CN114195932A - Sulfated polyacrylate emulsion and preparation method thereof - Google Patents
Sulfated polyacrylate emulsion and preparation method thereof Download PDFInfo
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- 125000000524 functional group Chemical group 0.000 claims description 10
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 9
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a preparation method of sulfated polyacrylate emulsion, which comprises the steps of activating polyacrylate-based spheres, carrying out bonding reaction twice on microspheres subjected to activation treatment, washing for multiple times and washing solution to obtain the sulfated polyacrylate emulsion finallyThe reaction condition is easy to control because the reaction pressure is close to normal pressure; the sulfated polyacrylate emulsion prepared by the preparation method has uniform particle size of 15-90 μm and pore diameter of
The sulfated polyacrylate emulsion has better hydrophilicity, avoids nonspecific adsorption with biological samples to the maximum extent, has larger pore diameter compared with other hydrophobic fillers, and is more suitable for separating and purifying the biological samples with larger molecular weight; meanwhile, the preparation method has simple flow, and the used raw materials are easy to obtain, so that the production cost is lower.
Description
Technical Field
The invention relates to the technical field of preparation of sulfated polyacrylate emulsion materials for liquid chromatography media, in particular to sulfated polyacrylate emulsion and a preparation method of the sulfated polyacrylate emulsion.
Background
The liquid phase adsorption chromatographic separation technology is a high-efficiency physical separation technology, and the core component of the technology is a chromatographic separation column. The separation principle is as follows: the mixed component sample is dissolved in a mobile phase, the mobile phase flows through a chromatographic packing (filler) filled in a chromatographic separation column at a certain flow rate under the condition of higher pressure, different components flow through the chromatographic packing at different flow rates due to different adsorption forces of the chromatographic packing on the different components, and the component outflow time and the component content are detected in a detector of a liquid chromatograph, so that the separation and detection purposes are achieved. At present, liquid chromatography packing materials are widely applied to the technical fields of drug development, substance analysis and separation and the like, wherein a High Performance Liquid Chromatography (HPLC) is the most common analysis and separation means and is mainly applied to the fields of chemistry and chemical engineering, food sanitation, drug detection, environmental monitoring and the like. Liquid chromatography packing (i.e., liquid chromatography media) is the key foundation upon which high performance liquid chromatography techniques rely for its establishment and development.
In a common liquid phase adsorption chromatographic separation column, only one solid phase adsorbent is generally filled in the separation column, and because the specific solid phase adsorbent has specific adsorption on specific chemical substances, the separation column with the structure can only separate and detect substances with a certain molecular diameter or chemical property in a sample at one time; in the liquid chromatography medium, polyesters, polyamino acids, polyacrylate and the like are common liquid chromatography medium materials, and the liquid chromatography medium materials have the characteristic of amphipathy, and because the molecules of the liquid chromatography medium materials simultaneously have hydrophilic groups and hydrophobic groups: the hydrophobic group is constructed into a matrix of a liquid chromatography medium to determine the mechanical strength, pressure resistance and chemical resistance of the liquid chromatography medium; the hydrophilic groups have different chemical functional groups which can be selected to determine the separation mode and loading of the liquid chromatography. With the development of high performance liquid chromatography and pharmaceutical liquid chromatography media, the particle size and pore size of the microspheres need to be precisely controlled, the particle size needs to be controlled in a uniform range, and the pore surfaces need to have certain hydrophobicity and specific chemical functional groups.
In the aspect of preparation method, the traditional micelle method can be adopted to prepare the uniform particle microspheres with dozens of nanometers to hundreds of nanometers, or the traditional suspension polymerization method and emulsion polymerization method can be adopted to prepare the microspheres with more than hundreds of micrometers and nonuniform particle sizes. The particle size and the pore size of the microsphere filler prepared by the traditional method cannot be accurately controlled, and the particle size and the pore size are not uniform, so that the practical application of the liquid chromatography of the microsphere filler is limited to a great extent, and the separation and analysis effects of the microsphere filler as a liquid chromatography medium are seriously influenced. Therefore, the invention provides a novel sulfated polyacrylate emulsion and a preparation method of the sulfated polyacrylate emulsion. The liquid chromatography medium prepared by the method can accurately control the particle size and the pore size structure, has uniform particle size and pore size, and has good liquid chromatography separation and analysis effects.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of sulfated polyacrylate emulsion, which comprises the steps of activating polyacrylate-based spheres, carrying out bonding reaction twice on the microspheres subjected to the activation treatment, washing for multiple times and washing solution for treatment, and finally obtaining the sulfated polyacrylate emulsion.
In order to achieve the above object, the present invention provides a method for preparing a sulfated polyacrylate emulsion, comprising the steps of:
s1, carrying out polyacrylate activation treatment, namely carrying out acid activation treatment on polyacrylate-based spheres with fixed components, certain particle sizes and certain pore sizes to obtain activated polyacrylate microspheres;
s2, performing a first bonding reaction, namely dispersing the activated polyacrylate microspheres in an alkaline solution, and adding an alkylene oxide solution to perform the first bonding reaction to obtain a polyacrylate epoxy ester filter cake;
s3, washing, namely adding the polyacrylic acid epoxy ester filter cake into an ethanol solution for washing to remove residual solvent and unreacted reagent;
s4, performing a second bonding reaction, namely dispersing the polyacrylic acid epoxy ester filter cake in a prepared sulfite solution in advance to perform the second bonding reaction, so that the surface of the polyacrylic acid epoxy ester filter cake is modified to form a functional group emulsion, and a sulfated polyacrylate emulsion crude product is obtained;
s5 acid washing, namely adding the sulfated polyacrylate emulsion into a dilute sulfuric acid solution or a dilute hydrochloric acid solution for washing so as to neutralize residual alkaline solvent and unreacted reagent;
s6, soaking, namely soaking and shaping the washed sulfated polyacrylate emulsion by using an ethanol water solution to obtain a sulfated polyacrylate emulsion finished product.
Further, a centrifugal cleaning step is included between steps S1 and S5, the centrifugal cleaning step is to put the substances obtained from steps S1 to S5 into a centrifuge and add pure water to carry out centrifugal separation and cleaning, the rotation speed of the centrifuge is 500rpm to 800rpm, and the time is 50min to 60min, so as to sufficiently remove the residual solvent and unreacted reagent.
Further, in step S1, the polyacrylate-based spheres are selected from one or a mixture of polymethyl methacrylate-based spheres, polyglycidyl methacrylate-based spheres, polyethylene glycol dimethacrylate, polyglycidyl methacrylate-polyethylene glycol dimethacrylate copolymer spheres, polymethyl methacrylate-glycidyl methacrylate copolymer spheres, and polymethyl methacrylate-polyethylene glycol dimethacrylate copolymer spheres;
the particle diameter of the polyacrylate-based sphere is 15-90 mu m, and the pore diameter is
The acid activation treatment is to prepare a concentrated sulfuric acid solution with the concentration of 0.4-0.6M by using concentrated sulfuric acid, and the polyacrylate-based spheres are added into the concentrated sulfuric acid solution and stirred uniformly to activate the polyacrylate-based spheres, wherein the stirring speed is 250-350 rpm, and the activation time is 60-120 min.
Step S2, the alkaline solution is selected from one or a mixture of NaOH solution and KOH solution, and the concentration of the alkaline solution is 30-32%; the alkylene oxide solution is an epoxy chloropropane aqueous solution, and the concentration of the epoxy chloropropane is 2.5-4.5%;
the reaction temperature of the first bonding reaction is 55-65 ℃, the reaction pressure is 0.1-0.2 MPa, and the reaction time is 10-20 h; the pH value of the first bonding reaction is 8-10 so as to provide a mild chemical reaction environment.
The washing time of the step S3 is 60-120 min, the cycle time is 6-8 times, and the concentration of the ethanol solution is 5-6%.
Step S4 the sulfite solution is selected from Na2SO3，K2SO3，NaHSO3，KHSO3，Na2S2O3One or mixed water solution with sulfite concentration of 10％～20％；
The reaction temperature of the second bonding reaction is 60-70 ℃, the reaction pressure is 0.1-0.2 MPa, and the reaction time is 14-18 h;
in the step S5, the concentration of the acid washing solution is 2.5-3.5%, the acid washing temperature is 35-45 ℃, the time is 60-120 min, and the cycle time is 5-6.
Step S6, the ethanol concentration of the ethanol aqueous solution is 18% -22%, the volume ratio (v/v) of the sulfated polyacrylate emulsion to the ethanol aqueous solution is 10: 7-8; the sulfated polyacrylate emulsion is stored in an ethanol water solution for a long time; the particle diameter of the sulfated polyacrylate emulsion is 15-90 mu m, and the pore diameter is
The modified particle size is more uniform and has good physical and chemical stability.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method of the sulfated polyacrylate emulsion adopts preformed base spheres for activation treatment, and carries out hierarchical bonding reaction on activated microspheres to obtain the sulfated polyacrylate emulsion, the preparation method takes a water phase as a reaction system, the reaction temperature and the pressure are relatively low, one is water as a dispersion medium, the preparation method is cheap and safe, and because the continuous phase is water, the preparation method can play a certain temperature balancing role in the reaction process, the system is not overheated, and the polymerization reaction is carried out in latex particles dispersed in the water phase, so the viscosity change of the system in the reaction process is not great; meanwhile, the pipeline conveying is convenient, and the continuous operation is easy to realize; secondly, the polymerization rate is high, the relative molecular mass of the product is high, the product can be carried out at a lower temperature, the chemical reaction condition is mild, emulsion particles repel each other due to the surface charges, the termination reaction of the reacted free radical chain is less, and the product can be polymerized with the monomer free radical all the time to increase the molecular weight to be very high; and the closed latex particles have isolation effect, so that a huge number of free radicals carry out chain growth reaction, the total concentration of the free radicals is much higher than that of other polymerization processes, and the reaction rate is high; thirdly, the method is more suitable for the situation of directly using the emulsion, and the emulsion obtained by the method is uniform and stable and is very suitable for industrial mass production.
2. The sulfated polyacrylate emulsion prepared by the preparation method has uniform particle size of 15-90 mu m and pore diameter of
Meanwhile, the preparation method has simple flow, and the used raw materials are easy to obtain, so that the production cost is low; the sulfated polyacrylate emulsion has better hydrophilicity, avoids nonspecific adsorption with biological samples to the maximum extent, has larger pore diameter compared with other hydrophobic fillers, and is more suitable for separating and purifying the biological samples with larger molecular weight.
3. The preparation method of the invention preferentially selects the polyacrylate-based spheres for activation treatment, the adopted activation solution is concentrated sulfuric acid which is prepared into 0.4-0.6M acid activation treatment solution, the activation condition is easy to control under the stirring condition, the activation solution is easy to obtain, and the activation effect is good; the method comprises the following steps of carrying out hierarchical bonding reaction on activated polyacrylate microspheres, firstly carrying out alkylene oxide grafting treatment in an alkaline environment to obtain polyacrylic epoxy ester, and then carrying out sulfite chain extension treatment on the polyacrylic epoxy ester to obtain sulfated polyacrylate emulsion.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a sulfated polyacrylate emulsion according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, so that those skilled in the art can fully understand the technical contents of the present invention. It should be understood that the following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the present invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing description are intended to be covered by the present invention. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
The invention provides a preparation method of sulfated polyacrylate emulsion, which comprises the following main steps:
s1, carrying out polyacrylate activation treatment, namely carrying out acid activation treatment on polyacrylate-based spheres with fixed components, certain particle sizes and certain pore sizes to obtain activated polyacrylate microspheres; the polyacrylate-based sphere has a particle size of 15-90 μm and a pore size of
Preparing concentrated sulfuric acid solution with the concentration of 0.4-0.6M by using concentrated sulfuric acid, adding the polyacrylate-based balls into the concentrated sulfuric acid solution, and uniformly stirring to activate the polyacrylate-based balls, wherein the stirring speed is 250-350 rpm, and the activation time is 60-120 min;
s2, performing a first bonding reaction, namely dispersing the activated polyacrylate microspheres in an alkaline solution, and adding an alkylene oxide solution to perform the first bonding reaction, wherein the reaction temperature is 55-65 ℃, the reaction pressure is 0.1-0.2 MPa, and the reaction time is 10-20 hours, so as to obtain a polyacrylate epoxy ester filter cake; the alkaline solution is NaOH solution or KOH solution, and the concentration is 30 to 32 percent; the alkylene oxide solution is an epoxy chloropropane aqueous solution, and the concentration of the epoxy chloropropane is 2.5 to 4.5 percent; the pH value of the first bonding reaction is 8-10;
s3, washing, namely adding the polyacrylic acid epoxy ester filter cake into an ethanol solution for washing, wherein the time is 60-120 min, the cycle time is 6-8 times, the concentration of the ethanol solution is 5% -6%, and removing residual solvent and unreacted reagents;
s4 second bonding reaction, dispersing the filter cake of polyacrylic epoxy ester in prepared sulfite solution for second bonding reactionThe reaction temperature is 60-70 ℃, the reaction pressure is 0.1-0.2 MPa, and the reaction time is 14-18 h; carrying out surface modification on a polyacrylic acid epoxy ester filter cake to form functional group emulsion to obtain a sulfated polyacrylate emulsion crude product; the sulfite solution is selected from Na2SO3，K2SO3，NaHSO3，KHSO3，Na2S2O3One or mixed saline solution, the concentration of sulfite is 10 to 20 percent;
s5 acid washing, namely adding the sulfated polyacrylate emulsion into a dilute sulfuric acid solution or a dilute hydrochloric acid solution with the concentration of 2.5-3.5%, the acid washing temperature of 35-45 ℃, the time of 60-120 min and the cycle number of 5-6 times for washing to neutralize residual alkaline solvent and unreacted reagent;
s6 soaking, and soaking and shaping the washed sulfated polyacrylate emulsion by using an ethanol water solution to obtain a sulfated polyacrylate emulsion finished product.
Further, a centrifugal cleaning step is included between the steps S1 and S5, the centrifugal cleaning step is that the substances obtained from the steps S1 to S5 are placed into a centrifuge, pure water is added into the substances for centrifugal separation and cleaning, the rotating speed of the centrifuge is 500rpm to 800rpm, and the time is 50min to 60min, so that residual solvent and unreacted reagents are fully removed.
Step S6, the ethanol concentration of the ethanol water solution is 18% -22%, the volume ratio (v/v) of the sulfated polyacrylate emulsion to the ethanol water solution is 10: 7-8; the sulfated polyacrylate emulsion is stored in ethanol water solution for a long time; the particle diameter of the sulfated polyacrylate emulsion is 15-90 mu m, and the pore diameter is
The modified particle size is more uniform and has good physical and chemical stability.
Specifically, the preparation method of the sulfated polyacrylate emulsion comprises the step of S1 activation treatment, namely, quantitatively conveying pure water in a charging basket to a first acid washing kettle by using a first pure water conveying pump, then pumping concentrated sulfuric acid in vacuum to prepare 0.4-0.6M sulfuric acid solution, adding polyacrylate base balls, uniformly stirring to preliminarily activate the base balls, conveying the mixture to a first washing kettle in a cleaning area by using a second conveying pump, and conveying the mixture to a first centrifuge by using a third conveying pump for centrifugal cleaning and separation.
S101, carrying out first centrifugal cleaning, conveying filter cakes to a first washing kettle of a clean area after centrifugal separation by a first centrifugal machine, adding pure water into the first washing kettle, and washing again to remove acidity of materials generated by sulfuric acid activation. And (3) centrifugally separating the washed mixed solution in a first centrifuge, conveying the separated filter cake into a first washing kettle, repeatedly washing for 6-8 times in the way, and conveying the filter cake after the last centrifugation to a bonding reaction A kettle.
S2, carrying out a first bonding reaction, and quantitatively conveying the epichlorohydrin in the charging bucket to a high-level tank for later use by using an epichlorohydrin fifth conveying pump; quantitatively conveying the liquid caustic soda in the charging bucket to a bonding reaction A kettle by using a liquid caustic soda third conveying pump, adding the activated base ball, stirring and mixing uniformly, dropwise adding epoxy chloropropane in the head tank into the bonding reaction A kettle, controlling the reaction temperature to be 55-65 ℃, the reaction pressure to be 0.1-0.2 MPa, and the reaction time to be 10-20 h. In the first bonding reaction process, a heating medium is introduced into a jacket of a bonding reaction B kettle, the opening of a heating medium inlet adjusting valve is adjusted according to the temperature of the reaction kettle, a heating medium inlet stop valve is closed in a temperature high-high interlocking mode, and a refrigerant bypass switch valve is opened to reduce the temperature; and after the first bonding reaction is finished, the pH value is 8-10, opening a refrigerant inlet adjusting valve, and conveying the first bonding reaction material to a first centrifuge for centrifugal separation by using a fourth conveying pump of the bonding reaction A kettle after the temperature is reduced to the room temperature.
S3, centrifugal washing and cleaning for the second time, sending filter cakes to a first washing kettle after centrifugal separation by a first centrifugal machine, adding ethanol into the first washing kettle for washing, further removing residual solvent and unreacted reagent, sending the washed mixed solution to the first centrifugal machine for centrifugal separation, repeatedly washing for 2-4 times, washing with pure water for 6-8 times after ethanol washing, then carrying out centrifugal separation, and sending the filter cakes to a bonding reaction kettle B.
S4, performing a second bonding reaction, namely allowing the mixed solution in the first solution preparation kettle to automatically flow into a bonding reaction B kettle, adding the modified polyacrylate-based spheres, opening a stirrer, introducing a heating medium into a jacket of the bonding reaction B kettle, heating to the reaction temperature of 60-70 ℃, the reaction pressure of 0.1-0.2 MPa, and the reaction time of 14-18 h; in the reaction process, a heating medium is introduced into a jacket of the bonding reaction B kettle, the opening of a heating medium inlet adjusting valve is adjusted according to the temperature of the reaction kettle, a heating medium inlet stop valve is closed in a temperature high-high interlocking mode, and a refrigerant bypass switch valve is opened to reduce the temperature; and after the reaction is finished, opening the refrigerant inlet regulating valve, and conveying the reaction liquid of the bonding reaction B kettle to a second centrifugal machine for centrifugal separation after the temperature is reduced to room temperature.
S401, carrying out centrifugal washing and cleaning for the third time, conveying filter cakes subjected to centrifugal separation by a second centrifugal machine to a second washing kettle, adding pure water into the second washing kettle for washing, further removing residual solvent and unreacted reagent, carrying out centrifugal separation on the washed mixed solution by the second centrifugal machine, conveying the separated filter cakes to the second washing kettle, repeatedly washing for 6-8 times, and conveying the filter cakes subjected to the final centrifugation to a fourth acid washing kettle.
S5 acid washing, wherein pure water is added into a fourth acid washing kettle, a cooling medium and a heating medium are introduced into a jacket of the fourth acid washing kettle, a pipeline valve of the cooling medium or the heating medium is determined to be opened according to the temperature of the fourth acid washing kettle, the acid washing temperature of the fourth acid washing kettle is 35-45 ℃, the time is 60-120 min, the circulation frequency is 5-6 times, and the washed feed liquid is pressurized by a fifth delivery pump and then is sent to a second centrifuge for centrifugal separation.
S501, performing centrifugal washing and cleaning, conveying filter cakes subjected to centrifugal separation by a second centrifugal machine to a second washing kettle, adding pure water into the second washing kettle, washing to further remove residual solvent and unreacted reagents, conveying the washed mixed solution to the second centrifugal machine for centrifugal separation, conveying the separated filter cakes to the second washing kettle, and repeatedly washing for 6-8 times.
S6, soaking the centrifuged wet emulsion by using 18-22% ethanol water solution, wherein the volume ratio (v/v) of the sulfated polyacrylate emulsion to the ethanol water solution is 10: 7-8, and obtaining a sulfated polyacrylate emulsion product.
Sulfuric acid obtained by the preparation methodThe polyacrylic ester emulsion has uniform particle size of 15-90 μm and pore diameter of
The sulfated polyacrylate emulsion has better hydrophilicity, avoids nonspecific adsorption with biological samples to the maximum extent, has larger pore diameter compared with other hydrophobic fillers, and is more suitable for separating and purifying the biological samples with larger molecular weight.
Example 1:
in the preparation method of sulfated polyacrylate emulsion provided in this example, firstly, pre-prepared poly (glycidyl methacrylate) -poly (ethylene glycol dimethacrylate) copolymer spheres with a particle size of 45 μm to 60 μm and a pore size of 45 μm to 60 μm were used
Using concentrated sulfuric acid to prepare a concentrated sulfuric acid solution with the concentration of 0.5M for acid activation treatment, adding the copolymerized polyacrylate-based sphere into the concentrated sulfuric acid solution, and uniformly stirring to activate the basic sphere, wherein the stirring speed is 280rpm, and the activation time is 100min so as to obtain activated polyacrylate copolymerized microspheres;
secondly, carrying out a first bonding reaction on the obtained activated polyacrylate copolymer microspheres, dispersing the copolymer microspheres in 30% NaOH alkaline solution, adding 3.0% epichlorohydrin solution, carrying out the first bonding reaction at the reaction temperature of 60 ℃, the reaction pressure of 0.12MPa and the reaction time of 20h, and keeping the pH value at about 8.5 to obtain a copolymer polyacrylate epoxy ester filter cake;
thirdly, adding the polyacrylic acid epoxy ester filter cake into an ethanol solution with the ethanol concentration of 5.5% for washing, wherein the washing time is 80min, and the cycle number is 8 times, so as to remove residual solvent and unreacted reagent;
from the next time, the co-polyacrylic epoxy ester filter cake was dispersed in 15% Na prepared in advance2SO3In the salt solution, the reaction temperature is controlled to be 65 ℃, the reaction pressure is 0.12MPa, the reaction time is 16h, and the second bonding reaction is carried out, so that the polypropylene copolymerPerforming surface modification on the acid epoxy ester filter cake to form functional group emulsion to obtain a crude product of polyacrylate copolymer emulsion;
then, adding the polyacrylate copolymer emulsion into a dilute hydrochloric acid solution with the concentration of 3% for acid washing, wherein the acid washing temperature is 40 ℃, the time is 80min, and the cycle number is 6 times for cleaning so as to neutralize residual alkaline solvent and unreacted reagent;
and finally, soaking and shaping the washed polyacrylate copolymer emulsion by using an ethanol water solution with the concentration of 20%, wherein the volume ratio (v/v) of the copolymer emulsion to the ethanol water solution is 10: 7, obtaining a finished product of the sulfated polyacrylate emulsion.
The sulfated polyacrylate emulsion prepared by the above method has uniform particle diameter, average particle diameter D50 of 27.0 μm, ratio of D90 to D10 of 1.13, loading capacity of 120.2g/l, and pore diameter of 120.2g/l
Example 2:
in the preparation method of sulfated polyacrylate emulsion provided in this example, firstly, pre-prepared polyglycidyl methacrylate-based spheres with a particle size of 15 μm to 25 μm and a pore size of 15 μm to 25 μm were used
Using concentrated sulfuric acid to prepare a concentrated sulfuric acid solution with the concentration of 0.45M for acid activation treatment, adding the polyacrylate-based spheres into the concentrated sulfuric acid solution, and uniformly stirring to activate the base spheres, wherein the stirring speed is 300rpm, and the activation time is 80min, so as to obtain activated polyacrylate microspheres;
secondly, carrying out a first bonding reaction on the obtained activated polyacrylate microspheres, dispersing the microspheres in 32% KOH alkaline solution, adding epoxy chloropropane solution with the concentration of 4.0%, carrying out the first bonding reaction at the reaction temperature of 60 ℃, the reaction pressure of 0.12MPa and the reaction time of 20h, and keeping the pH value at about 9.3 to obtain polyacrylic epoxy ester filter cakes;
thirdly, adding the polyacrylic acid epoxy ester filter cake into an ethanol solution with the ethanol concentration of 5.5% for washing, wherein the washing time is 80min, and the cycle number is 8 times, so as to remove residual solvent and unreacted reagent;
from the next time, the polyacrylate epoxy ester filter cake was dispersed in a previously prepared K of 12%2SO3In the salt solution, controlling the reaction temperature at 60 ℃, the reaction pressure at 0.18MPa and the reaction time at 14h, carrying out a second bonding reaction, and carrying out surface modification on the polyacrylic acid epoxy ester filter cake to form a functional group emulsion to obtain a crude product of the sulfated polyacrylate emulsion;
then, adding dilute sulfuric acid solution with the concentration of 3.2% into the sulfated polyacrylate emulsion for acid washing, wherein the acid washing temperature is 45 ℃, the time is 70min, and the cycle number is 8 times for cleaning so as to neutralize residual alkaline solvent and unreacted reagent;
finally, soaking and shaping the cleaned sulfated polyacrylate emulsion by using an ethanol water solution with the concentration of 18%, wherein the volume ratio (v/v) of the emulsion to the ethanol water solution is 10: 7.5, obtaining a finished product of the sulfated polyacrylate emulsion.
The sulfated polyacrylate emulsion prepared by the above method has uniform particle diameter, average particle diameter D50 of 53.7 μm, ratio of D90 to D10 of 1.31, loading capacity of 97.5g/l, and pore diameter of 97.5g/l
Example 3:
in the preparation method of sulfated polyacrylate emulsion provided in this example, firstly, pre-prepared poly (ethylene glycol dimethacrylate) based spheres with a particle size of 30 μm to 50 μm and a pore size of 30 μm to 50 μm were used
Using concentrated sulfuric acid to prepare a concentrated sulfuric acid solution with the concentration of 0.55M for acid activation treatment, adding the polyacrylate-based spheres into the concentrated sulfuric acid solution, and uniformly stirring to activate the base spheres, wherein the stirring speed is 350rpm, and the activation time is 110min, so as to obtain activated polyacrylate microspheres;
secondly, carrying out a first bonding reaction on the obtained activated polyacrylate microspheres, dispersing the microspheres in 31.5% NaOH alkaline solution, adding 3.5% epichlorohydrin solution, carrying out the first bonding reaction at the reaction temperature of 55 ℃, the reaction pressure of 0.15MPa and the reaction time of 15h, and keeping the pH value at about 9.5 to obtain a polyacrylate epoxy ester filter cake;
thirdly, adding the polyacrylic acid epoxy ester filter cake into an ethanol solution with the ethanol concentration of 5.8% for washing, wherein the washing time is 70min, and the cycle number is 7 times, so as to remove residual solvent and unreacted reagent;
from the next time, the poly (epoxy acrylate) filter cake was dispersed in 18% Na prepared beforehand2S2O3In the salt solution, controlling the reaction temperature at 65 ℃, the reaction pressure at 0.16MPa and the reaction time at 18h, carrying out a second bonding reaction, and carrying out surface modification on the polyacrylic acid epoxy ester filter cake to form a functional group emulsion to obtain a crude product of the sulfated polyacrylate emulsion;
then, adding the sulfated polyacrylate emulsion into a dilute hydrochloric acid solution with the concentration of 2.8% for acid washing, wherein the acid washing temperature is 38 ℃, the time is 80min, and the cycle number is 6 times for cleaning so as to neutralize residual alkaline solvent and unreacted reagent;
finally, soaking and shaping the cleaned sulfated polyacrylate emulsion by using 21% ethanol water solution, wherein the volume ratio (v/v) of the emulsion to the ethanol water solution is 10: 7, obtaining a finished product of the sulfated polyacrylate emulsion.
The sulfated polyacrylate emulsion prepared by the above method has uniform particle diameter, average particle diameter D50 of 17.3 μm, ratio of D90 to D10 of 1.01, loading capacity of 59.9g/l, and pore diameter of 59.9g/l
Example 4:
this example provides a method for preparing a sulfated polyacrylate emulsion, which comprises first preparing polymethyl methacrylate-based spheresThe particle diameter of the acrylate-based ball is 40-60 mu m and the pore diameter is
Using concentrated sulfuric acid to prepare a concentrated sulfuric acid solution with the concentration of 0.58M for acid activation treatment, adding the polyacrylate-based spheres into the concentrated sulfuric acid solution, and uniformly stirring to activate the base spheres, wherein the stirring speed is 350rpm, and the activation time is 110min, so as to obtain activated polyacrylate microspheres;
secondly, carrying out a first bonding reaction on the obtained activated polyacrylate microspheres, dispersing the microspheres in 30.5% NaOH alkaline solution, adding 2.8% epichlorohydrin solution, carrying out the first bonding reaction at the reaction temperature of 55 ℃, the reaction pressure of 0.15MPa and the reaction time of 15h, and keeping the pH value at about 9.0 to obtain a polyacrylate epoxy ester filter cake;
thirdly, adding the polyacrylic acid epoxy ester filter cake into an ethanol solution with the ethanol concentration of 5.8% for washing, wherein the washing time is 70min, and the cycle number is 7 times, so as to remove residual solvent and unreacted reagent;
from the next time, the polyacrylate epoxy ester filter cake was dispersed in the previously prepared NaHSO 16%3In the salt solution, controlling the reaction temperature at 65 ℃, the reaction pressure at 0.16MPa and the reaction time at 18h, carrying out a second bonding reaction, and carrying out surface modification on the polyacrylic acid epoxy ester filter cake to form a functional group emulsion to obtain a crude product of the sulfated polyacrylate emulsion;
then, adding a dilute sulfuric acid solution with the concentration of 2.8% into the sulfated polyacrylate emulsion for acid washing, wherein the acid washing temperature is 38 ℃, the time is 80min, and the cycle number is 6 times for cleaning so as to neutralize residual alkaline solvent and unreacted reagent;
finally, soaking and shaping the cleaned sulfated polyacrylate emulsion by using 21% ethanol water solution, wherein the volume ratio (v/v) of the emulsion to the ethanol water solution is 10: 7, obtaining a finished product of the sulfated polyacrylate emulsion.
The sulfated polyacrylate emulsion prepared by the above method has uniform particle diameter, average particle diameter D50 of 37.2 μm, D90 and D10The ratio is 1.11, the loading is 69.9g/l, and the pore diameter is
Example 5:
in the preparation method of sulfated polyacrylate emulsion provided in this example, firstly, the pre-prepared poly (methyl methacrylate) -poly (ethylene glycol dimethacrylate) copolymer spheres with the particle size of 65 μm-85 μm and the pore diameter of 65 μm-85 μm are used
Using concentrated sulfuric acid to prepare a concentrated sulfuric acid solution with the concentration of 0.43M for acid activation treatment, adding the copolymerized polyacrylate-based sphere into the concentrated sulfuric acid solution, and uniformly stirring to activate the basic sphere, wherein the stirring speed is 280rpm, and the activation time is 100min so as to obtain activated polyacrylate copolymerized microspheres;
secondly, carrying out a first bonding reaction on the obtained activated polyacrylate copolymer microspheres, dispersing the copolymer microspheres in 31% KOH alkaline solution, adding epoxy chloropropane solution with the concentration of 4.2%, carrying out the first bonding reaction at the reaction temperature of 60 ℃, the reaction pressure of 0.12MPa and the reaction time of 20h, and keeping the pH value at about 9.8 to obtain a copolymer polyacrylate epoxy ester filter cake;
thirdly, adding the polyacrylic acid epoxy ester filter cake into an ethanol solution with the ethanol concentration of 5.5% for washing, wherein the washing time is 80min, and the cycle number is 8 times, so as to remove residual solvent and unreacted reagent;
secondly, the co-polymerized polyacrylic epoxy ester filter cake is dispersed in the prepared KHSO with the concentration of 12.5 percent3In the salt solution, controlling the reaction temperature at 65 ℃, the reaction pressure at 0.12MPa and the reaction time at 16h, carrying out a second bonding reaction, and carrying out surface modification on the co-polymerized polyacrylic acid epoxy ester filter cake to form a functional group emulsion to obtain a crude product of the polyacrylate co-polymerized emulsion;
then, adding a dilute sulfuric acid solution or a dilute hydrochloric acid solution with the concentration of 3% into the polyacrylate copolymer emulsion for acid washing, wherein the acid washing temperature is 40 ℃, the time is 80min, and the cycle number is 6 times for cleaning so as to neutralize the residual alkaline solvent and unreacted reagents;
and finally, soaking and shaping the washed polyacrylate copolymer emulsion by using an ethanol water solution with the concentration of 20%, wherein the volume ratio (v/v) of the copolymer emulsion to the ethanol water solution is 10: 7, obtaining a finished product of the sulfated polyacrylate emulsion.
The sulfated polyacrylate emulsion prepared by the above method has uniform particle diameter, average particle diameter D50 of 42.5 μm, ratio of D90 to D10 of 1.03, loading capacity of 115.1g/l, and pore diameter of 115.1g/l
The preparation method of the sulfated polyacrylate emulsion adopts preformed base sphere activation treatment and carries out fractional bonding reaction on the activated microspheres to obtain the sulfated polyacrylate emulsion, the preparation method uses an aqueous phase system as a reaction system, the reaction temperature and the reaction pressure are relatively low, the chemical reaction conditions are mild, the prepared sulfated polyacrylate emulsion has uniform grain diameter of 15-90 mu m and the pore diameter of 15-90 mu m
Meanwhile, the preparation method has simple flow, and the used raw materials are easy to obtain, so that the production cost is lower. The sulfated polyacrylate emulsion also has high mechanical stability on the packing of the chromatographic column to ensure that it can withstand pressures of up to 10bar and can meet the requirements of high flow rates and reduced operating times in the development of industrial purification processes; the filler has high chemical stability, can resist the cleaning operation of pH14 and above, and the excellent filler performance enables the filler to meet the separation and purification requirements of various stages from laboratory process development, process amplification to production completion and the like; compared with the traditional agarose matrix, the polyacrylate matrix can improve the pressure resistance of the filler, realize sample purification at a higher flow rate, or can be provided with longer filler chromatographic columns, can process more biological samples in batches, save time and improve the biological quality of the samplesThe production efficiency is high. The liquid chromatography medium can also be used for rapidly separating and purifying mother liquor for unstable biological samples, so that the yield and quality control of products can be improved while the production efficiency is improved; the sulfated polyacrylate emulsion has better hydrophilicity, avoids nonspecific adsorption with biological samples to the maximum extent, has larger pore diameter compared with other hydrophobic fillers, and is more suitable for separating and purifying the biological samples with larger molecular weight.
It should be noted that the above-mentioned preferred embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A method for preparing sulfated polyacrylate emulsion, which is characterized by comprising the following steps:
s1, carrying out polyacrylate activation treatment, namely carrying out acid activation treatment on polyacrylate-based spheres with fixed components, certain particle sizes and certain pore sizes to obtain activated polyacrylate microspheres;
s2, performing a first bonding reaction, namely dispersing the activated polyacrylate microspheres in an alkaline solution, and adding an alkylene oxide solution to perform the first bonding reaction to obtain a polyacrylate epoxy ester filter cake;
s3 washing, namely adding the polyacrylic acid epoxy ester filter cake into an ethanol solution for washing;
s4, performing a second bonding reaction, namely dispersing the polyacrylic acid epoxy ester filter cake in a prepared sulfite solution in advance to perform the second bonding reaction, so that the surface of the polyacrylic acid epoxy ester filter cake is modified to form a functional group emulsion, and a sulfated polyacrylate emulsion crude product is obtained;
s5 acid washing, namely adding the sulfated polyacrylate emulsion into a dilute sulfuric acid solution or a dilute hydrochloric acid solution for washing, and neutralizing the residual alkaline solvent and unreacted reagents;
s6, soaking, namely soaking and shaping the washed sulfated polyacrylate emulsion by using an ethanol water solution to obtain a sulfated polyacrylate emulsion finished product.
2. The method for preparing a sulfated polyacrylate emulsion according to claim 1, wherein: the polyacrylate-based spheres in step S1 are selected from one or a mixture of polymethyl methacrylate-based spheres, polyglycidyl methacrylate-based spheres, polyethylene glycol dimethacrylate, polyglycidyl methacrylate-polyethylene glycol dimethacrylate copolymer spheres, polymethyl methacrylate-glycidyl methacrylate copolymer spheres, and polymethyl methacrylate-polyethylene glycol dimethacrylate copolymer spheres.
3. The method for preparing a sulfated polyacrylate emulsion according to claim 2, wherein: the particle diameter of the polyacrylate-based sphere is 15-90 mu m, and the pore diameter is
4. The method for preparing a sulfated polyacrylate emulsion according to claim 1, wherein: step S1, preparing a concentrated sulfuric acid solution of 0.4-0.6M by using concentrated sulfuric acid in the acid activation treatment, adding the polyacrylate-based spheres into the concentrated sulfuric acid solution, and uniformly stirring to activate the polyacrylate-based spheres, wherein the stirring speed is 250-350 rpm, and the activation time is 60-120 min.
5. The method for preparing a sulfated polyacrylate emulsion according to claim 1, wherein: step S2, the alkaline solution is selected from one or a mixture of NaOH solution and KOH solution, and the concentration of the alkaline solution is 30-32%; the alkylene oxide solution is an epoxy chloropropane aqueous solution, and the concentration of the epoxy chloropropane is 2.5-4.5%.
6. The method for preparing a sulfated polyacrylate emulsion according to claim 1, wherein: step S2, the reaction temperature of the first bonding reaction is 55-65 ℃, the reaction pressure is 0.1-0.2 MPa, and the reaction time is 10-20 h; the pH value of the first bonding reaction is 8-10.
7. The method for preparing a sulfated polyacrylate emulsion according to claim 1, wherein: step S4 the sulfite solution is selected from Na2SO3，K2SO3，NaHSO3，KHSO3，Na2S2O3One or a mixture of water solutions, wherein the concentration of the sulfite is 10 to 20 percent; the reaction temperature of the second bonding reaction is 60-70 ℃, the reaction pressure is 0.1-0.2 MPa, and the reaction time is 14-18 h.
8. The method for preparing a sulfated polyacrylate emulsion according to claim 1, wherein: in the step S5, the concentration of the acid washing solution is 2.5-3.5%, the acid washing temperature is 35-45 ℃, the time is 60-120 min, and the cycle time is 5-6.
9. The sulfated polyacrylate emulsion obtained by the method for preparing the sulfated polyacrylate emulsion according to any one of claims 1 to 8, wherein: the particle diameter of the sulfated polyacrylate emulsion is 15-90 mu m, and the pore diameter is
10. The sulfated polyacrylate emulsion of claim 9, wherein: the sulfated polyacrylate emulsion has base ball selected from one or more of polymethyl methacrylate base ball, polyglycidyl methacrylate base ball, polyethylene glycol dimethacrylate, polyglycidyl methacrylate-polyethylene glycol dimethacrylate copolymer base ball, polymethyl methacrylate-glycidyl methacrylate copolymer base ball, and polymethyl methacrylate-polyethylene glycol dimethacrylate copolymer base ball.
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| CN114195915A (en) * | 2021-11-04 | 2022-03-18 | 赛分科技扬州有限公司 | Polyacrylate-based sphere and sulfite modification method thereof |
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| CN105833855A (en) * | 2016-06-16 | 2016-08-10 | 青岛盛瀚色谱技术有限公司 | Preparation method of hydrophilic latex-agglomerated anion chromatographic packing |
| CN108889285A (en) * | 2018-07-12 | 2018-11-27 | 纳谱分析技术（苏州）有限公司 | It limits into type chromatograph packing material and preparation method thereof and comprising its stationary phase and application |
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