (3), adjusting the PH to 7 by using alkali liquor, and performing spray drying to obtain the styrene-acrylic copolymer dispersing agent.
Example 15: see fig. 1:
a preparation method of a styrene-acrylic acid copolymer type dispersing agent comprises the following steps:
a. preparation of an aqueous sodium styrenesulfonate solution:
adding 100 parts by mass of sodium styrenesulfonate into 280 parts by mass of water, stirring and mixing to prepare a sodium styrenesulfonate aqueous solution, and standing at normal temperature for later use;
b. preparing an acrylic mixed solution:
mixing 135 parts by mass of acrylic acid, 36 parts by mass of methacrylic acid, 38 parts by mass of methyl methacrylate and 39 parts by mass of hydroxypropyl acrylate by stirring with a high-speed stirrer to obtain an acrylic acid mixed solution, and standing at normal temperature for later use;
c. Preparing an aqueous initiator solution:
adding 33 parts by mass of persulfate initiator into 180 parts by mass of water, stirring and mixing to prepare an initiator aqueous solution, and standing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 11 parts by mass of sodium bisulphite into 460 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and standing at normal temperature for later use;
e. micromixing of sodium styrenesulfonate aqueous solution and acrylic mixed solution:
the sodium styrenesulfonate aqueous solution prepared in the step a and the acrylic acid mixed solution prepared in the step b are respectively conveyed by a conveying pump according to the volume flow ratio of 1:0.7 and simultaneously conveyed in a stable continuous flow mode and pass through a micromixer 1, and the temperature is quickly increased to 62 ℃ under the temperature control condition of a water bath 1, so that the sodium styrenesulfonate-acrylic acid mixed solution is obtained;
f. initiating reaction polymerization of sodium styrenesulfonate-acrylic acid mixed solution:
c, the initiator aqueous solution prepared in the step c is pumped by a delivery pump and the mixed solution of sodium styrenesulfonate and acrylic acid obtained in the step e passes through a micromixer 2 in a form of stable continuous flow according to the volume flow ratio of 1:3, and is rapidly heated to 87 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize, and the reaction residence time is controlled to be 4min (by adjusting the length of a reaction pipeline in the water bath 2), so that the mixed solution still in the polymerization stage is obtained;
g. Polymerization termination:
the chain transfer agent aqueous solution prepared in the step d and the mixed solution still in the polymerization stage obtained in the step f pass through a micromixer 3 in a form of stable continuous flow according to the volume flow ratio of 1:3, and are rapidly cooled to below 40 ℃ under the temperature control condition of a water bath 3, so that the polymerization reaction is stopped, and the mixed solution is obtained;
h. post-treatment:
and (3) after the mixed solution obtained in the step (g) is discharged out of the micromixer (3), adjusting the PH to 7.5 by using alkali liquor, and performing spray drying to obtain the styrene-acrylic copolymer type dispersing agent.
Example 16: see fig. 1:
a preparation method of a styrene-acrylic acid copolymer type dispersing agent comprises the following steps:
a. preparation of an aqueous sodium styrenesulfonate solution:
adding 100 parts by mass of sodium styrenesulfonate into 290 parts by mass of water, stirring and mixing to prepare a sodium styrenesulfonate aqueous solution, and standing at normal temperature for later use;
b. preparing an acrylic mixed solution:
110 parts by mass of acrylic acid, 30 parts by mass of methacrylic acid, 30 parts by mass of methyl methacrylate and 30 parts by mass of hydroxypropyl acrylate are stirred and mixed by a high-speed stirrer to prepare an acrylic acid mixed solution, and the acrylic acid mixed solution is placed at normal temperature for standby;
c. Preparing an aqueous initiator solution:
adding 45 parts by mass of persulfate initiator into 230 parts by mass of water, stirring and mixing to prepare an initiator aqueous solution, and standing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 15 parts by mass of sodium bisulphite into 550 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and standing at normal temperature for later use;
e. micromixing of sodium styrenesulfonate aqueous solution and acrylic mixed solution:
the sodium styrenesulfonate aqueous solution prepared in the step a and the acrylic acid mixed solution prepared in the step b are respectively conveyed by a conveying pump according to the volume flow ratio of 1:0.7 and simultaneously conveyed in a stable continuous flow mode and pass through a micromixer 1, and the temperature is quickly increased to 60 ℃ under the temperature control condition of a water bath 1, so that the sodium styrenesulfonate-acrylic acid mixed solution is obtained;
f. initiating reaction polymerization of sodium styrenesulfonate-acrylic acid mixed solution:
c, the initiator aqueous solution prepared in the step c is pumped by a delivery pump and the mixed solution of sodium styrenesulfonate and acrylic acid obtained in the step e passes through a micromixer 2 in a form of stable continuous flow according to the volume flow ratio of 1:3, and is rapidly heated to 89 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize, and the reaction residence time is controlled to be 3min (by adjusting the length of a reaction pipeline in the water bath 2) to obtain the mixed solution still in the polymerization stage;
g. Polymerization termination:
the chain transfer agent aqueous solution prepared in the step d and the mixed solution still in the polymerization stage obtained in the step f pass through a micromixer 3 in a form of stable continuous flow according to the volume flow ratio of 1:3, and are rapidly cooled to below 40 ℃ under the temperature control condition of a water bath 3, so that the polymerization reaction is stopped, and the mixed solution is obtained;
h. post-treatment:
and (3) after the mixed solution obtained in the step (g) is discharged out of the micromixer (3), adjusting the PH to 8 by using alkali liquor, and performing spray drying (the obtained powdery particle product) to obtain the styrene-acrylic acid copolymer type dispersing agent.
In examples 9-16 above: the persulfate initiator in the step c belongs to a water-soluble free radical polymerization initiator and can be any one of potassium persulfate, sodium persulfate and ammonium persulfate.
In examples 9-16 above: the alkali liquor in the step h is one or a mixture of two of sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
In examples 9-16 above: the water used in the step a, the step b and the step c is pure water, distilled water, deionized water and the like so as to reduce the influence of redundant ions in the water on free radical polymerization and other side reactions.
In examples 9-16 above: the conveying pump used in the step e, the step f and the step g can be a constant flow pump or a advection pump, the required flow is continuous and stable, and typically an MP2010D medium-pressure constant flow pump of Shanghai three of science and instruments, a TBP2H10S advection pump of Shanghai field same biotechnology Co, and the like are provided.
In examples 9-16 above: the micromixers used in step e, step f, step g may be static mixers, typically 0.5-2.6ml HP type mixers supplied by Shimadzu corporation, etc.
In examples 9-16 above: the high-speed mixer in the step b may be FA, FAB, FAS, FM, FMB, an emulsifying machine of FMS series, etc. manufactured by Fluko, germany.
In examples 9-16 above: the reaction tubes used in step e, step f and step g which are in communication with the micromixers and convey the material are preferablyThe length of each section of reaction pipeline and the flow of the pump are adjusted to freely control the residence reaction time in each section of water bath kettle.
In examples 9-16 above: and e, f and g, enabling each continuous flow in the step e, f and g to pass through a conveying pump and stably and continuously pass through the mixers in each stage in a constant flow ratio mode to realize mixing, initiation, polymerization and termination, so as to ensure the uniformity of the reaction environment and the stability of the final product.
In examples 9-16 above: the sodium styrenesulfonate in the step a can be of industrial grade, and the product suppliers include Shanghai microphone Biochemical technology Co., ltd.
In examples 9-16 above: the raw materials in the acrylic acid in the step b are preferably analytically pure, and suppliers include Shanghai microphone Biotechnology Co., ltd, shanghai Baishun Biotechnology Co., ltd, and the like.
In the above embodiment: the percentages used are not particularly indicated, and are all percentages by mass (weight) or percentages known to those skilled in the art; the proportions used are not particularly specified, but are mass (weight) proportions; the parts by weight may all be g or kg.
In the above embodiment: the process parameters (temperature, time, etc.) and the amount of each component in each step are within the range, and any point is applicable.
The technical contents of the invention and the technical contents not specifically described in the above embodiments are the same as the prior art, and the raw materials are all commercial products.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.
Claims (10)
1. A preparation method of a styrene-acrylic acid copolymer type dispersing agent is characterized by comprising the following steps:
a. Preparation of an aqueous sodium styrenesulfonate solution:
adding 100 parts by mass of sodium styrenesulfonate into 150-400 parts by mass of water, and stirring and mixing to prepare sodium styrenesulfonate water solution for later use;
b. preparing an acrylic mixed solution:
mixing 100-200 parts by mass of acrylic acid, 25-50 parts by mass of methacrylic acid, 25-50 parts by mass of methyl methacrylate and 25-50 parts by mass of hydroxypropyl acrylate by a high-speed stirrer to prepare an acrylic acid mixed solution for later use;
c. preparing an aqueous initiator solution:
adding 15-45 parts by mass of persulfate initiator into 85-250 parts by mass of water, and stirring and mixing to obtain an initiator aqueous solution for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 5-15 parts by mass of sodium bisulphite into 300-900 parts by mass of water, and stirring and mixing to prepare a chain transfer agent aqueous solution for later use;
e. micromixing of sodium styrenesulfonate aqueous solution and acrylic mixed solution:
the sodium styrenesulfonate aqueous solution prepared in the step a and the acrylic acid mixed solution prepared in the step b are respectively conveyed by a conveying pump according to the volume flow ratio of 1:0.7 and simultaneously conveyed in a stable continuous flow mode and pass through a micromixer 1, and are quickly heated to 50-70 ℃ under the temperature control condition of a water bath 1, so that the sodium styrenesulfonate-acrylic acid mixed solution is obtained;
f. Initiating reaction polymerization of sodium styrenesulfonate-acrylic acid mixed solution:
c, the initiator aqueous solution obtained in the step c is conveyed by a conveying pump and the mixed solution of sodium styrenesulfonate and acrylic acid obtained in the step e passes through a micromixer 2 in a form of stable continuous flow according to the volume flow ratio of 1:3, and the temperature is quickly increased to 85-90 ℃ under the temperature control condition of a water bath 2 so as to initiate and react for polymerization, so that the mixed solution still in a polymerization stage is obtained;
g. polymerization termination:
the chain transfer agent aqueous solution prepared in the step d and the mixed solution still in the polymerization stage obtained in the step f pass through a micromixer 3 in a form of stable continuous flow according to the volume flow ratio of 1:3, and are rapidly cooled to below 40 ℃ under the temperature control condition of a water bath 3 to obtain the mixed solution;
h. post-treatment:
and (3) after the mixed solution obtained in the step (g) is discharged out of the micromixer (3), adjusting the PH to 7-8 by using alkali liquor, and performing spray drying to obtain the styrene-acrylic copolymer type dispersing agent.
2. The method for preparing a styrene-acrylic acid copolymer dispersant as claimed in claim 1, wherein: the persulfate initiator in the step c is any one of potassium persulfate, sodium persulfate and ammonium persulfate.
3. A process for the preparation of a styrene-acrylic acid based co-polymer dispersant as claimed in claim 1 or 2, wherein: the mass dosage of the persulfate initiator in the step c is 5-15% of the total mass of the sodium styrene sulfonate in the step a and the acrylic acid mixed solution in the step b.
4. A process for the preparation of a styrene-acrylic acid based co-polymer dispersant as claimed in claim 1 or 2, wherein: the mass amount of the sodium bisulphite in the step d is 1/3 of that of the persulfate initiator in the step c.
5. A process for preparing a styrene-acrylic acid-based copolymer dispersant as claimed in claim 3, wherein: the mass amount of the sodium bisulphite in the step d is 1/3 of that of the persulfate initiator in the step c.
6. The process for preparing a styrene-acrylic acid-based copolymer dispersant as claimed in claim 1, 2 or 5, wherein: the alkali liquor in the step h is one or a mixture of two of sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
7. The method for preparing a styrene-acrylic acid based copolymer dispersant as claimed in claim 4, wherein: the alkali liquor in the step h is one or a mixture of two of sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
8. The process for preparing a styrene-acrylic acid-based copolymer dispersant as claimed in claim 1, 2, 5 or 7, wherein: the water in the step a, the step b and the step c is pure water, distilled water or deionized water.
9. The process for preparing a styrene-acrylic acid-based copolymer dispersant as claimed in claim 1, 2, 5 or 7, wherein: the conveying pump used in the step e, the step f and the step g is a constant flow pump or a advection pump.
10. The process for preparing a styrene-acrylic acid-based copolymer dispersant as claimed in claim 1, 2, 5 or 7, wherein: the micromixers used in step e, step f, step g are static mixers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110667232.2A CN113501902B (en) | 2021-06-16 | 2021-06-16 | Preparation method of styrene-acrylic acid copolymer type dispersing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110667232.2A CN113501902B (en) | 2021-06-16 | 2021-06-16 | Preparation method of styrene-acrylic acid copolymer type dispersing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113501902A CN113501902A (en) | 2021-10-15 |
| CN113501902B true CN113501902B (en) | 2023-08-18 |
Family
ID=78009940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110667232.2A Active CN113501902B (en) | 2021-06-16 | 2021-06-16 | Preparation method of styrene-acrylic acid copolymer type dispersing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113501902B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273113A (en) * | 2015-10-29 | 2016-01-27 | 清华大学 | Polyacrylic acid synthesis reaction apparatus and polyacrylic acid synthesis method |
| CN110950760A (en) * | 2019-12-11 | 2020-04-03 | 福州大学 | Process for synthesizing tert-butyl acrylate |
| WO2020255727A1 (en) * | 2019-06-20 | 2020-12-24 | Dic株式会社 | Block copolymer intermediate, block copolymer, and production methods for same |
-
2021
- 2021-06-16 CN CN202110667232.2A patent/CN113501902B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273113A (en) * | 2015-10-29 | 2016-01-27 | 清华大学 | Polyacrylic acid synthesis reaction apparatus and polyacrylic acid synthesis method |
| WO2020255727A1 (en) * | 2019-06-20 | 2020-12-24 | Dic株式会社 | Block copolymer intermediate, block copolymer, and production methods for same |
| CN110950760A (en) * | 2019-12-11 | 2020-04-03 | 福州大学 | Process for synthesizing tert-butyl acrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113501902A (en) | 2021-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW466246B (en) | Aqueous dispersion comprising anionic water-soluble or water-swellable polymers and its process for making the same and uses | |
| CN101717479B (en) | Amphiphilic gradient copolymer | |
| NO20060311L (en) | Aqueous dispersions of water-soluble polymerisates of ethylenically unsaturated anionic monomers production method and use thereof | |
| Liu et al. | Preparation of poly (acrylamide-co-acrylic acid) aqueous latex dispersions using anionic polyelectrolyte as stabilizer | |
| CN106866881A (en) | Hydrophobic association acrylamide copolymer emulsion and preparation method thereof | |
| TWI490236B (en) | Method for the preparation of styrenic fluoropolymers | |
| CN106492706A (en) | Comb-type polymer dispersant, preparation method and application thereof | |
| CN111087535B (en) | Method for preparing high-solid-content inverse emulsion polymer with high efficiency and energy conservation | |
| CN107216421B (en) | A kind of monodisperse polystyrene microsphere and the preparation method and application thereof | |
| CN101372525A (en) | Method for preparing non-ionic hydrophobic association polymerization water-soluble polymer from reverse micro emulsion | |
| Xu et al. | Preparation of cationic polyacrylamide by aqueous two-phase polymerization | |
| AU732835B2 (en) | Aqueous dispersions | |
| MXPA01003439A (en) | WATERPROOF DISPERSIONS | |
| CN107189009A (en) | A kind of method that aqueous dispersion polymerization prepares cation polyacrylamide emulsion | |
| US5696228A (en) | Process for producing substantially dry polymer particles from aqueous dispersions | |
| CN102086249A (en) | Method for preparing hyperbranched ethylene or acrylamide polymer by inverse emulsion polymerization | |
| CN113501902B (en) | Preparation method of styrene-acrylic acid copolymer type dispersing agent | |
| Chen et al. | Preparation and characterization of pure polyacrylate polymer colloid through emulsion polymerization using a novel initiator | |
| CN104151463B (en) | In a kind of miniemulsion, photoinduction active free radical polymerization prepares polymer and technique | |
| US5792366A (en) | Aqueous dispersions | |
| US5843320A (en) | Aqueous dispersions | |
| CN107236078B (en) | Preparation method of flexible soft monomer colloid photonic crystal emulsion | |
| US20010014712A1 (en) | Aqueous dispersions | |
| Aguirreurreta et al. | Anionic polymerizable surfactants and stabilizers in emulsion polymerization: A comparative study | |
| US20020058745A1 (en) | Aqueous dispersions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |