CN108976679B - Preparation method of polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel - Google Patents
Preparation method of polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel Download PDFInfo
- Publication number
- CN108976679B CN108976679B CN201810595906.0A CN201810595906A CN108976679B CN 108976679 B CN108976679 B CN 108976679B CN 201810595906 A CN201810595906 A CN 201810595906A CN 108976679 B CN108976679 B CN 108976679B
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- polyhydroxyalkanoate
- hydrogel
- particles
- micro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- 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
-
- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Artificial Filaments (AREA)
Abstract
The invention belongs to the field of hydrogel preparation, and particularly relates to a preparation method of polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel. Solves the problems of long preparation period and low mechanical strength of the existing polyvinyl alcohol hydrogel. The invention uses a glycerol-water binary mixed solvent to replace a single water solvent in the traditional hydrogel, and uses PHA micro-nano fibers as a reinforcing material to prepare the polyvinyl alcohol composite hydrogel. The method greatly shortens the preparation period of the polyvinyl alcohol hydrogel, and the prepared PHA micro-nano/polyvinyl alcohol hydrogel has the advantages of excellent mechanical property, good biocompatibility, biodegradability and the like.
Description
Technical Field
The invention belongs to the field of hydrogel preparation, and particularly relates to a preparation method of polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel.
Background
The hydrogel is a functional polymer material and is composed of polymers with a three-dimensional network structure and water molecule media filled in gaps of network chains of the polymers. Hydrogels are flexible and elastic, can swell in water, can generate significant response to external micro-stimuli, and are intelligent, so they have been widely studied in recent years. Research has focused primarily on the preparation of novel hydrogels and on the field of new hydrogel applications. The hydrogel has wide application, and can be used as drug controlled release material, tissue filling material, artificial cartilage, chemical valve, light modulation material, biosensor, tissue culture, etc.
Polyvinyl alcohol is a water-soluble polymer which is hydrolyzed from polyvinyl acetate and contains a large number of polar hydroxyl groups on the molecular chain. Because the molecular chain is easy to form hydrogen bond and the chain structure is symmetrical and regular, the coating has good film forming property, water solubility, emulsifying property and cohesiveness, and is widely applied to various aspects of biomedicine by virtue of high elasticity, chemical stability, easy molding, biodegradability, no toxicity, no adverse reaction and good compatibility with human tissues. The preparation of polyvinyl alcohol hydrogels can be divided into physical and chemical crosslinking, depending on the method of crosslinking. The chemical cross-linking agent method is to adopt a chemical cross-linking agent to cause chemical cross-linking between PVA molecules to form gel, and the commonly used cross-linking agents comprise aldehydes, boric acid, epoxy chloropropane and the like, and the chemical cross-linking agents have certain toxicity. Physical cross-linking is generally a method of repeating freeze-thaw cycles, in which long chains of high molecular polymers are intertwined with each other to form physical binding sites, but most natural and synthetic hydrogels have a certain mechanical strength only at a relatively low water content and are susceptible to chipping due to a significant decrease in strength at a relatively high water content, which greatly limits their practical applications. Therefore, the synthesis of high strength gel has become one of the hot spots of the current research, and in recent years, some scholars have conducted a lot of research on how to improve the mechanical strength of gel.
At present, the compounding of two or more polymers becomes the development direction of new biomaterials, and the composite materials often have excellent performance which is not possessed by a single polymer material. The high molecular blending and alloy are one of the effective methods for improving the performance of plastics, the form of a dispersed phase in the blend is an important factor influencing the final mechanical property of the material, and the form of fibers is more favorable for dispersing and transferring loads to achieve the aim of enhancing. When the diameter of the fiber is as small as submicron or nanometer, the fiber shows a series of unusual characteristics, such as: has extremely large specific surface area, leads to the increase of surface energy and activity, thereby generating surface effect, quantum size effect, small size effect and the like. In addition, the nanofiber has surprising characteristics in terms of flexibility, mechanical properties and the like. Since nanofibers have demonstrated specificity in many ways and have been used in many fields, more and more researchers have been focusing on and studying nanofibers. Nanocomposite gels are composite materials formed by dispersing nano-sized particles in a hydrogel. Because the functional properties of the nano material are maintained, and the physical and mechanical properties and the thermal stability of the hydrogel are obviously improved. Patent 201210282637.5 discloses a nanocellulose/polyvinyl alcohol gel composite material, which is prepared by firstly preparing nanocellulose, then blending the nanocellulose with a polyethylene solution, freezing the blend for 12 hours, taking out the mixture, thawing the mixture for 12 hours at room temperature, and performing freeze-thaw cycle for six times to obtain composite hydrogel.
In-situ fiber forming is a method for forming a fiber reinforced material in situ by drawing two thermodynamically incompatible polymers with different melting points at a temperature above the melting points of the polymers, forming microfibers with a certain length-diameter ratio by a dispersed phase under the combined action of a drawing flow field and a shearing flow field. In the research of the in-situ fiber-forming reinforcing technology, no related research report of reinforcing polyvinyl alcohol hydrogel by adopting in-situ fiber-forming exists at present.
Polyester Polyhydroxyalkanoate (PHA) is a thermoplastic aliphatic polyester synthesized by prokaryotic microorganisms as a carbon source and an energy source for storage under the condition of carbon and nitrogen nutrition imbalance, and early researches mainly utilize the biodegradability of the PHA to explore the application of the PHA in the aspects of biology and medicine, because the mechanical property of PH A is similar to that of certain thermoplastic materials such as polyethylene and polypropylene, but the PHA can be completely degraded into the ecological cycle of the nature, the PHA is considered to be a biodegradable plastic which can replace the traditional nondegradable plastic synthesized by petroleum. The method comprises the steps of firstly adopting a melt extrusion and stretching method to enable PHA to form in-situ microfibers in PVA, then utilizing the in-situ microfiber composite material to prepare hydrogel, and reserving the microfiber structure in the hydrogel to play a role in enhancing a matrix.
Disclosure of Invention
The invention provides a preparation method of polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel, which solves the problems of long preparation period and low mechanical strength of the existing polyvinyl alcohol hydrogel. The invention uses a glycerol-water binary mixed solvent to replace a single water solvent in the traditional hydrogel, and uses PHA micro-nano fibers as a reinforcing material to prepare the polyvinyl alcohol composite hydrogel. The method greatly shortens the preparation period of the polyvinyl alcohol hydrogel, and the prepared PHA micro-nano/polyvinyl alcohol hydrogel has the advantages of excellent mechanical property, good biocompatibility, biodegradability and the like.
The technical scheme of the invention is realized as follows:
the invention relates to a preparation method of polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel, which comprises the following steps (in parts by mass):
(1) 50-70 parts of polyvinyl alcohol and 30-50 parts of glycerol are put into a high-speed mixer, the mixing temperature is controlled to be 50-70 ℃, and the mixture is uniformly mixed; adopting a conventional method to melt, blend and granulate at 150-180 ℃ by using a double-screw extruder to obtain plasticized polyvinyl alcohol particles;
(2) putting 80-95 parts of plasticized polyvinyl alcohol obtained in the step (1) and 5-20 parts of polyhydroxyalkanoate micro-nano fiber into a high-speed mixer, controlling the mixing temperature to be 50-70 ℃, and uniformly mixing; melting, blending and extruding by using a double-screw extruder at 160-180 ℃, simultaneously stretching by 4-12 times by using traction equipment, and then cutting the stretched blended material strips into particles;
(3) adding the blended particles obtained in the step (2) into a blending solvent composed of deionized water and glycerol, wherein the mass ratio of the blended particles to the glycerol is (1): 1; stirring for 2-4 hours at the temperature of 80-95 ℃ until polyvinyl alcohol is completely dissolved to form a uniform solution, and then pouring the solution into a mould to be cooled to obtain the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel.
The polyvinyl alcohol used in the invention is selected from PVA1799 (polymerization degree 1700, alcoholysis degree 99%) and PVA1797 (polymerization degree 1700, alcoholysis degree 97%) or their mixture; the polyhydroxyalkanoate is 3-hydroxybutyric acid-3-hydroxyhexanoate copolyester, the weight average molecular weight Mw of the 3-hydroxybutyric acid-3-hydroxyhexanoate copolyester is 306000g/mol, and the molar percentage content of the hydroxycaproic acid in the 3-hydroxybutyric acid-3-hydroxyhexanoate copolyester is 9.4%.
The beneficial effect that this technical scheme can produce:
firstly, taking PHA and plasticized PVA as raw materials, extruding and stretching the raw materials by a double screw to prepare a composite material which takes the PVA as a matrix and the PHA as a disperse phase, wherein the PHA forms in-situ microfibers in the PVA matrix due to the shearing, stretching and other effects exerted by a continuous phase in the process; then placing the PHA/PVA composite material in a glycerol-water binary mixed solvent, heating and dissolving to prepare PHA/PVA composite hydrogel, wherein PVA is dissolved in the mixed solvent but PHA is not dissolved in the process, so that the micro-nano fiber structure of dispersed phase PHA is maintained to achieve the purpose of in-situ reinforcement. Meanwhile, the PVA and the PHA have hydrogen bonding action, the compatibility between the PVA and the PHA is increased, PHA microfibers can be uniformly dispersed in a polyvinyl alcohol matrix, the diameters of the microfibers can reach the nanometer level, and the mechanical properties of the polyvinyl alcohol are effectively improved.
The invention uses polyvinyl alcohol and PHA as raw materials, the polyvinyl alcohol and PHA have good biocompatibility and biodegradability, and no chemical crosslinking exists in the preparation process of the hydrogel, and the prepared hydrogel can be used in the field of biotechnology.
The glycerol-water binary mixed solvent is used for replacing a single water solvent in the traditional hydrogel, and compared with the traditional freezing-unfreezing circulation method, the high-strength polyvinyl alcohol composite hydrogel can be prepared only by a natural cooling mode, so that the preparation time can be obviously shortened, and the production efficiency can be improved; at the same time, the strong hydrogen bonding between glycerol and water in the mixed gel network firmly anchors the water molecules in the polymer network, so that the alcohol/water mixed gel has long-term stability.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The preparation method of the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel comprises the following steps:
putting 550 g of polyvinyl alcohol (PVA 1799) and 450 g of glycerol into a high-speed mixer, controlling the mixing temperature at 60 ℃, and uniformly mixing; and (3) carrying out melt blending and granulation by a double-screw extruder at 150 ℃ by adopting a conventional method to obtain plasticized polyvinyl alcohol particles. Putting 875 grams of plasticized polyvinyl alcohol and 125 grams of PHA into a high-speed mixer, controlling the mixing temperature at 70 ℃, and uniformly mixing; melt blending and extruding the mixture by a double-screw extruder at 180 ℃, simultaneously performing 7-fold stretching by a traction device, and then pelletizing the stretched blend strands. Adding 60 g of blending particles into a blending solvent composed of 170 g of deionized water and 170 g of glycerol, stirring for 3 hours at the temperature of 90 ℃ until polyvinyl alcohol is completely dissolved to form a uniform solution, and then pouring the solution into a mold to be cooled to obtain the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 2.5MPa, and the elongation at break was 510%.
Example 2
The preparation method of the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel comprises the following steps:
putting 700 g of polyvinyl alcohol (PVA 1799) and 300 g of glycerol into a high-speed mixer, controlling the mixing temperature at 70 ℃, and uniformly mixing; melt blending and granulating by a double-screw extruder at 180 ℃ to obtain plasticized polyvinyl alcohol particles. Putting 900 g of plasticized PVA and 100 g of PHA into a high-speed mixer, controlling the mixing temperature at 70 ℃, and uniformly mixing; and (3) melting, blending and extruding by using a double-screw extruder at 180 ℃, simultaneously performing 6-time stretching by using a traction device, and then pelletizing the stretched blend strips. Adding 50 g of the blended particles into a blending solvent composed of 225 g of deionized water and 225 g of glycerol, stirring for 3 hours at the temperature of 90 ℃ until polyvinyl alcohol is completely dissolved to form a uniform solution, and then pouring the solution into a mold to be cooled to obtain the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 3.2MPa and the elongation at break was 480%.
Example 3
The preparation method of the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel comprises the following steps:
adding 300 g of polyvinyl alcohol (PVA 1797), 300 g of polyvinyl alcohol (PVA 1799) and 400 g of glycerol into a high-speed mixer, controlling the mixing temperature at 70 ℃, and uniformly mixing; melt blending and granulating by a double-screw extruder at 165 ℃ by adopting a conventional method to obtain plasticized polyvinyl alcohol particles. Putting 850 g of plasticized polyvinyl alcohol and 150 g of PHA into a high-speed mixer, controlling the mixing temperature at 70 ℃, and uniformly mixing; and (3) melting, blending and extruding by using a double-screw extruder at 180 ℃, simultaneously carrying out 8-time stretching by using a traction device, and then cutting the stretched blend into particles. Adding 60 g of blending particles into a blending solvent composed of 140 g of deionized water and 140 g of glycerol, stirring for 3 hours at the temperature of 95 ℃ until polyvinyl alcohol is completely dissolved to form a uniform solution, and then pouring the solution into a mould to be cooled to obtain the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 4.3MPa, and the elongation at break was 380%.
Example 4
The preparation method of the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel comprises the following steps:
putting 500 g of polyvinyl alcohol (PVA 1799) and 500 g of glycerol into a high-speed mixer, controlling the mixing temperature at 70 ℃, and uniformly mixing; and (3) carrying out melt blending and granulation by a double-screw extruder at 160 ℃ by adopting a conventional method to obtain plasticized polyvinyl alcohol particles. Putting 950 g of plasticized polyvinyl alcohol and 50 g of PHA into a high-speed mixer, controlling the mixing temperature at 70 ℃, and uniformly mixing; melt blending and extruding the mixture by a double-screw extruder at 170 ℃, simultaneously performing 4 times of stretching by a traction device, and then pelletizing the stretched blend strands. Adding 50 g of blending particles into a blending solvent composed of 100 g of deionized water and 100 g of glycerol, stirring for 4 hours at the temperature of 80 ℃ until polyvinyl alcohol is completely dissolved to form a uniform solution, and then pouring the solution into a mold to be cooled to obtain the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 2.8MPa and the elongation at break was 620%.
Example 5
The preparation method of the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel comprises the following steps:
650 g of polyvinyl alcohol (PVA 1797) and 350 g of glycerol are put into a high-speed mixer, the mixing temperature is controlled at 60 ℃, and the mixture is uniformly mixed; and (3) carrying out melt blending and granulation by using a double-screw extruder at 170 ℃ by adopting a conventional method to obtain plasticized polyvinyl alcohol particles. Putting 800 g of plasticized polyvinyl alcohol and 200 g of PHA into a high-speed mixer, controlling the mixing temperature at 70 ℃, and uniformly mixing; melt blending and extruding the mixture by a double-screw extruder at 190 ℃, simultaneously drawing the mixture by 12 times by a drawing device, and then cutting the drawn mixture into particles. Adding 50 g of blending particles into a blending solvent composed of 100 g of deionized water and 100 g of glycerol, stirring for 2 hours at the temperature of 95 ℃ until polyvinyl alcohol is completely dissolved to form a uniform solution, and then pouring the solution into a mold to be cooled to obtain the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 5.1MPa, and the elongation at break was 220%.
Example 6
The preparation method of the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel comprises the following steps:
650 g of polyvinyl alcohol (PVA 1797) and 350 g of glycerol are put into a high-speed mixer, the mixing temperature is controlled at 70 ℃, and the mixture is uniformly mixed; melt blending and granulating by a double-screw extruder at 175 ℃ by adopting a conventional method to obtain plasticized polyvinyl alcohol particles. 925 g of plasticized polyvinyl alcohol and 75 g of PHA are put into a high-speed mixer, the mixing temperature is controlled at 70 ℃, and the mixture is uniformly mixed; melt blending and extruding the mixture by a double-screw extruder at 190 ℃, simultaneously performing 9 times of stretching by a traction device, and then pelletizing the stretched blend strands. Adding 60 g of blending particles into a blending solvent composed of 120 g of deionized water and 120 g of glycerol, stirring for 2 hours at the temperature of 95 ℃ until polyvinyl alcohol is completely dissolved to form a uniform solution, and then pouring the solution into a mold to be cooled to obtain the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 4.6MPa, and the elongation at break was 340%.
Example 7
The preparation method of the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel comprises the following steps:
adding 600 g of polyvinyl alcohol (PVA 1797) and 400 g of glycerol into a high-speed mixer, controlling the mixing temperature at 50 ℃, and uniformly mixing; and (3) carrying out melt blending and granulation by using a double-screw extruder at 170 ℃ by adopting a conventional method to obtain plasticized polyvinyl alcohol particles. Putting 850 g of plasticized PVA and 150 g of PHA into a high-speed mixer, controlling the mixing temperature at 50 ℃, and uniformly mixing; melt blending and extruding the mixture by a double-screw extruder at 180 ℃, simultaneously drawing the mixture by 10 times by a traction device, and then cutting the drawn mixture into particles. Adding 50 g of blending particles into a blending solvent composed of 100 g of deionized water and 100 g of glycerol, stirring for 2 hours at the temperature of 95 ℃ until polyvinyl alcohol is completely dissolved to form a uniform solution, and then pouring the solution into a mold to be cooled to obtain the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 4.0MPa, and the elongation at break was 490%.
Example 8
The preparation method of the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel comprises the following steps:
putting 200 g of polyvinyl alcohol (PVA 1797), 400 g of polyvinyl alcohol (PVA 1799) and 400 g of glycerol into a high-speed mixer, controlling the mixing temperature at 70 ℃, and uniformly mixing; melt blending and granulating by a double-screw extruder at 165 ℃ by adopting a conventional method to obtain plasticized polyvinyl alcohol particles. Putting 800 g of plasticized polyvinyl alcohol and 200 g of PHA into a high-speed mixer, controlling the mixing temperature at 70 ℃, and uniformly mixing; melt blending and extruding the mixture at 170 ℃ by using a double-screw extruder, simultaneously performing 11 times of stretching by a traction device, and then pelletizing the stretched blend strands. Adding 60 g of blending particles into a blending solvent composed of 140 g of deionized water and 140 g of glycerol, stirring for 2.5 hours at the temperature of 95 ℃ until polyvinyl alcohol is completely dissolved to form a uniform solution, and then pouring the solution into a mould to be cooled to obtain the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 4.8MPa, and the elongation at break was 310%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (1)
1. A preparation method of polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel is characterized by comprising the following steps:
(1) putting polyvinyl alcohol and glycerol into a mixer, controlling the mixing temperature to be 50-70 ℃, uniformly mixing, adding into a double-screw extruder, and carrying out melt blending granulation at the temperature of 150-180 ℃ to obtain plasticized polyvinyl alcohol particles;
(2) putting plasticized polyvinyl alcohol particles and polyhydroxyalkanoate into a mixer, uniformly mixing at 50-70 ℃, adding into a double-screw extruder, melting, blending and extruding at 160-180 ℃, stretching by 4-12 times by a traction device, and then cutting the stretched blending extrusion material into particles to obtain blending particles;
(3) adding the blended particles into a blending solvent, stirring for 2-4 hours at 80-95 ℃ until polyvinyl alcohol is completely dissolved to form a uniform solution, pouring the uniform solution into a mold, and cooling at room temperature to obtain the polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel;
the polyhydroxyalkanoate in the step (2) is 3-hydroxybutyric acid-3-hydroxyhexanoate copolyester, the weight average molecular weight Mw of the 3-hydroxybutyric acid-3-hydroxyhexanoate copolyester is 306000g/mol, and the molar percentage content of the hydroxycaproic acid in the 3-hydroxybutyric acid-3-hydroxyhexanoate copolyester is 9.4%;
the mass ratio of the polyvinyl alcohol to the glycerol in the step (1) is (5-7): (3-5), the polyvinyl alcohol is PVA1799, PVA1797 or a mixture of the two;
the mass ratio of the plasticized polyvinyl alcohol particles to the polyhydroxyalkanoate in the step (2) is (16-19): (1-4);
the mixed solvent in the step (3) consists of deionized water and glycerol, wherein the mass ratio of the deionized water to the glycerol is 1: 1;
the mass ratio of the blended particles to the blended solvent in the step (3) is (1-2): (8-9).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810595906.0A CN108976679B (en) | 2018-06-11 | 2018-06-11 | Preparation method of polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810595906.0A CN108976679B (en) | 2018-06-11 | 2018-06-11 | Preparation method of polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108976679A CN108976679A (en) | 2018-12-11 |
| CN108976679B true CN108976679B (en) | 2021-02-05 |
Family
ID=64540217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810595906.0A Active CN108976679B (en) | 2018-06-11 | 2018-06-11 | Preparation method of polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108976679B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101703805A (en) * | 2009-11-23 | 2010-05-12 | 天津工业大学 | Biocompatible and temperature-sensitive nano composite hydrogel and preparation method thereof |
-
2018
- 2018-06-11 CN CN201810595906.0A patent/CN108976679B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101703805A (en) * | 2009-11-23 | 2010-05-12 | 天津工业大学 | Biocompatible and temperature-sensitive nano composite hydrogel and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Facile preparation of hydrogen-bonded supramolecular polyvinyl alcohol-glycerol gels with excellent;Shengjie Shi;《Polymer》;20170224;第168-176页 * |
| 三螺杆直接挤出原位成纤机理及微纤复合体系结构与性能的研究;黄英;《国优秀硕士学位论文全文数据库工程科技I辑》;20180415;B020-146 * |
| 原位成纤技术研究进展;董珈豪等;《现代化工》;20150228;第23-26页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108976679A (en) | 2018-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108727752B (en) | Method for preparing high-strength polyvinyl alcohol composite hydrogel by utilizing in-situ fiber forming | |
| CN108794769B (en) | Preparation method of polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel | |
| Zhao et al. | Strategies and techniques for improving heat resistance and mechanical performances of poly (lactic acid)(PLA) biodegradable materials | |
| Li et al. | Cotton cellulose nanofiber-reinforced high density polyethylene composites prepared with two different pretreatment methods | |
| CN109111581B (en) | Preparation method of high-strength conductive polyvinyl alcohol composite hydrogel | |
| CN100497458C (en) | Biologically degradable starch base high molecular composition, film made thereof, and its preparing method | |
| CN108727753B (en) | Preparation method of thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel | |
| CN106009056A (en) | Polymeric nanofiber-based aerogel material and preparation method thereof | |
| Huang et al. | Poly (vinyl alcohol)/artificial marble wastes composites with improved melt processability and mechanical properties | |
| CN106674923B (en) | A kind of controllable PBAT/PLA composite membranes and preparation method thereof of degrading | |
| CN101974136B (en) | Method for preparing high-toughness degradable material by using melt-grafting blending method | |
| CN114230989A (en) | Preparation method of environment-friendly biodegradable PBAT (poly (butylene adipate-co-terephthalate)) foaming material | |
| CN113025002A (en) | Degradable foaming material and preparation method thereof | |
| CN108976678B (en) | Preparation method of PBAT micro-nanofiber reinforced carboxymethyl chitosan/polyvinyl alcohol composite hydrogel | |
| CN108822310B (en) | Preparation method of PBS micro-nanofiber/carboxymethyl chitosan/polyvinyl alcohol composite hydrogel | |
| CN104877352A (en) | Compatibilizer-containing fibroin/polylactic acid blended material and preparation method thereof | |
| CN109021257B (en) | Preparation method of PBAT micro-nanofiber/polyvinyl alcohol in-situ composite hydrogel | |
| CN104530670A (en) | Fibroin/polylactic acid blend material and melt-blending preparation method thereof | |
| CN108976679B (en) | Preparation method of polyhydroxyalkanoate micro-nanofiber/polyvinyl alcohol composite hydrogel | |
| CN101225222B (en) | Polylactic acid as well as derivative composite material and preparation method thereof | |
| CN108822457B (en) | Preparation method of carboxylated multi-walled carbon nanotube/PBS (poly (butylene succinate)) micro-nanofiber/polyvinyl alcohol composite conductive hydrogel | |
| CN107245232A (en) | A kind of PHBV composites being modified based on bacteria cellulose | |
| CN111704790A (en) | Preparation method of polylactic acid-based composite wire for 3D printing | |
| CN106751568A (en) | A kind of antibacterial PBAT/PLA composite membranes and preparation method thereof | |
| CN111286164B (en) | Biodegradable plastic and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| CB02 | Change of applicant information |
Address after: 451191 No. 1 Huaihe Road, Shuang Hu Economic and Technological Development Zone, Xinzheng, Zhengzhou, Henan Applicant after: Zhongyuan University of Technology Address before: 451191 No. 1 Huaihe Road, Shuanghu Town Economic and Technological Development Zone, Zhengzhou City, Henan Province Applicant before: Zhongyuan University of Technology |
|
| CB02 | Change of applicant information | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |