CN105622967A - Preparation method of monodisperse polyvinyl alcohol microspheres - Google Patents
Preparation method of monodisperse polyvinyl alcohol microspheres Download PDFInfo
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- CN105622967A CN105622967A CN201610040850.3A CN201610040850A CN105622967A CN 105622967 A CN105622967 A CN 105622967A CN 201610040850 A CN201610040850 A CN 201610040850A CN 105622967 A CN105622967 A CN 105622967A
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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
- C08F8/06—Oxidation
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/247—Heating methods
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or 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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or 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 alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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Abstract
The invention discloses a preparation method of monodisperse polyvinyl alcohol microspheres, belonging to the technical field of high-polymer material preparation. The preparation method comprises the following steps: heating polyvinyl alcohol in a water bath until the polyvinyl alcohol is dissolved in distilled water, cooling to room temperature, adding a water-soluble oxidizer, dissolving by stirring to obtain a uniform solution, transferring into a hydrothermal kettle, and sealing; heating the hydrothermal kettle in a drying oven for some time, cooling to normal temperature, carrying out vacuum filtration on the reaction liquid, collecting the filtrate, washing the filter cake with distilled water, and drying to obtain the monodisperse polyvinyl alcohol microspheres. The preparation method disclosed by the invention is simple and easy to implement, and has the advantages of environment friendliness and low production cost. The prepared polyvinyl alcohol microspheres have the advantages of high yield, uniform size and favorable monodispersity, and have favorable application prospects in the fields of biology, medicine, chemical industry, environmental protection and the like.
Description
Technical field
The invention belongs to field of polymer material preparing technology, the preparation method being specifically related to a kind of polyvinyl alcohol microparticles.
Background technology
Polyvinyl alcohol is a kind of water soluble polymer with biocompatibility, and molecular backbone is containing-CH2-CH (OH)-group, has higher activity, it is possible to carry out the Exemplary chemical reaction of low-alcohols, also can with many inorganic compound, organic compound reaction. There is good chemical modification. Crosslinked reaction rear stability and intensity significantly improve, and antibiont degradation property strengthens, and makes the study hotspot with a lot of fields carrier material. In biological engineering, polyvinyl alcohol material is nontoxic to bioactive substance, is normally used as the solidified carrier of enzyme or antibacterial, and its advantage is that mechanical strength is good, and stability is excellent. In medicine drug development field, cross-linking polyvinyl alcohol microsphere (CPVA microsphere) is a kind of biological compatibility carrier material received much attention, at the monomer that its surface grafting polymerization is different, the bio-medical material with difference in functionality can be formed, in biomacromolecule and the immobilization of cell, the separation of biomacromolecule, intellectual drug release, organizational project, blood purification treatment and biosensor etc., all there is highly important application prospect, be a kind of carrier material in the field such as biology, medicine, chemical industry, environmental protection with development potentiality.
The preparation method of the PVA polymer microballoon difference according to crosslinking method, specifically includes that in-situ cross-linked polymerization and crosslinked polymer method. With vinylacetate for polymerization single polymerization monomer, under the effect of cross-linking agent and other auxiliary agents, by suspension polymerization in-situ polymerization polyvinyl acetate sphere polymers, single dispersing type PVA polymer microsphere can be prepared through alkalescence alcoholysis. In-situ cross-linked polymerization exists that crosslinking time is long and microsphere shape size is difficult to the shortcomings such as control. Polyvinyl alcohol water solution adds cross-linking agent, then because of chemical reaction generation gelation. Conventional cross-linking agent includes glutaraldehyde, boric acid, Borax etc. The gel strength formed due to reactions such as polyvinyl alcohol and boric acid is relatively low, and not easy-formation, it is necessary to add sodium alginate etc. in cross-linking process, and the Microsphere Size of preparation is relatively big, limits it and has the application in application-specific requirement field at some. Patent CN103755983A discloses a kind of method that prepared by the poly-vinyl alcohol solution addition acidic organic solvent of oxidation polyvinyl alcohol microparticles, its preparation process includes the step such as the oxidation of poly-vinyl alcohol solution and the polymerization in acidic organic solvent thereof, particularly the use one of a large amount of organic solvents is the increase in real cost of production, two is that organic solvent needs further subsequent treatment, it is easy to contaminated environment. It is unfavorable for the popularization and application in fields such as biology, medical science of the polyvinyl alcohol microparticles carrier.
Summary of the invention
Problem in preparing for above-mentioned polyvinyl alcohol microparticles, it is desirable to provide the simple method for preparing of a kind of polyvinyl alcohol microparticles.
In order to realize above-mentioned technical purpose, the present invention is achieved by the following technical programs.
The preparation method that the invention provides a kind of single dispersing polyvinyl alcohol microparticles, comprises the steps:
(1) adding in distilled water by polyvinyl alcohol, warming-in-water, to 80��95 DEG C, is incubated 2��4h, so as to be completely dissolved formation poly-vinyl alcohol solution; Then by water-soluble oxidizers in mass ratio 0.4��14 1 ratio join in above-mentioned polyvinyl alcohol water solution, stirring so as to be completely dissolved and become uniform solution;
Described water-soluble oxidizers is any one in ferric chloride, sodium hypochlorite, ammonium perchlorate and Ammonium persulfate.;
(2) solution that step (1) is prepared is transferred in hydrothermal reaction kettle, heat in baking oven after sealing to 150��220 DEG C, stand 6��24h hour, afterwards reactor is cooled to room temperature, sucking filtration reaction feed liquid, collect filtrate, gained filter cake distilled water wash, dry, obtain target product: single dispersing polyvinyl alcohol microparticles.
Further, the poly-vinyl alcohol solution concentration in described step (1) is 0.2g/L��2g/L.
Further, the water-soluble oxidizers in described step (1) is ferric chloride, and its concentration is 1��10mmol/L.
Further, the water-soluble oxidizers in described step (1) is sodium hypochlorite, and its concentration is 10��50mmol/L.
Further, the water-soluble oxidizers in described step (1) is ammonium perchlorate, and its concentration is 2��20mmol/L.
Further, the water-soluble oxidizers in described step (1) is Ammonium persulfate., and its concentration is 1��10mmol/L.
Further, the filtrate that described step (2) is collected can prepare recycling in reaction in the present invention.
The formation mechenism of the polyvinyl alcohol of the present invention is as follows: under hydrothermal temperature, polyvinyl alcohol molecule chain in water-soluble there is oxidized dose of hydroxyl be oxidized to aldehyde radical, form the polyvinyl alcohol chain rupture molecule containing hydroxyl and aldehyde radical, there is aldol reaction in these molecules, be cross-linked with each other generation polyvinyl alcohol microparticles under hydrothermal conditions.
Compared with prior art, the Advantageous Effects that the present invention has is:
1, method provided by the invention is simple, and preparation technology is succinct, it is only necessary to 2 steps can complete the preparation of polyvinyl alcohol microparticles. The polyvinyl alcohol microparticles epigranular prepared by the method, size adjustable.
2, without the preparation of suspension in traditional preparation methods or emulsion in preparation process, do not need to add any cross-linking agent. And preparation is not related to the adjustment of any organic solvent or solution acid alkalinity, method environmental friendliness, cleanliness without any pollution.
3, filtrate can recycle in polyvinyl alcohol microparticles preparation process, makes full use of raw material, reduce production cost to greatest extent.
4, the method repeatability is high, the polyvinyl alcohol microparticles uniform particle sizes of preparation, it is expected to obtain applications well in the field such as biology, medicine, chemical industry, environmental protection.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment 1 gained polyvinyl alcohol microparticles.
Fig. 2 is the infrared spectrogram of embodiment 1 gained polyvinyl alcohol microparticles.
Fig. 3 is the scanning electron microscope (SEM) photograph of embodiment 2 gained polyvinyl alcohol microparticles.
Fig. 4 is the infrared spectrogram of embodiment 2 gained polyvinyl alcohol microparticles.
Fig. 5 is the scanning electron microscope (SEM) photograph of embodiment 3 gained polyvinyl alcohol microparticles.
Fig. 6 is the infrared spectrogram of embodiment 3 gained polyvinyl alcohol microparticles.
Fig. 7 is the scanning electron microscope (SEM) photograph of embodiment 4 gained polyvinyl alcohol microparticles.
Fig. 8 is the infrared spectrogram of embodiment 4 gained polyvinyl alcohol microparticles.
Detailed description of the invention
Below in conjunction with specific embodiment in detail the present invention is described in detail, but the present invention is not limited to following embodiment.
Embodiment 1
Weigh 2g polyvinylalcohol solids to add in 100mL distilled water, in 80 DEG C of waters bath with thermostatic control 4 hours, make polyvinylalcohol solids be completely dissolved and be cooled to room temperature. Poly-vinyl alcohol solution at room temperature adds 0.54g ferric chloride, stirring and dissolving. Mixed liquor is transferred in water heating kettle airtight, 180 DEG C of standings in baking oven. Taking out water heating kettle after 16h, with tap water to room temperature, sucking filtration reaction feed liquid is also collected. Gained solid product distilled water wash three times, 100 DEG C of dry 2h are standby. Adopting scanning electron microscope analysis product morphology (Fig. 1), be shown as the homogeneous spherical morphology that diameter is 5 microns, infrared spectrum is 3445cm as shown in Figure 2-1Place is wide and strong absworption peak to be PVA intermolecular or there is the characteristic absorption of-OH in molecule with associated forms; 2930cm-1Place is the characteristic absorption that methylene asymmetrical stretching vibration is formed; 1379cm-1Place is the absorption of the flexural deformation vibration generation of methyl and methylene; 1073cm-1It it is the absorption of the C-C-C stretching vibration generation relevant with PVA degree of crystallinity; 1700cm-1The peak at place is the deformation vibration peak of hydroxyl.
Embodiment 2
Weigh 0.5g polyvinylalcohol solids to add in 100mL distilled water, in 90 DEG C of water bath with thermostatic control 3h, make polyvinylalcohol solids be completely dissolved and be cooled to room temperature. Poly-vinyl alcohol solution at room temperature adds 0.74g sodium hypochlorite, stirring and dissolving. Mixed liquor is transferred in water heating kettle airtight, 150 DEG C of standings in baking oven. Take out in water heating kettle air after 24h and be cooled to room temperature, sucking filtration reaction feed liquid. Gained solid product distilled water wash three times, 100 DEG C of dry 2h are standby. Adopting scanning electron microscope analysis product morphology (Fig. 3), be shown as the homogeneous spherical morphology that diameter is 1.5 microns, infrared spectrum is as shown in Figure 4.
Embodiment 3
Weigh 1g polyvinylalcohol solids to add in 100mL distilled water, in 95 DEG C of waters bath with thermostatic control 2 hours, make polyvinylalcohol solids be completely dissolved and be cooled to room temperature. Poly-vinyl alcohol solution at room temperature adds 0.234g ammonium perchlorate, stirring and dissolving. Mixed liquor is transferred in water heating kettle airtight, 220 DEG C of standings in baking oven. Taking out water heating kettle after 6h, with tap water to room temperature, sucking filtration reaction feed liquid is also collected. Gained solid product distilled water wash three times, 100 DEG C of dry 2h are standby. Adopting scanning electron microscope analysis product morphology (Fig. 5), be shown as the homogeneous spherical morphology that diameter is 4 microns, infrared spectrum is as shown in Figure 6.
Embodiment 4
Weigh 1.5g polyvinylalcohol solids to add in 100mL distilled water, in 80 DEG C of waters bath with thermostatic control 4 hours, make polyvinylalcohol solids be completely dissolved and be cooled to room temperature. Poly-vinyl alcohol solution at room temperature adds 0.228g Ammonium persulfate., stirring and dissolving. Mixed liquor is transferred in water heating kettle airtight, 200 DEG C of standings in baking oven. Taking out in water heating kettle air after 10h and be cooled to room temperature, sucking filtration reaction feed liquid is also collected. Gained solid product distilled water wash three times, 100 DEG C of dry 2h are standby. Adopting scanning electron microscope analysis product morphology (Fig. 7), be shown as the homogeneous spherical morphology that diameter is 5 microns, infrared spectrum is as shown in Figure 8.
Embodiment 5
Weigh 2g polyvinylalcohol solids to add in the mixed solution collecting liquid in 50mL distilled water and 50mL embodiment 2, in 95 DEG C of water bath with thermostatic control 2h, make polyvinylalcohol solids be completely dissolved and be cooled to room temperature. Poly-vinyl alcohol solution at room temperature adds 3.70g sodium hypochlorite, stirring and dissolving. Mixed liquor is transferred in water heating kettle airtight, 200 DEG C of standings in baking oven. Taking out water heating kettle tap water after 16h to room temperature, sucking filtration reacts feed liquid. Gained solid product distilled water wash three times, 100 DEG C of dry 2h are standby. Product morphology is similar with embodiment 2 scanning electron microscope (SEM) photograph.
Embodiment 6
Weigh 1.5g polyvinylalcohol solids to add in the mixed solution collecting liquid in 50mL distilled water and 50mL embodiment 3, in 80 DEG C of water bath with thermostatic control 4h, make polyvinylalcohol solids be completely dissolved and be cooled to room temperature. Poly-vinyl alcohol solution at room temperature adds 2.34g ammonium perchlorate, stirring and dissolving. Mixed liquor is transferred in water heating kettle airtight, 160 DEG C of standings in baking oven. Take out in water heating kettle air after 10h and be cooled to room temperature, sucking filtration reaction feed liquid. Gained solid product distilled water wash three times, 100 DEG C of dry 2h are standby. Product morphology is similar with embodiment 3 scanning electron microscope (SEM) photograph.
Embodiment 7
Weigh 1g polyvinylalcohol solids to add in the mixed solution collecting liquid in 50mL distilled water and 50mL embodiment 4, in 95 DEG C of water bath with thermostatic control 2h, make polyvinylalcohol solids be completely dissolved and be cooled to room temperature. Poly-vinyl alcohol solution at room temperature adds 2.28g Ammonium persulfate., stirring and dissolving. Mixed liquor is transferred in water heating kettle airtight, 220 DEG C of standings in baking oven. Water heating kettle is taken out, by tap water to room temperature, sucking filtration reaction feed liquid after 8h. Gained solid product distilled water wash three times, 100 DEG C of dry 2h are standby. Product morphology is similar with embodiment 4 scanning electron microscope (SEM) photograph.
Embodiment 8
Weigh 0.5g polyvinylalcohol solids to add in 100mL distilled water, in 85 DEG C of water bath with thermostatic control 4h, make polyvinylalcohol solids be completely dissolved and be cooled to room temperature. Poly-vinyl alcohol solution at room temperature adds 0.27g ferric chloride, stirring and dissolving. Mixed liquor is transferred in water heating kettle airtight, 200 DEG C of standings in baking oven. Water heating kettle is taken out, by tap water to room temperature, sucking filtration reaction feed liquid after 10h. Gained solid product distilled water wash three times, 100 DEG C of dry 2h are standby. Product morphology is similar with embodiment 1 scanning electron microscope (SEM) photograph.
Claims (7)
1. the preparation method of a single dispersing polyvinyl alcohol microparticles, it is characterised in that comprise the steps:
(1) adding in distilled water by polyvinyl alcohol, warming-in-water, to 80��95 DEG C, is incubated 2��4h, so as to be completely dissolved formation poly-vinyl alcohol solution; Then by water-soluble oxidizers in mass ratio 0.4��14 1 ratio join in above-mentioned polyvinyl alcohol water solution, stirring so as to be completely dissolved and become uniform solution;
Described water-soluble oxidizers is any one in ferric chloride, sodium hypochlorite, ammonium perchlorate and Ammonium persulfate.;
(2) solution that step (1) is prepared is transferred in hydrothermal reaction kettle, heat in baking oven after sealing to 150��220 DEG C, stand 6��24h hour, afterwards reactor is cooled to room temperature, sucking filtration reaction feed liquid, collect filtrate, gained filter cake distilled water wash, dry, obtain target product: single dispersing polyvinyl alcohol microparticles.
2. the preparation method of single dispersing polyvinyl alcohol as claimed in claim 1, it is characterised in that the poly-vinyl alcohol solution concentration in described step (1) is 0.2g/L��2g/L.
3. the preparation method of single dispersing polyvinyl alcohol as claimed in claim 1, it is characterised in that the water-soluble oxidizers in described step (1) is ferric chloride, and its concentration is 1��10mmol/L.
4. the preparation method of single dispersing polyvinyl alcohol as claimed in claim 1, it is characterised in that the water-soluble oxidizers in described step (1) is sodium hypochlorite, and its concentration is 10��50mmol/L.
5. the preparation method of single dispersing polyvinyl alcohol as claimed in claim 1, it is characterised in that the water-soluble oxidizers in described step (1) is ammonium perchlorate, and its concentration is 2��20mmol/L.
6. the preparation method of single dispersing polyvinyl alcohol as claimed in claim 1, it is characterised in that the water-soluble oxidizers in described step (1) is Ammonium persulfate., and its concentration is 1��10mmol/L.
7. the preparation method of single dispersing polyvinyl alcohol as claimed in claim 1, it is characterised in that the filtrate that described step (2) is collected can recycle.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106076214A (en) * | 2016-07-15 | 2016-11-09 | 沈阳化工大学 | A kind of calcium alginate microsphere preparation method with nucleocapsid structure |
CN107555415A (en) * | 2017-09-26 | 2018-01-09 | 四川大学 | A kind of method that hydro-thermal method prepares PVA-based carbosphere |
CN107601476A (en) * | 2017-09-11 | 2018-01-19 | 长沙小新新能源科技有限公司 | A kind of preparation method of High-performance graphene perforated membrane |
-
2016
- 2016-01-21 CN CN201610040850.3A patent/CN105622967A/en active Pending
Non-Patent Citations (1)
Title |
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KAZUHIKO KANDORI ET AL.: ""Study on the hydrothermal reaction of FeCl3 solution in the presence of poly(vinyl alcohol)"", 《COLLOID POLYM SCI》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106076214A (en) * | 2016-07-15 | 2016-11-09 | 沈阳化工大学 | A kind of calcium alginate microsphere preparation method with nucleocapsid structure |
CN106076214B (en) * | 2016-07-15 | 2019-12-17 | 沈阳化工大学 | preparation method of calcium alginate microspheres with core-shell structure |
CN107601476A (en) * | 2017-09-11 | 2018-01-19 | 长沙小新新能源科技有限公司 | A kind of preparation method of High-performance graphene perforated membrane |
CN107555415A (en) * | 2017-09-26 | 2018-01-09 | 四川大学 | A kind of method that hydro-thermal method prepares PVA-based carbosphere |
CN107555415B (en) * | 2017-09-26 | 2020-02-14 | 四川大学 | Method for preparing polyvinyl alcohol-based carbon microspheres by hydrothermal method |
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