CN113501902A - Preparation method of styrene-acrylic acid copolymerization type dispersing agent - Google Patents
Preparation method of styrene-acrylic acid copolymerization type dispersing agent Download PDFInfo
- Publication number
- CN113501902A CN113501902A CN202110667232.2A CN202110667232A CN113501902A CN 113501902 A CN113501902 A CN 113501902A CN 202110667232 A CN202110667232 A CN 202110667232A CN 113501902 A CN113501902 A CN 113501902A
- Authority
- CN
- China
- Prior art keywords
- aqueous solution
- mass
- mixed solution
- parts
- acrylic
- 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.)
- Granted
Links
Images
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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a preparation method of a styrene-acrylic acid copolymerization type dispersing agent, which is characterized by comprising the following steps: preparing a sodium styrene sulfonate aqueous solution, an acrylic mixed solution, a persulfate initiator aqueous solution and a sodium bisulfite chain transfer agent aqueous solution, mixing the sodium styrene sulfonate aqueous solution and the acrylic mixed solution through a micro mixer, heating, mixing the mixture with the initiator aqueous solution again through the micro mixer, initiating polymerization at a fixed point, adding the chain transfer agent aqueous solution at a fixed point after the mixture passes through the micro mixer at the later stage of the reaction to terminate the reaction, and performing post-treatment to obtain the styrene-acrylic copolymer dispersant. The invention adopts the micro-mixer to carry out reaction, the reaction is immediately terminated after the reaction is finished 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 copolymerization type 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 copolymerization type dispersing agent. The styrene-acrylic acid copolymerization type dispersing agent prepared by the invention is suitable for the fields of pesticides, pigments, dyes and the like.
Background
The dispersant has important application in the fields of pesticides, pigments, dyes and the like. The traditional small-molecule dispersing agent is easy to dissociate from the surface of solid particles, so that the traditional small-molecule dispersing agent fails. The carboxylate copolymer dispersant is a water-soluble anionic polymer dispersant, and the system is dispersed stably mainly through electrostatic repulsion stabilization and steric hindrance, is insensitive to the temperature, pH value and ionic strength of the system, and can exert the dispersing capacity to the maximum extent in an aqueous system. The electrostatic repulsion stabilization mechanism is that the high molecular dispersing agent is ionized to form an electric double layer on the surface of the nanometer particles, and the nanometer particles are stably present in the medium through the electrostatic repulsion. The steric stabilization is based on the theory that the macromolecular dispersant forms a complete covering layer which is firmly adsorbed on the surface of the nanometer particles and has enough adsorption layer thickness (1-10 nm). Meanwhile, compared with the 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 dispersed particles, and has large adsorption quantity. In general, homopolymers are not good dispersants because they are good solvating chains or good anchoring groups, and good repulsive stabilization requires both, and most of them are copolymers, such as random, graft or block copolymers, which are both used as the polymer of the pigment dispersant in the aqueous system. Therefore, a high molecular type carboxylate copolymer such as a styrene-acrylic copolymer dispersant can make the dispersion system more stable by charge action and steric hindrance, and thus has a better dispersing effect than a small molecular type dispersant.
The traditional copolymer dispersant is usually synthesized by an intermittent kettle-type synthesis method, styrene, acrylic acid and the like are used as raw material monomers, a water-soluble redox system is used as an initiator, water and the like are used as a solvent, all the materials are fed in a dropwise manner at a constant temperature according to a certain proportion, polymerization is completed by heat preservation reaction and addition of a terminator, and then a powdery product is finally obtained by post-treatment processes such as acid-base neutralization, spray drying and the like. The above synthetic route belongs to the radical polymerization mechanism. The reaction process of free radical polymerization mostly belongs to quick and strong exothermic volatile control reaction, the common expression of the reaction is that the reaction can not be initiated when a certain condition is not reached, and the reaction is easy to be out of control when the condition is slightly higher than the certain condition; in the initial stage of free radical polymerization, the initiator is slowly initiated to form a primary free radical, once the primary free radical is generated, the monomer is rapidly initiated to carry out polymerization, and the step can be completed in a few seconds or even shorter time; the characteristics of slow initiation, fast growth and fast termination of free radical polymerization determine that a high molecular polymer is generated in a very short time, most of free radical polymerization reactions are strong exothermic reactions, fast heat release easily promotes the improvement of the reaction speed, and the phenomenon of automatic acceleration occurs. Therefore, the implementation route of the prior art has the problems of easy runaway and implosion of reaction, high safety risk, high equipment investment, poor product batch stability and the like of the traditional intermittent 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 acid copolymerization type dispersing agent. The invention provides a preparation method of styrene-acrylic acid copolymerization type dispersing agent with excellent dispersing effect by mixing a sodium styrene sulfonate aqueous solution and an acrylic acid mixed solution through a micro mixer, heating, mixing with an initiator aqueous solution again through the micro mixer, initiating at a fixed point to polymerize the initiator aqueous solution, adding a chain transfer agent aqueous solution at a fixed point after passing through the micro mixer at the later stage of reaction to terminate the reaction, and performing post-treatment.
The content of the invention is as follows: a preparation method of styrene-acrylic acid copolymerization type dispersing agent is characterized by comprising the following steps:
a. preparing an aqueous solution of sodium styrene sulfonate:
adding 100 parts by mass of sodium styrene sulfonate into 150-400 parts by mass of water, stirring and mixing to prepare a sodium styrene sulfonate aqueous solution with the concentration of 40-20%, and placing at normal temperature for later use; too low a concentration will result in too slow a subsequent reaction rate and a doubling 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:
stirring and 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 (and other acrylic monomers) by a high-speed stirrer to prepare an acrylic mixed solution, and placing the acrylic mixed solution at normal temperature for later use;
c. preparing an initiator aqueous 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 placing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 5-15 parts by mass of sodium bisulfite into 300-900 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and placing at normal temperature for later use;
e. micro-mixing of sodium styrene sulfonate aqueous solution and acrylic acid mixed solution:
respectively conveying the sodium styrene sulfonate aqueous solution prepared in the step a and the acrylic mixed solution prepared in the step b by using a conveying pump according to the volume flow ratio of 1:0.7 and in a stable continuous flow mode, passing through a micro mixer 1, and rapidly heating to 50-70 ℃ under the temperature control condition of a water bath 1 to obtain the sodium styrene sulfonate-acrylic mixed solution;
f. polymerization of the initiation reaction of the sodium styrene sulfonate-acrylic acid mixed solution:
b, enabling the initiator aqueous solution prepared in the step c to pass through a delivery pump and the mixed solution of sodium styrene sulfonate and acrylic acid obtained in the step e to pass through a micro mixer 2 in a stable continuous flow mode according to the volume flow ratio of 1:3, rapidly heating to 85-90 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize, and controlling the reaction residence time 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. termination of the polymerization:
d, enabling the chain transfer agent aqueous solution prepared in the step d to pass through a delivery pump, enabling the chain transfer agent aqueous solution and the mixed solution obtained in the step f and still in the polymerization stage to pass through a micro mixer 3 in a stable continuous flow mode according to the volume flow ratio of 1:3, and rapidly cooling to be below 40 ℃ under the temperature control condition of a water bath 3 to terminate the polymerization reaction to obtain mixed solution;
h. and (3) post-treatment:
and g, after the mixed solution obtained in the step g is discharged out of the micro mixer 3, adjusting the pH value to 7-8 by using alkali liquor, and performing spray drying to obtain a powdery particle product, namely the styrene-acrylic acid copolymerization type dispersing agent.
The invention comprises the following steps: 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.
The invention comprises the following steps: the mass usage amount 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 mixed solution in the step b; if the ratio (concentration) is too low, the initiation rate will be slow and the polymerization residence time in step f will be doubled; if the ratio (concentration) is too high, the reaction is too fast, and the efficiency of temperature control of the water bath cannot be matched.
The invention comprises the following steps: the mass amount of the sodium bisulfite in the step d is 1/3 of the mass amount of the persulfate initiator in the step c; the effect of rapid fixed-point termination reaction cannot be realized if the proportion of the sodium bisulfite is low, and other side reactions occur and the polymerization degree is reduced if the proportion is high.
The invention comprises the following steps: 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.
The invention comprises the following steps: the water used in steps a, b and c can be pure water, distilled water, deionized water and the like, so as to reduce the influence of redundant ions in the water on the free radical polymerization and the occurrence of other side reactions.
The invention comprises the following steps: the delivery pump used in the steps e, f and g can be a constant flow pump or a constant flow pump, and the flow rate is required to be continuously stable, and typically comprises an MP2010D medium-pressure constant flow pump of shanghai three scientific instruments ltd, a TBP2H10S type constant flow pump of shanghai field biotechnology ltd, and the like.
The invention comprises the following steps: the micromixer used in step e, step f, step g may be a static mixer, typically a 0.5-2.6ml HP-type mixer available from Shimadzu corporation, or the like.
The invention comprises the following steps: the high-speed stirrer used in step b may be an emulsifier of FA, FAB, FAS, FM, FMB or FMS series manufactured by Fluko of Germany, or the like.
The invention comprises the following steps: the reaction pipeline used in step e, step f and step g for communicating each micromixer and the material conveying pipeline is preferably a pipeline
The polytetrafluoroethylene (PTFE for short) pipeline can freely regulate and control the residence reaction time in the water bath kettle of each section by regulating the length of each section of reaction pipeline and the flow of the pump.
The invention comprises the following steps: the continuous flows in the steps e, f and g must be mixed, initiated, polymerized and terminated by a delivery pump and a mixer in each stage in a stable and continuous manner in a constant flow ratio, so as to ensure the uniformity of the reaction environment and the stability of the final product.
The invention comprises the following steps: the sodium styrene sulfonate in step a can be in industrial grade, and the product supplier is Shanghai Michelin Biochemical technology Co.
The invention comprises the following steps: the raw materials in the acrylic acid-based compound in step b are preferably analytical pure compounds, and the suppliers include Shanghai Michelin 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) the styrene-acrylic acid copolymerization type dispersing agent with good dispersing effect is prepared by mixing a sodium styrene sulfonate aqueous solution and an acrylic acid mixed solution through a micro mixer, heating, mixing with an initiator aqueous solution again through the micro mixer, initiating at a fixed point to polymerize the initiator aqueous solution, adding a chain transfer agent aqueous solution at a fixed point after passing through the micro mixer at the later stage of reaction to terminate the reaction, and performing post-treatment;
(2) the invention adopts the micro mixer to carry out reaction, the micro mixer has small internal size, so that the diffusion path of reactants is short, the time for realizing full mixing can be obviously shortened, and the micro mixer has good heat transfer performance and is easier to realize accurate temperature control due to the extremely large specific surface area; the micro mixer can more conveniently control the free radical polymerization reaction due to good heat and mass transfer characteristics, and simultaneously can change the intermittent reaction into a continuous flow process, initiate the reaction at a specified time and position, and immediately terminate the reaction after finishing the reaction in a short time, so that the reaction process is easy to control, the efficiency is high, and the effect is good;
(3) in the invention, the styrene-acrylic acid copolymerization type dispersing agent is prepared by adopting sectional micro-mixing and in a constant flow and continuous flow mode, the fixed-point initiation and fixed-point termination polymerization are realized by optimizing the catalyst and controlling the temperature and the residence time (the length of a reaction pipeline) of each stage, the uniformity of a reaction environment can be ensured, the molecular weight of the obtained product is controllable, the stability of the product batch is good, the reaction heat release is controllable, the equipment investment is small, and the operation and the use are safe;
(4) the preparation method has the advantages of simple preparation process, simple and convenient process, easy operation and strong practicability.
Drawings
FIG. 1 is a schematic diagram of a process for preparing styrene-acrylic copolymer dispersant according to the present invention.
Detailed Description
The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.
The following examples and comparative examples according to the invention relate to the test method:
(1) the number average relative molecular weight was measured by using a gel permeation chromatograph with an 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, then adding water to 100ml, and turning up and down for 30 times, wherein turning up and down for 180 degrees and then returning to the original position for 1 time; vertically placing the measuring cylinder in water bath at 25 deg.C without vibration, avoiding sunlight irradiation, removing the upper 90ml suspension with a pipette after 30min, transferring the rest 10ml suspension and precipitate to a weighed mass m1Washing the measuring cylinder with distilled water in the watch glass to ensure that all sediments in the measuring cylinder are transferred to the watch glass, putting the watch glass into an oven for drying, and weighing m2Calculating mass M of insoluble substance, M ═ M2-m1To determine its suspension rate.
The suspension ratio calculation formula is as follows:
suspension rate (1.400-M) ÷ 1.400X 10 ÷ 9X 100%
Wherein: m is the mass (g) of the dispersant and the solid particles contained in 10ml of the bottom of a 100ml measuring cylinder with a plug, and 1.400 is the total mass (g) of the dispersant and the solid particles contained in the 100ml measuring cylinder with a plug.
(3) The dispersibility test of the dispersant on water dispersible granule pesticides is as follows:
the dispersant was used to prepare a water dispersible granule pesticide, then 1.0g of this water dispersible granule pesticide was weighed out and transferred to a beaker, 50ml of distilled water was added, left to stand for 30s, stirred with a glass rod for 30s, the suspension was transferred with water to a 100ml measuring cylinder with a stopper, and distilled water was added to bring the suspension to 100 ml. Tightly plugging the measuring cylinder, and turning the measuring cylinder upside down for 30 times within 1 min; the measuring cylinder is immersed in a constant temperature water bath to 100ml of scale mark and kept stand for 30min, and the temperature in the constant temperature water bath is kept at 30 ℃. After 30min the upper 90ml suspension was removed with a pipette without shaking or stirring the sediment in the graduated cylinder, ensuring that the tip was always a few millimeters below the surface of the liquid. The remaining 10ml of suspension and precipitate are transferred to a weighed mass m1The measuring cylinder is flushed with distilled water to ensure that all precipitates in the measuring cylinder are transferred into the watch glass, the watch glass is put into an oven to be dried, and the watch glass is weighed to be m2The mass M (M) of the insoluble matter was calculated2-m1) And then the suspension ratio was calculated.
The suspension ratio calculation formula is as follows:
suspension rate (1.00-M) ÷ 1.00X 10 ÷ 9X 100%
The amounts of the substances used in the following examples are all 100% by weight, and are described in detail below.
Examples 1 to 8: referring to figure 1:
a preparation method of styrene-acrylic acid copolymerization type dispersant comprises the following steps:
a. preparing an aqueous solution of sodium styrene sulfonate:
adding 100 parts by mass of sodium styrene sulfonate into 150-400 parts by mass of water, stirring and mixing for 10min to prepare a sodium styrene sulfonate aqueous solution with the concentration of 40-20%, and placing at normal temperature for later use;
b. preparing an acrylic mixed solution:
stirring and 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 using a high-speed stirrer to prepare an acrylic mixed solution, and placing the acrylic mixed solution at normal temperature for later use;
c. preparing an initiator aqueous 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 placing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 5-15 parts by mass of sodium bisulfite into 300-900 parts by mass of water, stirring and mixing for 10min to prepare a chain transfer agent aqueous solution, and placing at normal temperature for later use;
e. micro-mixing of sodium styrene sulfonate aqueous solution and acrylic acid mixed solution:
respectively conveying the sodium styrene sulfonate aqueous solution prepared in the step a and the acrylic mixed solution prepared in the step b by using a conveying pump according to a volume flow ratio of 1:0.7 (the flow rate is adjustable within a range of 10-90% of a pump body), simultaneously conveying the sodium styrene sulfonate aqueous solution and the acrylic mixed solution in a stable continuous flow form, passing the sodium styrene sulfonate aqueous solution and the acrylic mixed solution through a micro mixer 1, and rapidly heating the sodium styrene sulfonate aqueous solution and the acrylic mixed solution to 50-70 ℃ under the temperature control condition of a water bath 1 (the temperature is ensured to stay for 1-2 min by adjusting the length of a reaction pipeline in the water bath 1), so as to obtain the sodium styrene sulfonate-acrylic mixed solution;
f. polymerization of the initiation reaction of the sodium styrene sulfonate-acrylic acid mixed solution:
c, enabling the initiator aqueous solution prepared in the step c to pass through a delivery pump, enabling the initiator aqueous solution to pass through a micro mixer 2 in a stable continuous flow mode according to the volume flow ratio of 1:3 (the flow rate is adjustable within the range of 10-90% of a pump body), rapidly heating to 85-90 ℃ under the temperature control condition of a water bath 2 to enable the initiator aqueous solution and the mixed solution of sodium styrene sulfonate and acrylic acid obtained in the step e to initiate and (rapidly) react and polymerize, and controlling the reaction residence time 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. termination of the polymerization:
b, enabling the chain transfer agent aqueous solution prepared in the step d to pass through a delivery pump, enabling the chain transfer agent aqueous solution and the mixed solution obtained in the step f and still in the polymerization stage to pass through a micro mixer 3 according to the volume flow ratio of 1:3 (the flow rate can be adjusted within the range of 10-90% of the range of a pump body), meanwhile, enabling the mixed solution to pass through a stable continuous flow mode, and rapidly cooling to be below 40 ℃ under the temperature control condition of a water bath 3 (the reaction residence time is maintained to be 0.5-1 min by adjusting the length of a reaction pipeline in the water bath 3, and the temperature is reduced), so that the polymerization reaction is terminated, and obtaining the mixed solution;
h. and (3) post-treatment:
and g, after the mixed solution obtained in the step g is discharged from the micro mixer 3, adjusting the pH to 7-8 by using alkali liquor, and performing spray drying to obtain a powdery particle product, namely the styrene-acrylic acid copolymerization type dispersing agent.
The specific dosage, process parameters, test results and the like of each of the examples 1-8 are shown in the following table:
table 1: examples 1-8 Process parameter Table for preparing sodium styrene sulfonate aqueous solution
Table 2: examples 1-8 Process parameter tables for preparing acrylic acid mixtures
Note: the examples above employ a high speed stirred emulsifier made by Fluko of Germany under the model FA 25.
Table 3: examples 1-8 Process parameter Table for preparing aqueous solution of initiator
Note: in Table 3, the "mass percentage of the initiator to the total mass of the monomers" is the mass percentage of the (persulfate) initiator to the total mass (i.e., the total mass) of the sodium styrene sulfonate in the step a and the acrylic mixed solution in the step b.
Table 4: examples 1-8 Table of Process parameters for preparing aqueous solutions of chain transfer agents
Table 5: examples 1-8 micro-mixing Process parameter tables for sodium styrene sulfonate aqueous solution and acrylic acid-based Mixed solution
Table 6: examples 1-8 polymerization Process parameters for the initiation of sodium styrene sulfonate-acrylic acid mixtures
Table 7: EXAMPLES 1-8 polymerization termination Process parameter tables
Table 8: test results of the products of examples 1 to 8
The post-treatment processes of adding alkali to adjust the pH, spray drying and the like for preparing the dispersing agent in the embodiments 1 to 8 of the invention are omitted, and the operation method is the same as that in the prior art.
Example 9: referring to figure 1:
a preparation method of styrene-acrylic acid copolymerization type dispersant comprises the following steps:
a. preparing an aqueous solution of sodium styrene sulfonate:
adding 100 parts by mass of sodium styrene sulfonate into 150 parts by mass of water, stirring and mixing to prepare a sodium styrene sulfonate aqueous solution with the concentration of 40%, and placing at normal temperature for later use;
b. preparing an acrylic mixed solution:
stirring and mixing 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 by a high-speed stirrer to prepare an acrylic mixed solution, and placing the acrylic mixed solution at normal temperature for later use;
c. preparing an initiator aqueous 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 placing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 5 parts by mass of sodium bisulfite into 300 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and placing at normal temperature for later use;
e. micro-mixing of sodium styrene sulfonate aqueous solution and acrylic acid mixed solution:
respectively conveying the sodium styrene sulfonate aqueous solution prepared in the step a and the acrylic mixed solution prepared in the step b by using a conveying pump according to the volume flow ratio of 1:0.7 and in a stable continuous flow mode, passing through a micro mixer 1, and rapidly heating to 50 ℃ under the temperature control condition of a water bath 1 to obtain the sodium styrene sulfonate-acrylic mixed solution;
f. polymerization of the initiation reaction of the sodium styrene sulfonate-acrylic acid mixed solution:
c, enabling the initiator aqueous solution prepared in the step c to pass through a delivery pump, enabling the initiator aqueous solution and the mixed solution of sodium styrene sulfonate and acrylic acid obtained in the step e to pass through a micro mixer 2 in a stable continuous flow mode according to the volume flow ratio of 1:3, and rapidly heating to 85 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize to obtain a mixed solution in a polymerization stage;
g. termination of the polymerization:
d, enabling the chain transfer agent aqueous solution prepared in the step d to pass through a delivery pump, enabling the chain transfer agent aqueous solution and the mixed solution obtained in the step f and still in the polymerization stage to pass through a micro mixer 3 in a stable continuous flow mode according to the volume flow ratio of 1:3, and rapidly cooling to be below 40 ℃ under the temperature control condition of a water bath 3 to terminate the polymerization reaction to obtain mixed solution;
h. and (3) post-treatment:
and g, after the mixed solution obtained in the step g is discharged out of the micro mixer 3, adjusting the pH to 7 by using alkali liquor, and performing spray drying to obtain a powdery particle product, namely the styrene-acrylic acid copolymerization type dispersing agent.
Example 10: referring to figure 1:
a preparation method of styrene-acrylic acid copolymerization type dispersant comprises the following steps:
a. preparing an aqueous solution of sodium styrene sulfonate:
adding 100 parts by mass of sodium styrene sulfonate into 400 parts by mass of water, stirring and mixing to prepare a sodium styrene sulfonate aqueous solution with the concentration of 20%, and placing at normal temperature for later use;
b. preparing an acrylic mixed solution:
stirring and mixing 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 by a high-speed stirrer to prepare an acrylic mixed solution, and placing the acrylic mixed solution at normal temperature for later use;
c. preparing an initiator aqueous 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 placing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 15 parts by mass of sodium bisulfite into 900 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and placing at normal temperature for later use;
e. micro-mixing of sodium styrene sulfonate aqueous solution and acrylic acid mixed solution:
respectively conveying the sodium styrene sulfonate aqueous solution prepared in the step a and the acrylic mixed solution prepared in the step b by using a conveying pump according to the volume flow ratio of 1:0.7 and in a stable continuous flow mode, passing through a micro mixer 1, and rapidly heating to 70 ℃ under the temperature control condition of a water bath 1 to obtain the sodium styrene sulfonate-acrylic mixed solution;
f. polymerization of the initiation reaction of the sodium styrene sulfonate-acrylic acid mixed solution:
c, enabling the initiator aqueous solution prepared in the step c to pass through a delivery pump, enabling the initiator aqueous solution and the mixed solution of sodium styrene sulfonate and acrylic acid obtained in the step e to pass through a micro mixer 2 in a stable continuous flow mode according to the volume flow ratio of 1:3, and rapidly heating to 90 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize to obtain a mixed solution in a polymerization stage;
g. termination of the polymerization:
d, enabling the chain transfer agent aqueous solution prepared in the step d to pass through a delivery pump, enabling the chain transfer agent aqueous solution and the mixed solution obtained in the step f and still in the polymerization stage to pass through a micro mixer 3 in a stable continuous flow mode according to the volume flow ratio of 1:3, and rapidly cooling to be below 40 ℃ under the temperature control condition of a water bath 3 to terminate the polymerization reaction to obtain mixed solution;
h. and (3) post-treatment:
and g, after the mixed solution obtained in the step g is discharged out of the micro mixer 3, adjusting the pH to 8 by using alkali liquor, and performing spray drying to obtain a powdery particle product, namely the styrene-acrylic acid copolymerization type dispersing agent.
Example 11: referring to figure 1:
a preparation method of styrene-acrylic acid copolymerization type dispersant comprises the following steps:
a. preparing an aqueous solution of sodium styrene sulfonate:
adding 100 parts by mass of sodium styrene sulfonate into 235 parts by mass of water, stirring and mixing to prepare a sodium styrene sulfonate aqueous solution, and placing at normal temperature for later use;
b. preparing an acrylic mixed solution:
stirring and mixing 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 by using a high-speed stirrer to prepare an acrylic mixed solution, and placing the acrylic mixed solution at normal temperature for later use;
c. preparing an initiator aqueous 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 placing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 10 parts by mass of sodium bisulfite into 450 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and placing at normal temperature for later use;
e. micro-mixing of sodium styrene sulfonate aqueous solution and acrylic acid mixed solution:
respectively conveying the sodium styrene sulfonate aqueous solution prepared in the step a and the acrylic mixed solution prepared in the step b by using a conveying pump according to the volume flow ratio of 1:0.7 and in a stable continuous flow mode, passing through a micro mixer 1, and rapidly heating to 60 ℃ under the temperature control condition of a water bath 1 to obtain the sodium styrene sulfonate-acrylic mixed solution;
f. polymerization of the initiation reaction of the sodium styrene sulfonate-acrylic acid mixed solution:
c, enabling the initiator aqueous solution prepared in the step c to pass through a delivery pump, enabling the initiator aqueous solution and the mixed solution of sodium styrene sulfonate and acrylic acid obtained in the step e to pass through a micro mixer 2 in a stable continuous flow mode according to the volume flow ratio of 1:3, and rapidly heating to 88 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize to obtain a mixed solution in a polymerization stage;
g. termination of the polymerization:
d, enabling the chain transfer agent aqueous solution prepared in the step d to pass through a delivery pump, enabling the chain transfer agent aqueous solution and the mixed solution obtained in the step f and still in the polymerization stage to pass through a micro mixer 3 in a stable continuous flow mode according to the volume flow ratio of 1:3, and rapidly cooling to be below 40 ℃ under the temperature control condition of a water bath 3 to terminate the polymerization reaction to obtain mixed solution;
h. and (3) post-treatment:
and g, after the mixed solution obtained in the step g is discharged out of the micro mixer 3, adjusting the pH value to 7.5 by using alkali liquor, and performing spray drying to obtain a powdery particle product, namely the styrene-acrylic acid copolymerization type dispersing agent.
Example 12: referring to figure 1:
a preparation method of styrene-acrylic acid copolymerization type dispersant comprises the following steps:
a. preparing an aqueous solution of sodium styrene sulfonate:
adding 100 parts by mass of sodium styrene sulfonate into 265 parts by mass of water, stirring and mixing to prepare a sodium styrene sulfonate aqueous solution, and placing at normal temperature for later use;
b. preparing an acrylic mixed solution:
stirring and 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 using a high-speed stirrer to prepare an acrylic mixed solution, and placing the acrylic mixed solution at normal temperature for later use;
c. preparing an initiator aqueous 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 placing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 10 parts by mass of sodium bisulfite into 430 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and placing at normal temperature for later use;
e. micro-mixing of sodium styrene sulfonate aqueous solution and acrylic acid mixed solution:
respectively conveying the sodium styrene sulfonate aqueous solution prepared in the step a and the acrylic mixed solution prepared in the step b by using a conveying pump according to the volume flow ratio of 1:0.7 and in a stable continuous flow mode, passing through a micro mixer 1, and rapidly heating to 62 ℃ under the temperature control condition of a water bath 1 to obtain the sodium styrene sulfonate-acrylic mixed solution;
f. polymerization of the initiation reaction of the sodium styrene sulfonate-acrylic acid mixed solution:
b, enabling the initiator aqueous solution prepared in the step c to pass through a delivery pump and the mixed solution of sodium styrene sulfonate and acrylic acid obtained in the step e to pass through a micro mixer 2 in a stable continuous flow mode according to the volume flow ratio of 1:3, rapidly heating to 89 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize, and controlling the reaction residence time (by adjusting the length of a reaction pipeline in the water bath 2) to be 3min to obtain the mixed solution still in the polymerization stage;
g. termination of the polymerization:
d, enabling the chain transfer agent aqueous solution prepared in the step d to pass through a delivery pump, enabling the chain transfer agent aqueous solution and the mixed solution obtained in the step f and still in the polymerization stage to pass through a micro mixer 3 in a stable continuous flow mode according to the volume flow ratio of 1:3, and rapidly cooling to be below 40 ℃ under the temperature control condition of a water bath 3 to terminate the polymerization reaction to obtain mixed solution;
h. and (3) post-treatment:
and g, after the mixed solution obtained in the step g is discharged out of the micro mixer 3, adjusting the pH to 7 by using alkali liquor, and performing spray drying to obtain a powdery particle product, namely the styrene-acrylic acid copolymerization type dispersing agent.
Example 13: referring to figure 1:
a preparation method of styrene-acrylic acid copolymerization type dispersant comprises the following steps:
a. preparing an aqueous solution of sodium styrene sulfonate:
adding 100 parts by mass of sodium styrene sulfonate into 280 parts by mass of water, stirring and mixing to prepare a sodium styrene sulfonate aqueous solution, and placing at normal temperature for later use;
b. preparing an acrylic mixed solution:
stirring and mixing 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 by using a high-speed stirrer to prepare an acrylic mixed solution, and placing the acrylic mixed solution at normal temperature for later use;
c. preparing an initiator aqueous 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 placing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 10 parts by mass of sodium bisulfite into 400 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and placing at normal temperature for later use;
e. micro-mixing of sodium styrene sulfonate aqueous solution and acrylic acid mixed solution:
respectively conveying the sodium styrene sulfonate aqueous solution prepared in the step a and the acrylic mixed solution prepared in the step b by using a conveying pump according to the volume flow ratio of 1:0.7 and in a stable continuous flow mode, passing through a micro mixer 1, and rapidly heating to 58 ℃ under the temperature control condition of a water bath 1 to obtain the sodium styrene sulfonate-acrylic mixed solution;
f. polymerization of the initiation reaction of the sodium styrene sulfonate-acrylic acid mixed solution:
b, enabling the initiator aqueous solution prepared in the step c to pass through a delivery pump and the mixed solution of sodium styrene sulfonate and acrylic acid obtained in the step e to pass through a micro mixer 2 in a stable continuous flow mode according to the volume flow ratio of 1:3, rapidly heating to 86 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize, and controlling the reaction residence time (obtained by adjusting the length of a reaction pipeline in the water bath 2) to be 5min to obtain the mixed solution still in the polymerization stage;
g. termination of the polymerization:
d, enabling the chain transfer agent aqueous solution prepared in the step d to pass through a delivery pump, enabling the chain transfer agent aqueous solution and the mixed solution obtained in the step f and still in the polymerization stage to pass through a micro mixer 3 in a stable continuous flow mode according to the volume flow ratio of 1:3, and rapidly cooling to be below 40 ℃ under the temperature control condition of a water bath 3 to terminate the polymerization reaction to obtain mixed solution;
h. and (3) post-treatment:
and g, after the mixed solution obtained in the step g is discharged out of the micro mixer 3, adjusting the pH to 8 by using alkali liquor, and performing spray drying to obtain a powdery particle product, namely the styrene-acrylic acid copolymerization type dispersing agent.
Example 14: referring to figure 1:
a preparation method of styrene-acrylic acid copolymerization type dispersant comprises the following steps:
a. preparing an aqueous solution of sodium styrene sulfonate:
adding 100 parts by mass of sodium styrene sulfonate into 260 parts by mass of water, stirring and mixing to prepare a sodium styrene sulfonate aqueous solution, and placing at normal temperature for later use;
b. preparing an acrylic mixed solution:
stirring and mixing 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 by using a high-speed stirrer to prepare an acrylic mixed solution, and placing the acrylic mixed solution at normal temperature for later use;
c. preparing an initiator aqueous 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 placing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 6.1 parts by mass of sodium bisulfite into 500 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and placing at normal temperature for later use;
e. micro-mixing of sodium styrene sulfonate aqueous solution and acrylic acid mixed solution:
respectively conveying the sodium styrene sulfonate aqueous solution prepared in the step a and the acrylic mixed solution prepared in the step b by using a conveying pump according to the volume flow ratio of 1:0.7 and in a stable continuous flow mode, passing through a micro mixer 1, and rapidly heating to 59 ℃ under the temperature control condition of a water bath 1 to obtain the sodium styrene sulfonate-acrylic mixed solution;
f. polymerization of the initiation reaction of the sodium styrene sulfonate-acrylic acid mixed solution:
b, enabling the initiator aqueous solution prepared in the step c to pass through a delivery pump and the mixed solution of sodium styrene sulfonate and acrylic acid obtained in the step e to pass through a micro mixer 2 in a stable continuous flow mode according to the volume flow ratio of 1:3, rapidly heating to 85-90 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize, and controlling the reaction residence time 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. termination of the polymerization:
d, enabling the chain transfer agent aqueous solution prepared in the step d to pass through a delivery pump, enabling the chain transfer agent aqueous solution and the mixed solution obtained in the step f and still in the polymerization stage to pass through a micro mixer 3 in a stable continuous flow mode according to the volume flow ratio of 1:3, and rapidly cooling to be below 40 ℃ under the temperature control condition of a water bath 3 to terminate the polymerization reaction to obtain mixed solution;
h. and (3) post-treatment:
and g, after the mixed liquor obtained in the step g is discharged out of the micro mixer 3, adjusting the pH value to 7 by using alkali liquor, and performing spray drying to obtain the styrene-acrylic acid copolymerization type dispersing agent.
Example 15: referring to figure 1:
a preparation method of styrene-acrylic acid copolymerization type dispersant comprises the following steps:
a. preparing an aqueous solution of sodium styrene sulfonate:
adding 100 parts by mass of sodium styrene sulfonate into 280 parts by mass of water, stirring and mixing to prepare a sodium styrene sulfonate aqueous solution, and placing at normal temperature for later use;
b. preparing an acrylic mixed solution:
stirring and 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 using a high-speed stirrer to prepare an acrylic mixed solution, and placing the acrylic mixed solution at normal temperature for later use;
c. preparing an initiator aqueous 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 placing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 11 parts by mass of sodium bisulfite into 460 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and placing at normal temperature for later use;
e. micro-mixing of sodium styrene sulfonate aqueous solution and acrylic acid mixed solution:
respectively conveying the sodium styrene sulfonate aqueous solution prepared in the step a and the acrylic mixed solution prepared in the step b by using a conveying pump according to the volume flow ratio of 1:0.7 and in a stable continuous flow mode, passing through a micro mixer 1, and rapidly heating to 62 ℃ under the temperature control condition of a water bath 1 to obtain the sodium styrene sulfonate-acrylic mixed solution;
f. polymerization of the initiation reaction of the sodium styrene sulfonate-acrylic acid mixed solution:
b, enabling the initiator aqueous solution prepared in the step c to pass through a delivery pump and the mixed solution of sodium styrene sulfonate and acrylic acid obtained in the step e to pass through a micro mixer 2 in a stable continuous flow mode according to the volume flow ratio of 1:3, rapidly heating to 87 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize, and controlling the reaction residence time (obtained by adjusting the length of a reaction pipeline in the water bath 2) to be 4min to obtain the mixed solution still in the polymerization stage;
g. termination of the polymerization:
d, enabling the chain transfer agent aqueous solution prepared in the step d to pass through a delivery pump, enabling the chain transfer agent aqueous solution and the mixed solution obtained in the step f and still in the polymerization stage to pass through a micro mixer 3 in a stable continuous flow mode according to the volume flow ratio of 1:3, and rapidly cooling to be below 40 ℃ under the temperature control condition of a water bath 3 to terminate the polymerization reaction to obtain mixed solution;
h. and (3) post-treatment:
and g, after the mixed liquor obtained in the step g is discharged out of the micro mixer 3, adjusting the pH value to 7.5 by using alkali liquor, and performing spray drying to obtain the styrene-acrylic acid copolymerization type dispersing agent.
Example 16: referring to figure 1:
a preparation method of styrene-acrylic acid copolymerization type dispersant comprises the following steps:
a. preparing an aqueous solution of sodium styrene sulfonate:
adding 100 parts by mass of sodium styrene sulfonate into 290 parts by mass of water, stirring and mixing to prepare a sodium styrene sulfonate aqueous solution, and placing at normal temperature for later use;
b. preparing an acrylic mixed solution:
stirring and mixing 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 by using a high-speed stirrer to prepare an acrylic mixed solution, and placing the acrylic mixed solution at normal temperature for later use;
c. preparing an initiator aqueous 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 placing at normal temperature for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 15 parts by mass of sodium bisulfite into 550 parts by mass of water, stirring and mixing to prepare a chain transfer agent aqueous solution, and placing at normal temperature for later use;
e. micro-mixing of sodium styrene sulfonate aqueous solution and acrylic acid mixed solution:
respectively conveying the sodium styrene sulfonate aqueous solution prepared in the step a and the acrylic mixed solution prepared in the step b by using a conveying pump according to the volume flow ratio of 1:0.7 and in a stable continuous flow mode, passing through a micro mixer 1, and rapidly heating to 60 ℃ under the temperature control condition of a water bath 1 to obtain the sodium styrene sulfonate-acrylic mixed solution;
f. polymerization of the initiation reaction of the sodium styrene sulfonate-acrylic acid mixed solution:
b, enabling the initiator aqueous solution prepared in the step c to pass through a delivery pump and the mixed solution of sodium styrene sulfonate and acrylic acid obtained in the step e to pass through a micro mixer 2 in a stable continuous flow mode according to the volume flow ratio of 1:3, rapidly heating to 89 ℃ under the temperature control condition of a water bath 2 to initiate and (rapidly) react and polymerize, and controlling the reaction residence time (by adjusting the length of a reaction pipeline in the water bath 2) to be 3min to obtain the mixed solution still in the polymerization stage;
g. termination of the polymerization:
d, enabling the chain transfer agent aqueous solution prepared in the step d to pass through a delivery pump, enabling the chain transfer agent aqueous solution and the mixed solution obtained in the step f and still in the polymerization stage to pass through a micro mixer 3 in a stable continuous flow mode according to the volume flow ratio of 1:3, and rapidly cooling to be below 40 ℃ under the temperature control condition of a water bath 3 to terminate the polymerization reaction to obtain mixed solution;
h. and (3) post-treatment:
and g, after the mixed solution obtained in the step g is discharged out of the micro mixer 3, adjusting the pH to 8 by using alkali liquor, and performing spray drying to obtain a powdery particle product, namely the styrene-acrylic acid copolymerization 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: and h, the alkali liquor 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 steps a, b and c is pure water, distilled water, deionized water and the like so as to reduce the influence of redundant ions in the water on the free radical polymerization and the occurrence of other side reactions.
In examples 9-16 above: the delivery pump used in the steps e, f and g can be a constant flow pump or a constant flow pump, and the flow rate is required to be continuously stable, and typically comprises an MP2010D medium-pressure constant flow pump of shanghai three scientific instruments ltd, a TBP2H10S type constant flow pump of shanghai field biotechnology ltd, and the like.
In examples 9-16 above: the micromixer used in step e, step f, step g may be a static mixer, typically a 0.5-2.6ml HP-type mixer available from Shimadzu corporation, or the like.
In examples 9-16 above: the high-speed stirrer used in step b may be an emulsifier of FA, FAB, FAS, FM, FMB or FMS series manufactured by Fluko of Germany, or the like.
In examples 9-16 above: the reaction pipeline used in step e, step f and step g for communicating each micromixer and the material conveying pipeline is preferably a pipeline
The polytetrafluoroethylene (PTFE for short) pipeline can freely regulate and control the residence reaction time in the water bath kettle of each section by regulating the length of each section of reaction pipeline and the flow of the pump.
In examples 9-16 above: and e, the continuous flows in the steps f and g simultaneously pass through a transfer 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 that the uniformity of the reaction environment and the stability of the final product are ensured.
In examples 9-16 above: the sodium styrene sulfonate in step a can be in industrial grade, and the product supplier is Shanghai Michelin Biochemical technology Co.
In examples 9-16 above: the raw materials in the acrylic acid-based compound in step b are preferably analytical pure compounds, and the suppliers include Shanghai Michelin Biotechnology Co., Ltd, Shanghai Baishun Biotechnology Co., Ltd, and the like.
In the above embodiment: the percentages used, not specifically indicated, are percentages by weight or known to those skilled in the art; the proportions used, not specifically noted, are mass (weight) proportions; the parts by weight may each be grams or kilograms.
In the above embodiment: the process parameters (temperature, time, etc.) and the numerical values of the components in each step are in the range, and any point can be applicable.
The present invention and the technical contents not specifically described in the above examples are the same as those of the prior art, and the raw materials are all commercially available 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 styrene-acrylic acid copolymerization type dispersing agent is characterized by comprising the following steps:
a. preparing an aqueous solution of sodium styrene sulfonate:
adding 100 parts by mass of sodium styrene sulfonate into 150-400 parts by mass of water, and stirring and mixing to prepare a sodium styrene sulfonate aqueous solution for later use;
b. preparing an acrylic mixed solution:
stirring and 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 mixed solution for later use;
c. preparing an initiator aqueous solution:
adding 15-45 parts by mass of persulfate initiator into 85-250 parts by mass of water, and stirring and mixing to prepare an initiator aqueous solution for later use;
d. preparation of an aqueous chain transfer agent solution:
adding 5-15 parts by mass of sodium bisulfite into 300-900 parts by mass of water, and stirring and mixing to prepare a chain transfer agent aqueous solution for later use;
e. micro-mixing of sodium styrene sulfonate aqueous solution and acrylic acid mixed solution:
respectively conveying the sodium styrene sulfonate aqueous solution prepared in the step a and the acrylic mixed solution prepared in the step b by using a conveying pump according to the volume flow ratio of 1:0.7 and in a stable continuous flow mode, passing through a micro mixer 1, and rapidly heating to 50-70 ℃ under the temperature control condition of a water bath 1 to obtain the sodium styrene sulfonate-acrylic mixed solution;
f. polymerization of the initiation reaction of the sodium styrene sulfonate-acrylic acid mixed solution:
c, enabling the initiator aqueous solution prepared in the step c to pass through a delivery pump, enabling the initiator aqueous solution and the mixed solution of sodium styrene sulfonate and acrylic acid obtained in the step e to simultaneously pass through a micro mixer 2 in a stable continuous flow mode according to the volume flow ratio of 1:3, and rapidly heating to 85-90 ℃ under the temperature control condition of a water bath 2 to enable the initiator aqueous solution and the mixed solution to initiate and react for polymerization to obtain mixed solution still in a polymerization stage;
g. termination of the polymerization:
d, enabling the chain transfer agent aqueous solution prepared in the step d to pass through a delivery pump, enabling the chain transfer agent aqueous solution and the mixed solution obtained in the step f and still in the polymerization stage to pass through a micro mixer 3 in a stable continuous flow mode according to the volume flow ratio of 1:3, and rapidly cooling to be below 40 ℃ under the temperature control condition of a water bath 3 to obtain mixed solution;
h. and (3) post-treatment:
and g, after the mixed liquid obtained in the step g is discharged from the micro mixer 3, adjusting the pH value to 7-8 by using alkali liquor, and performing spray drying to obtain the styrene-acrylic acid copolymerization type dispersing agent.
2. The method for preparing a styrene-acrylic copolymer dispersant as set forth in claim 1, wherein: the persulfate initiator in the step c is any one of potassium persulfate, sodium persulfate, ammonium persulfate and the like.
3. The process for producing a styrene-acrylic copolymer dispersant as claimed in claim 1 or 2, wherein: the mass usage amount 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 mixed solution in the step b.
4. The process for producing a styrene-acrylic copolymer dispersant as claimed in claim 1 or 2, wherein: the mass amount of the sodium bisulfite in the step d is 1/3 of the mass amount of the persulfate initiator in the step c.
5. The method for preparing a styrene-acrylic copolymer dispersant as set forth in claim 3, wherein: the mass amount of the sodium bisulfite in the step d is 1/3 of the mass amount of the persulfate initiator in the step c.
6. A process for producing a styrene-acrylic copolymer dispersant as claimed in claim 1, 2 or 5, characterized by: and h, the alkali liquor 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 copolymer dispersant as set forth in claim 4, wherein: and h, the alkali liquor is one or a mixture of two of sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
8. A process for preparing a styrene-acrylic copolymer dispersant as claimed in claim 1, 2, 5 or 7, characterized by: the water in the steps a, b and c is pure water, distilled water or deionized water.
9. A process for preparing a styrene-acrylic copolymer dispersant as claimed in claim 1, 2, 5 or 7, characterized by: the conveying pump used in the steps e, f and g is a constant flow pump or a constant flow pump.
10. A process for preparing a styrene-acrylic copolymer dispersant as claimed in claim 1, 2, 5 or 7, characterized by: the micromixer used in step e, step f and step g is a static mixer.
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 true CN113501902A (en) | 2021-10-15 |
| CN113501902B 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 |
|---|---|
| CN113501902B (en) | 2023-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101293936B (en) | Method for preparing monodisperse polystyrene microsphere with controllable grain diameter | |
| US4380600A (en) | Aqueous dispersion of water-soluble polymer composition | |
| CN101717479B (en) | Amphiphilic gradient copolymer | |
| CN103910832A (en) | Polycarboxylate pesticide dispersing agent and preparation method thereof | |
| Liu et al. | Preparation of poly (acrylamide-co-acrylic acid) aqueous latex dispersions using anionic polyelectrolyte as stabilizer | |
| CN102649826A (en) | Preparation method of particle diameter controllable monodisperse polystyrene microspheres | |
| CN111087535B (en) | Method for preparing high-solid-content inverse emulsion polymer with high efficiency and energy conservation | |
| MXPA01003439A (en) | WATERPROOF DISPERSIONS | |
| AU732835B2 (en) | Aqueous dispersions | |
| Wu et al. | Dispersion polymerization of acrylamide with 2‐acrylamido‐2‐methyl‐1‐propane sulfonate in aqueous solution | |
| CN106188405A (en) | Graft modification super high molecular weight micronized polyethylene and solid phase grafting method thereof | |
| US5696228A (en) | Process for producing substantially dry polymer particles from aqueous dispersions | |
| CN105777973B (en) | A kind of amphipathic copolymer dispersant, preparation method and application | |
| Aguirre et al. | Particle nucleation and growth in seeded semibatch miniemulsion polymerization of hybrid CeO2/acrylic latexes | |
| CN104277171A (en) | Preparation method of nano calcium carbonate modified styrene-acrylic emulsion | |
| Schneider et al. | High solids content emulsions. II. Preparation of seed latices | |
| Ouzineb et al. | High‐solid‐content emulsions. V. Applications of miniemulsions to high solids and viscosity control | |
| Mayoux et al. | Inverse suspension polymerization of sodium acrylate: Synthesis and characterization | |
| Chen et al. | Preparation and characterization of pure polyacrylate polymer colloid through emulsion polymerization using a novel initiator | |
| Wang et al. | Kinetics of dispersion polymerization of dimethyl diallyl ammonium chloride and acrylamide | |
| US5792366A (en) | Aqueous dispersions | |
| CN104151463B (en) | In a kind of miniemulsion, photoinduction active free radical polymerization prepares polymer and technique | |
| CN113501902A (en) | Preparation method of styrene-acrylic acid copolymerization type dispersing agent | |
| Ouzineb et al. | Continuous tubular reactors for latex production: conventional emulsion and miniemulsion polymerizations | |
| CN108484839A (en) | A kind of amphipathic carboxylic dispersants and preparation method thereof |
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 |