CN114262465A - Polyacrylate-based sphere and amine salt modification method thereof - Google Patents
Polyacrylate-based sphere and amine salt modification method thereof Download PDFInfo
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Abstract
The invention provides an amine salt modification method of polyacrylate-based spheres, which comprises the steps of carrying out bonding reaction on the polyacrylate-based spheres after activation treatment, and carrying out cleaning and solution washing treatment for multiple times to finally obtain polyacrylate emulsion, wherein the amine salt modification method is carried out in a water phase system, the reaction temperature is mild, the pressure is close to normal pressure, so that the control of the reaction condition is easy to realize, the particle size of the obtained emulsion is 15-90 mu m, and the pore diameter is 15-90 mu m
The 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 separation and purification of biological samples with larger molecular weight; meanwhile, the amine salt modification 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 amine salt modification of polyacrylate-based sphere materials for carriers, in particular to a polyacrylate-based sphere and an amine salt modification method of the polyacrylate-based sphere.
Background
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 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 polyacrylate-based sphere and a method for modifying amine salt of the polyacrylate-based sphere. 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 an amine salt modification method of polyacrylate-based spheres, which comprises the steps of carrying out bonding reaction on the polyacrylate-based spheres after activation treatment, and carrying out multiple cleaning and solution washing treatment to finally obtain polyacrylate emulsion.
In order to achieve the above object, the present invention provides a method for modifying an amine salt of polyacrylate-based spheres, the method comprising the steps of:
s1 mixing amine salt modifiers, conveying the amine hydrochloride prepared in advance into a stirrer filled with a certain amount of pure water for mixing to form an amine salt solution, wherein the stirring speed of the stirrer is 250-350 rpm, and the time is 60-120 min;
s2 bonding reaction, namely dispersing the activated polyacrylate-based spheres in the amine salt solution obtained in the step S1 for bonding reaction at the temperature of 60-70 ℃, the reaction pressure of 0.1-0.2 MPa and the reaction time of 14-18 h; carrying out surface modification on the polyacrylate-based spheres to form functional group emulsion to obtain a crude polyacrylate emulsion;
s3, carrying out first centrifugal cleaning, namely putting the crude polyacrylate emulsion obtained in the step S2 into a centrifugal machine, adding pure water, and carrying out first centrifugal separation cleaning, wherein the rotating speed of the centrifugal machine is 500-800 rpm, and the time is 50-60 min, so as to fully remove residual solvent and unreacted reagent.
S4, washing, namely adding the crude product of the polyacrylate emulsion into an ethanol solution for washing for 60-120 min, wherein the cycle time is 6-8 times, the concentration of the ethanol solution is 5% -6%, and removing residual solvent and unreacted reagent;
s5, carrying out second centrifugal cleaning, namely putting the washed crude polyacrylate emulsion into the centrifuge again and adding pure water to carry out second centrifugal separation cleaning, wherein the rotation speed of the centrifuge is 500-800 rpm, and the time is 50-60 min, so as to fully remove the residual ethanol solvent;
s6, soaking, namely soaking and shaping the cleaned polyacrylate emulsion by using an ethanol water solution to obtain an amine salt modified polyacrylate emulsion finished product.
Further, in step S1, the amine salt solution is selected from one or a mixture of hydrochloric acid aqueous solutions of trimethylamine, triethylamine, diethanolamine and dimethylamine, and the concentration of the amine salt is 45% to 55%;
the polyacrylate-based spheres in the step S2 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, polymethyl methacrylate-polyethylene glycol dimethacrylate copolymer spheres, polystyrene-glycidyl methacrylate copolymer spheres, and polystyrene-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 0.3-0.7M 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.
The alkane solution is a chloropropane aqueous solution, and the concentration of the chloropropane is 4.5-5.5%;
step S6, the ethanol concentration of the ethanol water solution is 18% -22%, the volume ratio (v/v) of the polyacrylate-based spheres to the ethanol water solution is 10: 7-8; the polyacrylate-based spheres are stored in an ethanol water solution for a long time; the particle diameter of the polyacrylate-based sphere is 15-90 mu m, and the pore diameter is
The particle size after amine salt modification is more uniform, and the product has good physical and chemical stability.
Compared with the prior art, the invention has the following beneficial effects:
1. the amine salt modification method of polyacrylate-based sphere adopts preformed base sphere activation treatment and carries out graded bonding reaction on activated microspheres to obtain polyacrylate emulsion, the amine salt modification method adopts a water phase system as a reaction system, the reaction temperature and the reaction pressure are relatively low, the chemical reaction conditions are mild, the polyacrylate emulsion obtained by amine salt modification has uniform particle size, the particle size is 15-90 mu m, and the pore size is 15-90 mu m
(ii) a Meanwhile, the amine salt modification method has simple flow, and the used raw materials are easy to obtain, so that the production cost is lower. The 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 separation and purification of biological samples with larger molecular weight.
2. The amine salt modification method of the invention preferentially selects polyacrylate-based spheres for activation treatment, adopts the activation solution of concentrated sulfuric acid in 0.3-0.7M of acidic activation treatment solution, and has the advantages of easy control of the activation condition, easy obtainment of the activation solution and good activation effect under the stirring condition.
3. The amine salt modification method of the invention carries out the hierarchical bonding reaction on the activated polyacrylate microspheres, carries out the amine salt chain extension treatment on the polyacrylate to obtain the polyacrylate emulsion, adopts the control mode of the hierarchical reaction, has easily controlled reaction conditions, high utilization rate of raw materials, more complete chemical reaction, higher conversion rate of products and further reduces the production cost.
Drawings
FIG. 1 is a process flow diagram of a method for modifying amine salts of polyacrylate-based spheres in accordance with 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 method for modifying amine salt of polyacrylate-based spheres, which comprises the following main steps:
s1 mixing amine salt modifiers, conveying the amine hydrochloride prepared in advance into a stirrer filled with a certain amount of pure water for mixing to form an amine salt solution, wherein the stirring speed of the stirrer is 250-350 rpm, and the time is 60-120 min; the amine salt solution is selected from one or a mixed hydrochloric acid aqueous solution of trimethylamine, triethylamine, diethanolamine and dimethylamine, and the concentration of the amine salt is 45 to 55 percent;
s2 bonding reaction, namely dispersing the activated polyacrylate-based spheres in the amine salt solution obtained in the step S1 to perform bonding reaction, wherein the 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 the polyacrylate-based spheres to form functional group emulsion to obtain a crude polyacrylate emulsion;
s3, centrifugal cleaning for the first time, namely putting the crude product of the polyacrylate emulsion obtained in the step S2 into a centrifuge, adding pure water, and carrying out centrifugal separation and cleaning for the first time, wherein the rotation speed of the centrifuge is 500-800 rpm, and the time is 50-60 min, so as to fully remove residual solvent and unreacted reagent.
S4, washing, namely adding the crude product of the polyacrylate emulsion into an ethanol solution for washing for 60-120 min, wherein the cycle time is 6-8 times, the concentration of the ethanol solution is 5-6%, and removing residual solvent and unreacted reagent;
s5, carrying out second centrifugal cleaning, namely putting the washed crude product of the polyacrylate emulsion into the centrifuge again, adding pure water for second centrifugal separation and cleaning, wherein the rotation speed of the centrifuge is 500-800 rpm, and the time is 50-60 min, so as to fully remove the residual ethanol solvent;
s6, soaking, namely soaking and shaping the cleaned polyacrylate emulsion by using an ethanol water solution to obtain an amine salt modified polyacrylate emulsion finished product; the ethanol concentration of the ethanol aqueous solution is 18-22%, and the volume ratio (v/v) of the polyacrylate-based spheres to the ethanol aqueous solution is 10: 7-8; the polyacrylate-based spheres are stored in an ethanol water solution for a long time; the particle diameter of the polyacrylate-based sphere is 15-60 mu m, and the pore diameter is
The particle size after amine salt modification is more uniform, and the product has good physical and chemical stability.
Further, the polyacrylate-based spheres of step S2 are selected from the group consisting of polymethyl methacrylate-based spheres, polyglycidyl methacrylate-based spheres, polyethylene glycol dimethacrylate, polyglycidyl methacrylate-polyethylene glycol dimethacrylate copolymer-based spheres, and polymethyl methacrylateOne or a mixture of methyl acrylate-glycidyl methacrylate copolymer ball, polymethyl methacrylate-polyethylene glycol dimethacrylate copolymer ball, polystyrene-glycidyl methacrylate copolymer ball and polystyrene-polyethylene glycol dimethacrylate copolymer ball; the polyacrylate-based spheres have a particle size of 15 to 90 μm and a pore diameter of
(ii) a The acid activation treatment uses concentrated sulfuric acid to prepare 0.3-0.7M concentrated sulfuric acid solution, and the polyacrylate-based balls are added into the concentrated sulfuric acid solution and stirred uniformly to activate the polyacrylate-based balls, wherein the stirring speed is 250-350 rpm, and the activation time is 60-120 min.
Specifically, the amine salt modification method of the polyacrylate-based spheres comprises the step S1 of preparing and mixing materials, quantitatively conveying the pure water in the charging basket to the first liquid preparation kettle by using a pure water first conveying pump, quantitatively conveying the amine salt solution in the charging basket to the first liquid preparation kettle by using an amine salt solution second conveying pump, and uniformly stirring and mixing for later use.
S2 bonding reaction, namely allowing the mixed solution in the first solution preparation kettle to flow into a bonding reaction B kettle automatically, 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.
S3 centrifugal cleaning for the first time, sending filter cakes to a second washing kettle after centrifugal separation by a second centrifugal machine, adding pure water into the second washing kettle for washing, further removing residual solvent and unreacted reagent, sending the washed mixed solution to the second centrifugal machine for centrifugal separation, sending the separated filter cakes to the second washing kettle, washing for 6-8 times repeatedly, and sending the filter cakes after the last centrifugal separation to a fourth acid washing kettle.
And S4, washing, namely adding pure water into a fourth pickling kettle, introducing a refrigerant and a heating medium into a jacket of the fourth pickling kettle, determining whether a refrigerant or heating medium pipeline valve is opened according to the temperature of the fourth pickling kettle, wherein the pickling temperature of the fourth pickling 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.
S5, centrifugal cleaning for the second time, sending filter cakes to a second washing kettle after centrifugal separation by a second centrifugal machine, adding pure water into the second washing kettle, washing to further remove residual solvent and unreacted reagent, sending the washed mixed solution to the second centrifugal machine for centrifugal separation, sending the separated filter cakes to the second washing kettle, and repeatedly washing for 6-8 times.
S6, soaking the centrifuged wet material emulsion in 18-22% ethanol water solution, wherein the volume ratio (v/v) of the polyacrylate emulsion to the ethanol water solution is 10: 7-8, and obtaining the amine salt modified polyacrylate emulsion product.
The polyacrylate emulsion obtained by the amine salt modification method has uniform particle size of 15-90 μm and pore diameter of
The polyacrylate emulsion has better hydrophilicity, avoids nonspecific adsorption with biological samples to the maximum extent, has larger pore diameter compared with other hydrophobic fillers or carriers, and is more suitable for protein carriers with larger molecular weight or separation.
Example 1:
the method for modifying the amine salt of polyacrylate-based spheres provided by the embodiment mainly comprises the following steps: firstly, the poly glycidyl methacrylate base ball modified by amine salt in advance is adopted, the particle diameter of the poly glycidyl acrylate base ball is 15-25 mu m, and the pore diameter is
Concentrated sulfuric acid is used to prepare 0.45M concentrated sulfuric acidCarrying out acid activation treatment on a sulfuric acid solution, adding a polyacrylate-based sphere into a concentrated sulfuric acid solution, and uniformly stirring to activate the base sphere, wherein the stirring speed is 300rpm, and the activation time is 80min so as to obtain an activated polyacrylate microsphere;
secondly, dispersing the polyacrylic epoxy ester filter cake into a 53% dimethylamine salt hydrochloric acid solution modified by amine salt in advance, controlling the reaction temperature to be 60 ℃, the reaction pressure to be 0.18MPa and the reaction time to be 14h, and carrying out bonding reaction to modify the surface of the polyacrylic epoxy ester filter cake to form functional group emulsion so as to obtain a crude product of the polyacrylic ester emulsion;
then, adding dilute sulfuric acid solution or dilute hydrochloric acid solution with the concentration of 3.2% into the polyacrylate emulsion for acid cleaning, wherein the acid cleaning 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 polyacrylate emulsion by using an ethanol aqueous solution with the concentration of 18%, wherein the volume ratio (v/v) of the emulsion to the ethanol aqueous solution is 10: 7.5, obtaining a finished product of the polyacrylate emulsion.
The polyacrylate emulsion obtained by the amine salt modification method has uniform particle size, average particle size D50 of 40.8 μm, ratio of D90 to D10 of 1.41, loading capacity of 101.3g/l, and pore diameter of 101.3g/l
Example 2:
the method for modifying the amine salt of polyacrylate-based spheres provided by the embodiment mainly comprises the following steps: firstly, the polyethylene glycol dimethacrylate-based spheres modified by amine salt in advance are adopted, the particle diameter of the polyacrylate-based spheres is 30-50 mu m, and the pore diameter is
Using concentrated sulfuric acid to prepare 0.35M concentrated sulfuric acid solution for acid activation treatment, adding polyacrylate-based balls into the concentrated sulfuric acid solution, and uniformly stirring to activate the base balls, wherein the stirring speed is 350rpm, and the activation time is 110min, so thatObtaining activated polyacrylate microspheres;
secondly, dispersing the polyacrylic epoxy ester filter cake into 48% triethylamine salt hydrochloric acid solution modified by amine salt in advance, controlling the reaction temperature to be 65 ℃, the reaction pressure to be 0.16MPa and the reaction time to be 18h, and carrying out bonding reaction to modify the surface of the polyacrylic epoxy ester filter cake to form functional group emulsion so as to obtain a crude product of the polyacrylic ester emulsion;
then, adding a dilute sulfuric acid solution or a dilute hydrochloric acid solution with the concentration of 2.8% into the 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 the residual alkaline solvent and unreacted reagents;
finally, soaking and shaping the cleaned 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 polyacrylate emulsion.
The polyacrylate emulsion obtained by the amine salt modification method has uniform particle size, average particle size D50 of 17.3 μm, ratio of D90 to D10 of 1.31, loading capacity of 102.1g/l, and pore diameter of 102.1g/l
Example 3:
the method for modifying the amine salt of polyacrylate-based spheres provided by the embodiment mainly comprises the following steps: firstly, poly glycidyl methacrylate-poly ethylene glycol dimethacrylate copolymer ball modified by amine salt in advance is adopted, the particle diameter of the copolymer polyacrylate ball is 45-60 mu m, and the pore diameter is
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, dispersing the copolymerized polyacrylic acid epoxy ester filter cake into a 45% trimethylamine hydrochloride solution modified by amine salt in advance, controlling the reaction temperature to be 65 ℃, the reaction pressure to be 0.12MPa and the reaction time to be 16h, carrying out bonding reaction, and carrying out surface modification on the copolymerized polyacrylic acid epoxy ester filter cake to form functional group emulsion so as to obtain a crude product of the polyacrylate copolymerized 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 polyacrylate emulsion.
The polyacrylate emulsion obtained by the amine salt modification method has uniform particle size, the average particle size D50 is 27.8 μm, the ratio of D90 to D10 is 1.35, the loading capacity is 104.4g/l, and the pore diameter is 104.4g/l
(ii) a The polyacrylate emulsion is suitable for a buffer salt system of tris (hydroxymethyl) aminomethane, phosphate and acetate buffer solution, and the conventional organic phase is a system of acetonitrile, ethanol and a water phase; the polyacrylate emulsion also has high mechanical stability on a chromatographic column filler so as to ensure that the polyacrylate emulsion can bear the pressure of 10bar at most, and can meet the requirements of high flow rate and reduced operation time in the development of an industrial purification process; 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 emulsion can improve the pressure resistance of the filler, can realize sample purification at a higher flow rate, or can be provided with longer filler chromatographic columns, can process more biological samples in batches, saves time and improves the production efficiency. In the aspect of drug carriersAnd unstable biological samples can be subjected to mother liquor required to be quickly separated and purified, so that the production efficiency is improved, and the yield and quality control of products can be improved.
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 modifying an amine salt of polyacrylate-based spheres, comprising the steps of:
s1 mixing amine salt modifiers, conveying the amine salt prepared in advance into a stirrer filled with a certain amount of pure water for mixing to form an amine salt solution, wherein the stirring speed of the stirrer is 250-350 rpm, and the time is 60-120 min;
s2 bonding reaction, namely dispersing the activated polyacrylate-based spheres in the amine salt solution obtained in the step S1 for bonding reaction at the temperature of 60-70 ℃, the reaction pressure of 0.1-0.2 MPa and the reaction time of 14-18 h; carrying out surface modification on the polyacrylate-based spheres to form functional group emulsion to obtain a crude polyacrylate emulsion;
s3, carrying out first centrifugal cleaning, namely putting the crude polyacrylate emulsion obtained in the step S2 into a centrifugal machine, adding pure water, and carrying out first centrifugal separation and cleaning, wherein the rotating speed of the centrifugal machine is 500-800 rpm, and the time is 50-60 min;
s4, washing, namely adding the crude product of the polyacrylate emulsion into an ethanol solution for washing, wherein the washing time is 60-120 min, the cycle time is 6-8 times, and the concentration of the ethanol solution is 5% -6%;
s5, carrying out second centrifugal cleaning, namely putting the washed crude polyacrylate emulsion into the centrifuge again and adding pure water to carry out second centrifugal separation cleaning, wherein the rotation speed of the centrifuge is 500-800 rpm, and the time is 50-60 min;
s6, soaking, namely soaking and shaping the cleaned polyacrylate emulsion by using an ethanol water solution to obtain an amine salt modified polyacrylate emulsion finished product.
2. The method of modifying an amine salt of a polyacrylate based sphere according to claim 1, wherein: and step S1, the amine salt is selected from one or a mixture of trimethylamine, triethylamine, diethanolamine and dimethylamine.
3. The method of modifying an amine salt of a polyacrylate based sphere according to claim 2, wherein: the concentration of the amine salt is 45-55%.
4. The method of modifying an amine salt of a polyacrylate based sphere according to claim 1, wherein: the polyacrylate based spheres in step S2 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, polymethyl methacrylate-polyethylene glycol dimethacrylate copolymer spheres, polystyrene-glycidyl methacrylate copolymer spheres, and polystyrene-polyethylene glycol dimethacrylate copolymer spheres.
5. The method of modifying an amine salt of a polyacrylate based sphere according to claim 4, wherein: the particle diameter of the polyacrylate-based sphere is 15-90 mu m, and the pore diameter is
6. The method of modifying an amine salt of a polyacrylate based sphere according to claim 1, wherein: and step S2, preparing a 0.3-0.7M concentrated sulfuric acid solution by using concentrated sulfuric acid in the activation treatment, and adding the polyacrylate-based spheres into the concentrated sulfuric acid solution and uniformly stirring to activate the polyacrylate-based spheres.
7. The method of modifying an amine salt of a polyacrylate based sphere according to claim 6, wherein: the stirring speed is 250 rpm-350 rpm, and the activation time is 60 min-120 min.
8. The method of modifying an amine salt of a polyacrylate based sphere according to claim 1, wherein: step S6, the ethanol concentration of the ethanol water solution is 18% -22%, the volume ratio (v/v) of the polyacrylate-based spheres to the ethanol water solution is 10: 7 to 8.
9. The polyacrylate emulsion obtained by the method for modifying an amine salt of a polyacrylate based sphere according to any one of claims 1 to 8, wherein: the particle size of the polyacrylate emulsion is 15-90 mu m, and the pore diameter is
10. The polyacrylate emulsion of claim 9 wherein: the base ball of the polyacrylate emulsion is selected from one or a mixture 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, polymethyl methacrylate-polyethylene glycol dimethacrylate copolymer base ball, polystyrene-glycidyl methacrylate copolymer base ball and polystyrene-polyethylene glycol dimethacrylate copolymer base ball.
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| CN115414921A (en) * | 2022-08-30 | 2022-12-02 | 赛分科技扬州有限公司 | Surface modification method of ion exchange filler |
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