CN110790853A - Preparation process of washing-free carboxyl polystyrene microsphere - Google Patents
Preparation process of washing-free carboxyl polystyrene microsphere Download PDFInfo
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- CN110790853A CN110790853A CN201911234025.7A CN201911234025A CN110790853A CN 110790853 A CN110790853 A CN 110790853A CN 201911234025 A CN201911234025 A CN 201911234025A CN 110790853 A CN110790853 A CN 110790853A
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention discloses a preparation process of a washing-free carboxyl polystyrene microsphere, which comprises the following steps: (1) pouring a functional monomer solution into the external water phase solution at one time, wherein the functional monomer is one or more of acrylic acid, methacrylic acid and ethyl acrylate, and adding an initiator to initiate polymerization reaction after stirring; (2) and when the polymerization is initiated for 5 min-2 h, adding a mixture of styrene and divinylbenzene for reaction for a period of time, cooling and filtering to obtain the carboxyl polystyrene microspheres. The carboxyl polystyrene microsphere prepared by the process has controllable particle size and carboxyl content, shortens the reaction time, and does not need or only needs a little time for post-treatment.
Description
Technical Field
The invention relates to the field of medical inspection, in particular to a preparation process of a washing-free carboxyl polystyrene microsphere.
Background
In the latex-enhanced immunoturbidimetry, latex microspheres are an indispensable main constituent, and the general preparation process is as follows: as described in patent CN 101775094B: removing polymerization inhibitor from styrene; adding styrene, methacrylic acid and water into a three-neck flask, and stirring for 10-30 min; after stirring, introducing a proper amount of N2 to drive oxygen in the system; adding an initiator to initiate polymerization at the temperature of 60-80 ℃ after deoxidation, reacting for 12-24h, and cooling to room temperature; then centrifugally settling, cleaning and redissolving for many times; thereby obtaining the polystyrene microsphere with carboxyl on the surface.
The following problems are mainly present in the conventional latex preparation methods using the above:
firstly, under the condition of no emulsifier and no cross-linking agent, styrene and methacrylic acid are added into water and stirred, and a uniform oil-in-water emulsion cannot be formed, so that the final latex has nonuniform particle size and nonuniform carboxyl distribution, and the application performance of the final latex is poor; also, the simultaneous addition of styrene and functional monomer initiates polymerization, which results in the presence of 3 polymerization forms in the system: polymerizing styrene and styrene, polymerizing styrene and a functional monomer, and self-polymerizing the functional monomer; the three polymerization rates are different, so that the non-uniform distribution of surface carboxyl groups and the uncontrollable content of the carboxyl groups are easily caused, and the influence on the repeatability among latex batches is large.
Secondly, the reaction time in the method is generally 6-8h, and the reaction time is longer.
Disclosure of Invention
In order to solve the technical problems, the invention discloses a preparation process of a washing-free carboxyl polystyrene microsphere.
The invention is realized by the following technical scheme:
a preparation process of a washing-free carboxyl polystyrene microsphere comprises the following steps:
(1) pouring a functional monomer solution into the external water phase solution at one time, wherein the functional monomer is one or more of acrylic acid, methacrylic acid and ethyl acrylate, and adding an initiator to initiate polymerization reaction after stirring;
(2) after polymerization is initiated for 5 min-2 h, the mixture of styrene and divinyl benzene is added at one time for reaction for a period of time, and then cooling and filtering are carried out to obtain the carboxyl polystyrene microspheres.
In the invention, functional monomers are poured into an external water phase solution containing an emulsifier to initiate polymerization, so that oligomers are acrylic oligomers, the oligomers can replace the function of the emulsifier to form a plurality of micelles, the polymerization reaction of styrene is continued in the micelles, the hollow micelles can limit the particle size of the formed carboxyl polystyrene microspheres to a certain extent, the particle size of the carboxyl polystyrene microspheres is controllable, divinylbenzene is added to serve as a crosslinking agent of the styrene and the acrylic monomers, the polymerization of the styrene and the acrylic monomers is better than the self-polymerization of the styrene and the self-polymerization of the functional monomers, the surface carboxyl content of the latex can be adjusted, and the mixture of the styrene and the divinylbenzene is added at one time in different time after the polymerization of the functional monomers begins; the adjustment of the latex particle size and the surface carboxyl content is realized.
The oligomer of the functional monomer serves as a partial emulsifier, so that the dosage of the emulsifier is small, and the content of the emulsifier is controlled to be less than 1 to 10-5The concentration range of mol/L is far lower than the critical micelle concentration, so that the reaction can be smoothly carried out, the manufacturing cost of the carboxyl polystyrene microsphere is reduced, and more importantly, the post-process treatment is reduced (if the concentration of the emulsifier is too high, the emulsifier needs to be removed by a centrifugal liquid exchange or ultrafiltration mode or greatly reduced, so that the application can be realized). The sodium chloride is added into the latex, the sodium chloride destroys the stability of the latex, and precipitates appear, so that only a supernatant is discarded, after the precipitates are diluted by 10 times by buffer, the redundant residual emulsifier in the latex can be removed, the latex can be more stable, and the diluted latex can be directly applied to latex enhanced immune turbidimetry after being filtered by a PP (polypropylene) filter membrane of 0.65 mu m.
In the step (1), the preparation method of the external water phase solution comprises the following steps:
putting the emulsifier into a three-neck flask, adding HEPES-NaoH buffer solution with the pH value of 8.0, stirring and dissolving to ensure that the concentration of the emulsifier in the water phase is lower than the critical micelle concentration of 1/2; introducing nitrogen or argon into the system, and simultaneously heating to 80-90 ℃, wherein the emulsifier is Sodium Dodecyl Sulfate (SDS) and/or Sodium Dodecyl Benzene Sulfonate (SDBS).
Further, in the step (1), under the conditions of high-speed stirring and nitrogen or argon gas introduction, adding a functional monomer into the external water phase solution, wherein the molar ratio of the functional monomer to styrene is 0.05: 1-0.5: 1, the stirring time is 10-30min, and the nitrogen or argon gas introduction is stopped before adding the initiator.
Further, in the step (1), the initiator is potassium persulfate or ammonium persulfate, and the concentration is 1.0 g/L-10 g/L.
Further, in the step (2), the styrene and divinylbenzene mixture is previously treated with a sodium hydroxide solution to remove the polymerization inhibitor.
Further, in the step (2), in the mixture of styrene and divinylbenzene, the molar ratio of styrene to divinylbenzene is 100: 1.
further, in the step (2), the mixture of styrene and divinylbenzene is added for reaction time of 1-3h, and then cooled to room temperature.
A preparation process of a washing-free carboxyl polystyrene microsphere comprises the following steps in step (2):
1) after the reaction system is cooled, filtering out residues by using filter cloth;
2) adding 35-40 g of sodium chloride into every 100ml of latex, standing overnight at 2-8 ℃, and then removing supernatant;
3) re-dissolving with a buffer according to the solid content requirement, and then filtering with a PP filter membrane of 0.65 mu m to obtain the carboxyl polystyrene microsphere.
The washing-free carboxyl polystyrene microsphere is prepared by the preparation process of the washing-free carboxyl polystyrene microsphere.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention relates to a preparation process of a washing-free carboxyl polystyrene microsphere, which comprises the steps of pouring a functional monomer into an external aqueous phase solution containing an emulsifier to initiate polymerization to form an acrylic oligomer, the oligomer can replace the function of an emulsifier to form a plurality of micelles, so that the polymerization reaction of styrene is continuously carried out in the micelles, the hollow micelles can limit the particle size of the formed carboxyl polystyrene microspheres to a certain extent, the particle size of the carboxyl polystyrene microspheres is controllable, divinylbenzene is added as a cross-linking agent of styrene and acrylic monomers, the polymerization of styrene and acrylic monomers is better than the self-polymerization of styrene and the self-polymerization of functional monomers, the surface carboxyl content of the latex can be adjusted, and the mixture of styrene and divinylbenzene is added at one time at different time after the polymerization of the functional monomer begins; the adjustment of the latex particle size and the surface carboxyl content is realized;
2. the invention relates to a preparation process of a washing-free carboxyl polystyrene microsphere, which has the advantages that the low polymer of a functional monomer serves as a part of emulsifier, so the dosage of the emulsifier is less, and the content of the emulsifier is controlled to be less than 1 x 10-5The concentration range of mol/L is far lower than the critical micelle concentration, so that the reaction can be smoothly carried out, the manufacturing cost of the carboxyl polystyrene microsphere is reduced, and more importantly, the post-process treatment is reduced (if the concentration of the emulsifier is too high, the emulsifier needs to be removed by a centrifugal liquid exchange or ultrafiltration mode or is greatly reduced, so that the application can be realized). Sodium chloride is added into latex, the sodium chloride destroys the stability of the latex, and precipitates appear, so that only a supernatant is discarded, and after the precipitates are diluted by 10 times by buffer, the redundant residual emulsifier in the latex can be removed, the latex can be more stable, and the diluted latex can be directly applied to latex enhanced immunoturbidimetry after being filtered by a PP (polypropylene) filter membrane of 0.65 mu m.
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 with reference to the following examples, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not used as limitations of the present invention.
Example 1
The invention relates to a preparation process of a washing-free carboxyl polystyrene microsphere, which comprises the following steps:
the first step is as follows: the polymerization inhibitor in styrene was removed with sodium hydroxide solution.
The second step is that: preparing an external water phase: weighing emulsifier, placing into a 1L three-neck flask, adding 400ml HEPES-NaoH buffer (pH 8.0), stirring to dissolve until the concentration of emulsifier in water phase is lower than the critical micelle concentration of 1/2; introducing nitrogen or argon into the system, and simultaneously heating to 80-90 ℃, wherein the emulsifier is Sodium Dodecyl Sulfate (SDS) and/or Sodium Dodecyl Benzene Sulfonate (SDBS).
The third step: under the condition of high-speed stirring, 1 (2 or 3) of acrylic acid, methacrylic acid and ethyl acrylate is poured into the reactor at one time; the molar ratio of the styrene to the styrene is 0.05: 1-0.5: 1; stirring for 10-30min to obtain milky white emulsion.
The fourth step: stopping introducing nitrogen or argon; weighing an appropriate amount of initiator and dissolving the initiator in HEPES-NaoH buffer (pH 8.0); then, 1.0g of potassium persulfate as an initiator was immediately added to initiate polymerization.
The fifth step: when the reaction proceeded for 5min, a mixture of styrene and divinylbenzene was added in one portion.
And a sixth step: reacting for 1-3 h; then cooling it to room temperature; the residue was filtered off with a filter cloth.
The seventh step: 35-40 g of sodium chloride is added into each 100ml of latex, the mixture is kept overnight at the temperature of 2-8 ℃, and then the supernatant is discarded.
Eighth step: according to the solid content requirement; redissolving the lower layer of solid in 9 times volume of buffer; then filtering with a PP filter membrane of 0.65 mu m to obtain a target product, wherein the target product can be directly applied to the preparation of the latex immunoenhancement turbidimetric reagent without centrifugation or ultrafiltration.
Examples 2 to 6
Examples 2 to 6 the non-cleaned carboxy polystyrene microspheres were prepared according to the procedure of example 1, and the raw materials, amounts, concentrations and reaction conditions specifically mentioned are shown in table 1:
the properties of the carboxy polystyrene microsphere latex prepared in examples 2 to 6 were measured, and the measurement results are shown in table 2:
the measurement results in table 2 show that: after first adding different volumes of functional monomer for polymerization, mixtures of styrene and divinylbenzene were added at different times, which had different effects on the particle size and surface carboxyl content of the latex. Therefore, the particle size and the carboxyl content can be controlled in a certain range.
Latex properties of the examples of the invention application properties:
the latex of example 2 and the CBO104D from polymicrospheres were applied to the cystatin C (Cys-C) assay reagent R2:
| calibration article | 0.0mg/L | 0.6mg/L | 1.2mg/L | 3.6mg/l | 6.0mg/L | 12.0mg/L |
| CBO104D | -5 | 123 | 345 | 660 | 1250 | 2500 |
| Example 2 | -10 | 210 | 650 | 1420 | 3000 | 4800 |
The reagent prepared by using the latex in the example 2 has higher reaction absorbance at each calibration point than the reagent prepared by using the CBO104D latex, namely, the sensitivity is higher; and completely meets the application requirements of the reagent.
Latex from example 3 and CBO91E from polymicrospheres were applied to Retinol Binding Protein (RBP) assay reagent R2:
| calibration article | 0.0mg/L | 15.0mg/L | 30.0mg/L | 60.0mg/l | 120.0mg/L | Amount of antibody used |
| CBO91E | -7 | 750 | 1706 | 3623 | 6300 | 90.0ml |
| Example 3 | 15 | 1412 | 3756 | 9151 | 17983 | 63.0ml |
The reaction absorbance of the reagent prepared by using the latex in the example 3 at each calibration point is higher than that of the reagent prepared by using the CBO91E latex, so that the sensitivity is higher; and completely meets the application requirements of the reagent; meanwhile, the dosage of the antibody can be reduced by about 30 percent, and the reagent cost is greatly reduced.
The latex of example 4 and the CBO172E from polymicrospheres were applied to β 2-mg microglobulin assay reagent R2:
| calibration article | 0.00mg/L | 2.00mg/L | 6.00mg/L | 12.00mg/L | 24.00mg/L |
| CBO172E | 3985 | 5160 | 8133 | 9513 | 11236 |
| Example 4 | 4250 | 5613 | 9120 | 12137 | 18221 |
The reagent prepared using the latex of example 4 had a higher reaction absorbance at each calibration point than the reagent prepared using CBO172E latex; not only completely meets the application requirements of the reagent.
Latex from example 5 and CBO207E from polymicrospheres were applied to Myoglobin (MYO) assay reagent R2:
| calibration article | 0ng/mL | 100ng/mL | 200ng/mL | 400ng/mL | 800ng/mL |
| CBO207E | -16 | 116 | 368 | 790 | 1679 |
| Example 5 | 38 | 367 | 745 | 1566 | 2951 |
The reagent prepared using the latex of example 5 had a higher reaction absorbance at each calibration point than the reagent prepared using CBO207E latex; the low-end analysis sensitivity of the kit is about 3 times higher than that of a reagent prepared from CBO207E latex, and the accuracy of the measurement result of a low-concentration sample of the reagent is greatly improved.
The latex of example 6 and the CBO258D from polymicrospheres were applied to a D-dimer assay reagent R2:
| calibration article | 0mg/L | 1.5mg/L | 3.0mg/L | 7.5mg/L | 15.0mg/L | 30.0mg/L |
| CBO258D | 178 | 229 | 698 | 1356 | 2075 | 3013 |
| Example 6 | 230 | 415 | 1266 | 2349 | 4122 | 5230 |
The reagent prepared using the latex of example 6 had a higher reaction absorbance at each calibration point than the reagent prepared using the CBO258D latex.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation process of a washing-free carboxyl polystyrene microsphere is characterized by comprising the following steps:
(1) pouring a functional monomer solution into the external water phase solution at one time, wherein the functional monomer is one or more of acrylic acid, methacrylic acid and ethyl acrylate, and adding an initiator to initiate polymerization reaction after stirring;
(2) after the polymerization is initiated for 5 min-2 h, the mixture of styrene and divinyl benzene is added at one time for reaction for a period of time, and then the carboxyl polystyrene microspheres are obtained by cooling and filtering.
2. The preparation process of the washing-free carboxyl polystyrene microsphere as claimed in claim 1, wherein in the step (1), the preparation method of the external water phase solution is as follows:
putting the emulsifier into a three-neck flask, adding HEPES-NaoH buffer solution with the pH value of 8.0, and stirring to dissolve the emulsifier so that the concentration of the emulsifier in the water phase is lower than the critical micelle concentration of 1/2; introducing nitrogen or argon into the system, and simultaneously heating to 80-90 ℃, wherein the emulsifier is Sodium Dodecyl Sulfate (SDS) and/or Sodium Dodecyl Benzene Sulfonate (SDBS).
3. The preparation process of the washing-free carboxyl polystyrene microsphere as claimed in claim 1, wherein in the step (1), under the conditions of high-speed stirring and introduction of nitrogen or argon, the functional monomer is added into the external water phase solution, the molar ratio of the functional monomer to styrene is 0.05: 1-0.5: 1, the stirring time is 10-30min, and the introduction of nitrogen or argon is stopped before the initiator is added.
4. The preparation process of the washing-free carboxyl polystyrene microsphere as claimed in claim 1, wherein in the step (1), the initiator is potassium persulfate or ammonium persulfate, and the concentration is 1.0 g/L-10 g/L.
5. The process for preparing washing-free carboxy polystyrene microspheres as claimed in claim 1, wherein in the step (2), the polymerization inhibitor is removed from the mixture of styrene and divinylbenzene by sodium hydroxide solution.
6. The process for preparing washing-free carboxy polystyrene microspheres of claim 1, wherein in the step (2), the molar ratio of styrene to divinylbenzene in the mixture of styrene and divinylbenzene is 100: 1.
7. the process for preparing non-washing carboxy polystyrene microspheres of claim 1, wherein in the step (2), the mixture of styrene and divinylbenzene is added for 1-3h, and then cooled to room temperature.
8. The preparation process of the washing-free carboxyl polystyrene microsphere as claimed in claim 1, wherein in the step (2), the filtration process is as follows:
1) after the reaction system is cooled, filtering out residues by using filter cloth;
2) adding 35-40 g of sodium chloride into every 100ml of latex, standing overnight at 2-8 ℃, and then removing supernatant;
3) re-dissolving with a buffer according to the solid content requirement, and then filtering with a PP filter membrane of 0.65 mu m to obtain the carboxyl polystyrene microsphere.
9. A washing-free carboxy polystyrene microsphere, which is prepared by the preparation process of the washing-free carboxy polystyrene microsphere as claimed in any one of claims 1 to 8.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111892736A (en) * | 2020-08-13 | 2020-11-06 | 上海科华生物工程股份有限公司 | Polystyrene microsphere for improving sensitivity of latex turbidimetry and preparation method thereof |
| CN113150200A (en) * | 2021-03-16 | 2021-07-23 | 苏州为度生物技术有限公司 | Preparation method and application of carboxyl latex microspheres |
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Cited By (3)
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| CN111892736A (en) * | 2020-08-13 | 2020-11-06 | 上海科华生物工程股份有限公司 | Polystyrene microsphere for improving sensitivity of latex turbidimetry and preparation method thereof |
| CN111892736B (en) * | 2020-08-13 | 2022-08-26 | 上海科华生物工程股份有限公司 | Polystyrene microsphere for improving sensitivity of latex turbidimetry and preparation method thereof |
| CN113150200A (en) * | 2021-03-16 | 2021-07-23 | 苏州为度生物技术有限公司 | Preparation method and application of carboxyl latex microspheres |
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