CN110721644A - Radiation preparation method of vinyl polymer microcapsule - Google Patents
Radiation preparation method of vinyl polymer microcapsule Download PDFInfo
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- CN110721644A CN110721644A CN201911006185.6A CN201911006185A CN110721644A CN 110721644 A CN110721644 A CN 110721644A CN 201911006185 A CN201911006185 A CN 201911006185A CN 110721644 A CN110721644 A CN 110721644A
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- 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
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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Abstract
The invention relates to a radiation preparation method of vinyl polymer microcapsules, in particular to a method for preparing vinyl polymer microcapsules by radiation emulsion polymerization, belonging to the technical field of micro-packaging. The method comprises the steps of dropwise adding an oil phase solution into an emulsifier solution under continuous stirring to obtain an oil-in-water emulsion; placing the oil-in-water emulsion in a glass bottle, and irradiating on an electron accelerator; and washing and filtering the irradiated emulsion to obtain the vinyl polymer microcapsule. The reaction time is extremely short, and the efficiency is high; in terms of emission power, a 5KW accelerator is equivalent to a 40-kilo-curie cobalt-60 radioactive source, and the cobalt-60 radioactive source emits rays in a spherical shape, so that the utilization rate of the rays is low, about 20 percent is low, and the rays in other directions are wasted; the ray direction of the accelerator is one direction, and the utilization rate of the ray is high and reaches more than 93%. Therefore, the microcapsule is prepared by irradiation of the electron accelerator, the reaction time is extremely short, and the efficiency is high.
Description
Technical Field
The invention relates to a radiation preparation method of vinyl polymer microcapsules, in particular to a method for preparing vinyl polymer microcapsules by radiation emulsion polymerization, belonging to the technical field of micro-packaging.
Background
The microcapsule technology is a technology of wrapping trace substances in a polymer film, is a micro-packaging technology for storing solid, liquid and gas, and the obtained micro-particles are called microcapsules. The particle diameter of the prepared microcapsule is 1-500 um, and the wall thickness is 0.5-150 um. Due to the special structure, various performances and stable encapsulation capacity of the microcapsule, the microcapsule has wide application in the fields of medicine, biology, food, chemical industry and the like. At present, the materials used as microcapsule wall are mainly synthetic high molecular polymers, such as melamine resin, phenolic resin, urea resin and the like, but the capsule wall materials contain more or less free formaldehyde, which can harm human health and greatly restrict the development of the microcapsule wall materials. Subsequently, non-toxic vinyl polymers, such as polystyrene and polymethacrylate-based synthetic polymers, have been developed and studied in succession. At present, the preparation method of the vinyl polymer microcapsule is mainly a chemical emulsion polymerization method initiated by an initiator, and the method has the advantages of high initiation temperature, high polymerization temperature, difficult control of reaction process, longer reaction time and high energy consumption. With the development of irradiation techniques in recent years, the production of vinyl polymer microcapsules using irradiation techniques has been reported. Currently, irradiation sources mainly include electron beams, cobalt sources (gamma rays), ultraviolet rays, microwaves, and the like. Ultraviolet rays and microwaves are used as irradiation sources, and a photoinitiator with certain toxicity still needs to be added. And high-energy electron beams and cobalt sources (gamma rays) are used as irradiation sources, so that the free radical polymerization can be directly carried out without adding an initiator. Most of the radiation sources used for preparing the vinyl polymer microcapsules at the present stage are cobalt sources, but the problems of long radiation processing time, high selling price, difficult waste source treatment, low ray utilization rate and the like exist. Compared with cobalt sources, electron accelerators have the following advantages: (1) carrying out rapid irradiation; (2) the utilization rate of rays is high (3) the absorbed dose is uniform; (4) no environmental pollution is caused; (5) has no toxicity and residue.
Disclosure of Invention
The invention aims to solve the problems of long processing time, high cost and the like in the prior art, and provides a radiation preparation method of vinyl polymer microcapsules. The method has the advantages of reaction at normal temperature, no need of initiating agent and extremely short reaction time.
The purpose of the invention is realized by the following technical scheme.
A radiation preparation method of vinyl polymer microcapsules comprises the following steps:
preparation of the aqueous phase: dissolving an emulsifier into distilled water to obtain an emulsifier solution; the concentration of the emulsifier solution is 1-3%;
preparation of oil phase: uniformly mixing a vinyl monomer, a cross-linking agent and a core material to obtain an oil phase solution; the mass ratio of the vinyl monomer to the cross-linking agent to the core material is 1: 0.1: 1;
emulsification: dropwise adding the oil phase solution into the emulsifier solution under continuous stirring to obtain an oil-in-water emulsion;
placing the oil-in-water emulsion in a glass bottle, and irradiating on an electron accelerator; and washing and filtering the irradiated emulsion to obtain the vinyl polymer microcapsule.
The emulsifier comprises: sodium dodecyl sulfate, polyvinylpyrrolidone, dodecyl trimethyl ammonium bromide, Tween-80 or Span-80, etc.;
the vinyl monomers include: styrene, methyl methacrylate, methyl acrylate, vinyl acetate, or the like;
the crosslinking agent comprises: divinylbenzene, pentaerythritol tetraacrylate, allyl methacrylate, or the like;
the core material can be an oil capsule core material which is insoluble in water and miscible with a vinyl monomer, such as hydroxyl-terminated silicone oil, ethyl orthosilicate, methyltrimethoxysilane, dibutyltin dilaurate or liquid paraffin;
in the emulsification process, after the oil phase solution is completely dripped, stirring is continuously carried out for 15-45 minutes to obtain a stable oil-in-water emulsion;
the parameters of the electron accelerator are set as electron beam 10MeV, beam current 1.5-2 mA, and rated power 15-20 KW;
the irradiation dose is 5-50 kGy, and the irradiation time is 10-30 minutes.
Advantageous effects
1. The radiation preparation method of the vinyl polymer microcapsule has extremely short reaction time and high efficiency; in terms of emission power, a 5KW accelerator is equivalent to a 40-kilo-curie cobalt-60 radioactive source, and the cobalt-60 radioactive source emits rays in a spherical shape, so that the utilization rate of the rays is low, about 20 percent is low, and the rays in other directions are wasted; the ray direction of the accelerator is one direction, and the utilization rate of the ray is high and reaches more than 93%. Therefore, the microcapsule is prepared by irradiation of the electron accelerator, the reaction time is extremely short, and the efficiency is high;
2. according to the radiation preparation method of the vinyl polymer microcapsule, a toxic initiator is not required to be added into a reaction system;
3. the radiation preparation method of the vinyl polymer microcapsule has low reaction temperature and can be carried out at room temperature;
4. the radiation preparation method of the vinyl polymer microcapsule has the advantages of simple equipment and production process and convenient operation.
Drawings
FIG. 1 is a scanning electron microscope image of the vinyl polymer microcapsule prepared in example 1.
FIG. 2 is a thermogravimetric analysis chart of the vinyl polymer microcapsule prepared in example 1.
Detailed Description
The invention is further described with reference to the following figures and examples.
Example 1
A radiation preparation method of vinyl polymer microcapsules comprises the following steps:
(1) preparation of the aqueous phase: weighing 1.8g of emulsifier polyvinylpyrrolidone (PVPK-30) in a beaker, adding 120g of distilled water, and fully dissolving;
(2) preparation of oil phase: uniformly mixing 12g of monomer styrene, 1.2g of divinyl benzene and 12g of liquid paraffin;
(3) emulsification: placing an emulsifying machine with a stirrer in the water phase, starting a stirring motor, slowly dripping the oil phase into the water phase under vigorous stirring, and continuously stirring for 20 minutes to prepare an oil-in-water emulsion;
(4) placing the emulsion in a glass bottle, and irradiating on an irradiation accelerator;
(5) after the irradiation is carried out for 10 minutes, the irradiation source is closed, and the reaction is stopped;
(6) washing and filtering the irradiated emulsion;
(7) and (4) obtaining the vinyl polymer microcapsule after passing the inspection.
Example 2
A radiation preparation method of vinyl polymer microcapsules comprises the following steps:
(1) preparation of the aqueous phase: weighing 1.5g of polyvinylpyrrolidone (PVPK-30) in a beaker, adding 120g of distilled water, and fully dissolving;
(2) preparation of oil phase: uniformly mixing 12g of monomer styrene, 1.2g of cross-linking agent divinylbenzene and 12g of oily capsule core hydroxyl-terminated silicone oil;
(3) emulsification: placing an emulsifying machine with a stirrer in the water phase, starting a stirring motor, slowly dripping the oil phase into the water phase under vigorous stirring, and continuously stirring for 20 minutes to prepare an oil-in-water emulsion;
(4) placing the emulsion in a glass bottle, and irradiating on an irradiation accelerator;
(5) after the irradiation is carried out for 15 minutes, the irradiation source is closed, and the reaction is stopped;
(6) washing and filtering the irradiated emulsion;
(7) and (4) obtaining the vinyl polymer microcapsule after passing the inspection.
Example 3
A radiation preparation method of vinyl polymer microcapsules comprises the following steps:
(1) preparation of the aqueous phase: weighing 1.8g of emulsifier polyvinyl pyrrolidone (PVPK-88-96) in a beaker, adding 120g of distilled water, and fully dissolving;
(2) preparation of oil phase: uniformly mixing 9g of monomer methyl methacrylate, 3g of monomer acrylic acid, 1.2g of cross-linking agent pentaerythritol tetraacrylate and 12g of oily capsule core hydroxyl-terminated silicone oil;
(3) emulsification: placing an emulsifying machine with a stirrer in the water phase, starting a stirring motor, slowly dripping the oil phase into the water phase under vigorous stirring, and continuously stirring for 20 minutes to prepare an oil-in-water emulsion;
(4) placing the emulsion in a glass bottle, and irradiating on an irradiation accelerator;
(5) after the irradiation is carried out for 15 minutes, the irradiation source is closed, and the reaction is stopped;
(6) washing and filtering the irradiated emulsion;
(7) and (4) obtaining the vinyl polymer microcapsule after passing the inspection.
Example 4
A radiation preparation method of vinyl polymer microcapsules comprises the following steps:
(1) preparation of the aqueous phase: weighing 1.5g of emulsifier sodium dodecyl sulfate in a beaker, adding 120g of distilled water, and fully dissolving;
(2) preparation of oil phase: uniformly mixing 12g of monomer methyl methacrylate, 1.2g of cross-linking agent pentaerythritol tetraacrylate and 12g of oily capsule core hydroxyl-terminated silicone oil;
(3) emulsification: placing an emulsifying machine with a stirrer in the water phase, starting a stirring motor, slowly dripping the oil phase into the water phase under vigorous stirring, and continuously stirring for 20 minutes to prepare an oil-in-water emulsion;
(4) placing the emulsion in a glass bottle, and irradiating on an irradiation accelerator;
(5) after the irradiation is carried out for 20 minutes, the irradiation source is closed, and the reaction is stopped;
(6) washing and filtering the irradiated emulsion;
(7) and (4) obtaining the vinyl polymer microcapsule after passing the inspection.
Example 5
A radiation preparation method of vinyl polymer microcapsules comprises the following steps:
(1) preparation of the aqueous phase: weighing 1.5g of emulsifier sodium dodecyl sulfate in a beaker, adding 120g of distilled water, and fully dissolving;
(2) preparation of oil phase: uniformly mixing 12 monomers of methyl methacrylate, 1.2g of cross-linking agent pentaerythritol tetraacrylate and 12g of oily capsule core hydroxyl-terminated silicone oil;
(3) emulsification: placing an emulsifying machine with a stirrer in the water phase, starting a stirring motor, slowly dripping the oil phase into the water phase under vigorous stirring, and continuously stirring for 20 minutes to prepare an oil-in-water emulsion;
(4) placing the emulsion in a glass bottle, and irradiating on an irradiation accelerator;
(5) after 30 minutes of irradiation, the irradiation source is closed, and the reaction is stopped;
(6) washing and filtering the irradiated emulsion;
(7) and (4) obtaining the vinyl polymer microcapsule after passing the inspection.
And (4) conclusion:
as described in the above examples, the vinyl polymer microcapsules were successfully prepared by an electron accelerator. The shapes of the particles are spherical, the surfaces of the particles are smooth, the particles are uniformly distributed, and a typical figure of the particles is shown in figure 1. By further performing thermogravimetric analysis on the vinyl polymer microcapsules, as shown in fig. 2, when the temperature is raised to about 350 ℃, the microcapsules begin to generate thermogravimetric weight, and the weight loss at the moment is caused by the beginning of decomposition of the microcapsule wall materials; with further increases in temperature, the rate of thermal weight loss decreases as the temperature increases to 480 ℃, due to the initial decomposition of the microcapsule core, thus demonstrating the successful preparation of vinyl polymer microcapsules. Compared with the preparation of the vinyl polymer microcapsule by cobalt source radiation for 5-6 hours, the preparation of the vinyl polymer microcapsule by using the electron accelerator has the advantages that the time for preparing the vinyl polymer microcapsule is greatly reduced, and the preparation of the vinyl polymer microcapsule can be completed by irradiating for 10min as described in example 1, so that the preparation efficiency of the microcapsule is greatly improved.
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, 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 radiation preparation method of vinyl polymer microcapsules is characterized in that: the preparation process comprises the following steps:
preparation of the aqueous phase: dissolving an emulsifier into distilled water to obtain an emulsifier solution; the concentration of the emulsifier solution is 1-3%;
preparation of oil phase: uniformly mixing a vinyl monomer, a cross-linking agent and a core material to obtain an oil phase solution; the mass ratio of the vinyl monomer to the cross-linking agent to the core material is 1: 0.1: 1;
emulsification: dropwise adding the oil phase solution into the emulsifier solution under continuous stirring to obtain an oil-in-water emulsion;
placing the oil-in-water emulsion in a glass bottle, and irradiating on an electron accelerator; and washing and filtering the irradiated emulsion to obtain the vinyl polymer microcapsule.
2. The method of claim 1, wherein: the emulsifier comprises: sodium dodecyl sulfate, polyvinylpyrrolidone, dodecyl trimethyl ammonium bromide, Tween-80 or Span-80.
3. The method of claim 1, wherein: the vinyl monomers include: styrene, methyl methacrylate, methyl acrylate or vinyl acetate.
4. The method of claim 1, wherein: the crosslinking agent comprises: divinylbenzene, pentaerythritol tetraacrylate or allyl methacrylate.
5. The method of claim 1, wherein: the core material is an oil capsule core material which is insoluble in water and miscible with vinyl monomers.
6. The method of claim 5, wherein: the oil capsule core material comprises: hydroxyl-terminated silicone oil, ethyl orthosilicate, methyltrimethoxysilane, dibutyltin dilaurate or liquid paraffin.
7. The method of claim 1, wherein: in the emulsification process, the oil phase solution is completely dripped and then continuously stirred for 15-45 minutes to obtain the stable oil-in-water emulsion.
8. The method of claim 1, wherein: the parameters of the electron accelerator are set as 10MeV of electron beams, 1.5-2 mA of beam current and 15-20 KW of rated power.
9. The method of claim 1, wherein: the irradiation dose is 5-50 kGy, and the irradiation time is 5-30 minutes.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679790A (en) * | 2020-12-24 | 2021-04-20 | 杭州海虹精细化工有限公司 | Acrylic resin thermal expansion physical foaming microsphere and irradiation preparation method |
| CN114029012A (en) * | 2021-08-25 | 2022-02-11 | 西湖大学 | Preparation method of microcapsule with metal organic coordination polymer as wall material |
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| CN112679790A (en) * | 2020-12-24 | 2021-04-20 | 杭州海虹精细化工有限公司 | Acrylic resin thermal expansion physical foaming microsphere and irradiation preparation method |
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