CN115141388B - Polyvinyl alcohol microsphere and preparation method thereof - Google Patents
Polyvinyl alcohol microsphere and preparation method thereof Download PDFInfo
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- CN115141388B CN115141388B CN202210724357.9A CN202210724357A CN115141388B CN 115141388 B CN115141388 B CN 115141388B CN 202210724357 A CN202210724357 A CN 202210724357A CN 115141388 B CN115141388 B CN 115141388B
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- 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
- C08J3/12—Powdering or granulating
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- 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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- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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Abstract
The invention discloses a preparation method of polyvinyl alcohol microspheres. The preparation method comprises the following steps of ultrasonically dispersing modified chitin whiskers in an oil phase; adding polyvinyl alcohol water solution, emulsifying and dispersing; adding a cross-linking agent, and stirring to obtain a suspension; centrifuging the suspension; cleaning; drying to obtain the product. The polyvinyl alcohol microsphere of the invention uses hydrophobic chitin whisker as an emulsifier. The polyvinyl alcohol microspheres prepared by the method have wide application prospects in the aspects of tissue engineering, drug delivery systems, embolism, cell culture and the like.
Description
Technical Field
The invention belongs to the technical field of biological materials, and relates to a polyvinyl alcohol microsphere and a preparation method thereof.
Background
Polyvinyl Alcohol (PVA) is an artificially synthesized water-soluble polymer, and is used in biomedical fields such as cartilage, ophthalmology, anticoagulant materials, drug sustained release and the like due to its characteristics of good moldability, no toxicity, good biocompatibility, biodegradability and the like. A plurality of researches show that the sustained-release compound can play a certain sustained-release role when being used as a drug carrier material in the aspect of medicine. However, in view of the current state of research at home and abroad, the research on the material as a drug carrier is mostly limited to the preparation of PVA in the form of a hydrogel film. On the contrary, relatively little research has been conducted on other forms of PVA material, which would have significantly limited the use of this material in biomedical applications. Compared with materials in the forms of hydrogel, porous scaffold, membrane, fiber, coating and the like, the microsphere material has the unique advantages of small granularity, large specific surface area, good fluidity and the like, and can be prepared into an injection type artificial bone repair material if being dispersed into a buffer solution. In addition, the microsphere has the characteristics of low toxicity, high efficiency, slow release, long acting and the like in the aspect of drug release, and is an ideal carrier for growth factors, antibiotics, anticancer drugs and the like at present. Therefore, the polyvinyl alcohol microspheres become a potential biomaterial.
At present, polyvinyl alcohol microspheres can be prepared by an emulsion crosslinking method, which comprises the steps of dissolving polyvinyl alcohol in water, dropwise adding the solution into an organic solvent to form water-in-oil emulsion droplets, stabilizing the emulsion droplets by using surfactants such as span and the like, and obtaining the polyvinyl alcohol microspheres by a crosslinking process after the emulsion is formed.
The emulsion crosslinking method uses an emulsifier, the emulsifier is inconvenient to clean, and the obtained product has more or less emulsifier residues. Therefore, the emulsifier with better biocompatibility is used for preparing the polyvinyl alcohol microspheres, which has important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of polyvinyl alcohol microspheres, which can improve the biocompatibility of the polyvinyl alcohol microspheres. Therefore, the invention adopts the following technical scheme:
a preparation method of polyvinyl alcohol microspheres is characterized by comprising the following steps: (1) ultrasonically dispersing modified chitin whiskers in an oil phase; (2) adding a polyvinyl alcohol aqueous solution, and emulsifying and dispersing; (3) adding a cross-linking agent, and stirring to obtain a suspension; (5) centrifuging the suspension; (6) cleaning; and (7) drying to obtain the product polyvinyl alcohol microspheres.
The modified chitin whisker is one or more of alkylated chitin whisker, acylated chitin whisker and etherified chitin whisker.
The oil phase is one or more of light liquid paraffin, vegetable oil, dichloromethane, ethyl acetate, n-hexane and n-heptane.
Another object of the present invention is to provide polyvinyl alcohol microspheres with better biocompatibility, which are characterized in that the polyvinyl alcohol microspheres are prepared by the preparation method.
The Chitin Whiskers (CW) are Chitin fibers existing in a single crystal form, and the inventor believes that the modulus is higher due to regular arrangement of crystal grains and less internal defects, the transverse modulus and the longitudinal modulus of the Chitin fibers are respectively as high as 15 GPa and 150GPa, the Chitin whiskers retain the structure and the bioactivity of Chitin, have biodegradability, unique antibacterial property and good biocompatibility, and are suitable for being used as a reinforced material.
The chitin whisker has amphipathy and can be well dispersed in a water phase, so the chitin whisker can be used as an emulsifier of oil-in-water. The chitin whisker surface often has positive charges, and can attract charges of high polymer materials in a water phase to generate precipitates, so that the prepared microspheres are irregular and uneven in density and are not suitable for being used as a water-in-oil emulsifier.
How to develop a green, environment-friendly and degradable biological material based on chitin as a water-in-oil emulsifier and prepare microspheres or particles is a key problem to be solved by the invention.
The invention uses modified chitin whisker with better biocompatibility as an emulsifier, and provides a more convenient preparation method of polyvinyl alcohol microspheres. The polyvinyl alcohol microspheres prepared by the method have wide application prospects in the aspects of tissue engineering, drug delivery systems, embolism, cell culture and the like.
The invention is further explained below with reference to the figures and examples.
Drawings
FIG. 1 is an optical microscope photograph of polyvinyl alcohol microspheres prepared according to the present invention.
FIG. 2 is a particle size distribution diagram of the polyvinyl alcohol microspheres prepared by the present invention.
Detailed Description
In order to further understand the present invention, the following examples are given to illustrate the preparation method of polyvinyl alcohol microspheres provided by the present invention, but the present invention is not limited to these examples, and those skilled in the art can make insubstantial modifications and adjustments under the core teaching of the present invention, and still fall within the scope of the present invention.
Example 1 preparation of hydrophobic chitin whiskers
(1) Weighing 2g of chitin whisker, and ultrasonically dispersing in 160 mLDMSO.
(2) 8g of sodium hydroxide as catalyst was added and stirred in an ice-water bath for 30 minutes.
(3) 20g of bromohexadecane was added and the reaction was stirred at 50 ℃ for 12 hours.
(4) The reaction was adjusted to neutral with 0.1M hydrochloric acid.
(5) Refluxing with 500mL of 75% ethanol aqueous solution for 5h, standing, pouring out the upper layer liquid, and repeating for 8 times.
(6) Drying at 50 ℃ to obtain yellow solid, namely the hydrophobic chitin whisker.
Example 2 preparation of polyvinyl alcohol microspheres PVA-1
(1) 0.1g of hydrophobic chitin whisker is weighed and ultrasonically dispersed in 100mL of light liquid paraffin to obtain modified chitin whisker dispersion liquid.
(2) 2g of polyvinyl alcohol was weighed and dissolved in 20mL of purified water with stirring to obtain a polyvinyl alcohol solution.
(3) And adding the polyvinyl alcohol solution into the stirred chitin whisker dispersion liquid at 50 ℃, and continuously stirring for 1h to obtain the emulsion.
(4) 0.5mL of a 25% glutaraldehyde aqueous solution was added, and the mixture was stirred for 10 minutes.
(5) 1.5mL of a 1M hydrochloric acid solution was added thereto, and the mixture was stirred for 1 hour.
(7) The suspension was centrifuged and the supernatant removed.
(8) The residue was washed with n-hexane, ethyl acetate, and absolute ethanol.
(9) Drying at 50 ℃ to obtain the polyvinyl alcohol microsphere PVA-1.
The microscopic morphology of the polyvinyl alcohol microspheres prepared in the step is characterized by an optical microscope, and the result is shown in figure 1, and the prepared microspheres are round and have smooth surfaces. The particle size distribution of the polyvinyl alcohol microspheres prepared in the step is shown in figure 2, and the particle size distribution is mainly 10-100 microns.
Example 3 preparation of polyvinyl alcohol microspheres PVA-2
(1) 0.1g of hydrophobic chitin whisker is weighed and ultrasonically dispersed in 100mL of light liquid paraffin to obtain modified chitin whisker dispersion liquid.
(2) 1g of polyvinyl alcohol was weighed and dissolved in 20mL of purified water with stirring to obtain a polyvinyl alcohol solution.
(3) And adding the polyvinyl alcohol solution into the stirred chitin whisker dispersion liquid at 50 ℃, and continuously stirring for 1h to obtain the emulsion.
(4) 0.5mL of a 25% glutaraldehyde aqueous solution was added, and the mixture was stirred for 10 minutes.
(5) 1.5mL of a 1M hydrochloric acid solution was added thereto, and the mixture was stirred for 1 hour.
(7) The suspension was centrifuged and the supernatant removed.
(8) The residue was washed with n-hexane, ethyl acetate, and absolute ethanol.
(9) Drying at 50 ℃ to obtain the polyvinyl alcohol microsphere PVA-2.
Example 4 preparation of polyvinyl alcohol microspheres PVA-3
(1) 0.1g of hydrophobic chitin whisker is weighed and ultrasonically dispersed in 100mL of light liquid paraffin to obtain modified chitin whisker dispersion liquid.
(2) 2g of polyvinyl alcohol was weighed and dissolved in 20mL of purified water with stirring to obtain a polyvinyl alcohol solution.
(3) And adding the polyvinyl alcohol solution into the stirred chitin whisker dispersion liquid at the temperature of 25 ℃, and continuously stirring for 1h to obtain the emulsion.
(4) 0.5mL of a 25% aqueous solution of glutaraldehyde was added thereto, and the mixture was stirred for 10 minutes.
(5) 1.5mL of a 1M hydrochloric acid solution was added thereto, and the mixture was stirred for 1 hour.
(7) The suspension was centrifuged and the supernatant removed.
(8) The residue was washed with n-hexane, ethyl acetate, and absolute ethanol.
(9) Drying at 50 ℃ to obtain the polyvinyl alcohol microsphere PVA-3.
The foregoing general description and specific examples have been provided merely for the purpose of illustrating the invention, and are not intended to be limiting, but to better explain the principles and practical application of the invention. Modifications and improvements by those skilled in the art without departing from the spirit or essential characteristics of the invention are intended to be covered by the appended claims.
Claims (2)
1. A preparation method of polyvinyl alcohol microspheres is characterized by comprising the following steps: (1) Ultrasonically dispersing hydrophobic chitin whiskers into light liquid paraffin; (2) adding a polyvinyl alcohol aqueous solution, and emulsifying and dispersing; (3) adding a cross-linking agent, and stirring to obtain a suspension; (4) centrifuging the suspension; (5) cleaning; (6) drying to obtain the product polyvinyl alcohol microspheres;
the preparation of the hydrophobic chitin whisker comprises the following steps:
(1) Weighing 2g of chitin whisker, and ultrasonically dispersing in 160 mLDMSO;
(2) Adding 8g of sodium hydroxide as a catalyst, and stirring for 30 minutes in an ice-water bath;
(3) Adding 20g of bromohexadecane, and stirring and reacting for 12 hours at 50 ℃;
(4) Adjusting the reaction system to be neutral by using 0.1M hydrochloric acid;
(5) Refluxing with 500mL of 75% ethanol water solution for 5h, standing, pouring out the upper layer liquid, and repeating for 8 times;
(6) Drying at 50 ℃ to obtain yellow solid, namely the hydrophobic chitin whisker.
2. Polyvinyl alcohol microspheres, characterized by being produced by the production method according to claim 1.
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| GB0818419D0 (en) * | 2008-10-08 | 2008-11-12 | Imp Innovations Ltd | Nanocomposites |
| CN103124762B (en) * | 2010-09-29 | 2016-03-16 | 塞恩心血管公司 | Prepare the purposes of the method for microballoon and the microballoon of preparation and microballoon |
| CN102641671A (en) * | 2012-04-18 | 2012-08-22 | 江南大学 | Natural nanometer crystal whisker oily polymer emulsion dispersing system and preparation method thereof |
| FR2996848B1 (en) * | 2012-10-16 | 2014-10-31 | Agronomique Inst Nat Rech | COMPOSITION COMPRISING AN INTERNAL PHASE DISPERSE IN A HYDROPHILIC CONTINUOUS PHASE |
| CN104130423B (en) * | 2014-07-18 | 2016-06-08 | 武汉大学 | The preparation method of a kind of hydrophobicity chitin nanometer film |
| CN111803450B (en) * | 2020-06-15 | 2022-05-17 | 广东省医疗器械研究所 | Nano-reinforced degradable polymer microsphere and preparation method and application thereof |
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