CN108794769B - Preparation method of polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel - Google Patents
Preparation method of polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel Download PDFInfo
- Publication number
- CN108794769B CN108794769B CN201810594156.5A CN201810594156A CN108794769B CN 108794769 B CN108794769 B CN 108794769B CN 201810594156 A CN201810594156 A CN 201810594156A CN 108794769 B CN108794769 B CN 108794769B
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- polylactic acid
- particles
- hydrogel
- preparation
- 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.)
- Expired - Fee Related
Links
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 109
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 109
- 239000000017 hydrogel Substances 0.000 title claims abstract description 62
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 56
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000002121 nanofiber Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 73
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 72
- 239000002245 particle Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000002074 melt spinning Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012779 reinforcing material Substances 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 description 9
- 239000000499 gel Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 238000010382 chemical cross-linking Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 229920001410 Microfiber Polymers 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000003658 microfiber Substances 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- 229920001046 Nanocellulose Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- -1 artificial cartilage Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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
- 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
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/095—Oxygen containing compounds
-
- 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)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Artificial Filaments (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention belongs to the field of hydrogel preparation, and particularly relates to a preparation method of polylactic acid 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 polylactic acid 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 polylactic acid micro-nano fiber/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 polylactic acid 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. Due to their unique size and interface effects, nanomaterials exhibit great potential in the fields of electronics, optics, mechanics, biology, etc. 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.
Polylactic acid (PLA) is a nontoxic and completely biodegradable polymer, has better chemical inertness, easy processability and good biocompatibility, does not pollute the environment, is considered as a high molecular material with the most development prospect, and is concerned at home and abroad. In recent years, the preparation technology of the nanofiber is continuously developed and innovated, so that the performance and the application of the nanofiber are further embodied.
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. The invention utilizes the in-situ fiber forming technology to prepare the polylactic acid micro-nanofiber reinforced polyvinyl alcohol hydrogel, and the method is not reported in domestic and foreign documents.
Disclosure of Invention
The invention provides a preparation method of polylactic acid 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 polylactic acid 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 polylactic acid micro-nano fiber/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 discloses a preparation method of polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel, which comprises the following steps (in parts by mass):
(1) plasticizing modification of polyvinyl alcohol: 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) preparation of blend particles: putting 80-95 parts of plasticized polyvinyl alcohol obtained in the step (1) and 5-20 parts of polylactic acid 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 170-190 ℃, simultaneously stretching by 4-12 times by using traction equipment, and then cutting the stretched blended material into particles;
(3) preparation of composite hydrogel: 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 deionized water 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 polylactic acid 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 a mixture of the two; the polylactic acid used is a conventional melt-spinning pellet.
The invention has the beneficial effects that:
firstly, polylactic acid and plasticized polyvinyl alcohol are used as raw materials, a composite material which takes PVA as a matrix and PLA as a disperse phase is prepared by twin-screw extrusion and stretching, and the PLA forms in-situ microfiber in the PVA matrix due to the shearing, stretching and other effects exerted by a continuous phase in the process; and then placing the PLA/PVA composite material in a glycerol-water binary mixed solvent for heating and dissolving to prepare the PLA/PVA composite hydrogel, wherein the PVA is dissolved in the mixed solvent and the PLA is not dissolved in the mixed solvent in the process, so that the micro-nano fiber structure of the dispersed phase PLA is maintained and the in-situ reinforcement purpose is achieved. Meanwhile, hydrogen bond action exists between the polyvinyl alcohol and the polylactic acid, compatibility between the polyvinyl alcohol and the polylactic acid is improved, polylactic acid microfiber can be uniformly dispersed in a polyvinyl alcohol matrix, the diameter of the microfiber can reach a nanometer level, and mechanical properties of the polyvinyl alcohol are effectively improved.
The invention takes polyvinyl alcohol and polylactic acid as raw materials, the polyvinyl alcohol and the polylactic acid have good biocompatibility and biodegradability, and no chemical crosslinking exists in the preparation process of the gel, 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 polylactic acid 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 polylactic acid 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 polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 2.8MPa and the elongation at break was 620%.
Example 2
The preparation method of the polylactic acid 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; and (3) carrying out melt blending and granulation by a double-screw extruder at 180 ℃ by adopting a conventional method to obtain plasticized polyvinyl alcohol particles. Putting 900 g of plasticized polyvinyl alcohol and 100 g of polylactic acid 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 polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 3.1MPa, and the elongation at break was 510%.
Example 3
The preparation method of the polylactic acid 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 polyvinyl alcohol and 150 g of polylactic acid 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 polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 4.6MPa, and the elongation at break was 480%.
Example 4
The preparation method of the polylactic acid 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 polylactic acid 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 polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 7.4MPa, and the elongation at break was 380%.
Example 5
The preparation method of the polylactic acid 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 polylactic acid 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 polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 3.5MPa, and the elongation at break was 560%.
Example 6
The preparation method of the polylactic acid 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 polylactic acid are put into a high-speed mixer, the mixing temperature is controlled at 50 ℃, 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 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 polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 6.9MPa, and the elongation at break was 390%.
Example 7
The preparation method of the polylactic acid 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 polylactic acid 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 4 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 polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 5.1MPa, and the elongation at break was 420%.
Example 8
The preparation method of the polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel comprises the following steps:
100 g of polyvinyl alcohol (PVA 1797), 500 g of polyvinyl alcohol (PVA 1799) and 400 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. Putting 810 g of plasticized polyvinyl alcohol and 190 g of polylactic acid 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 drawing the mixture by 10 times by a traction device, and then cutting the drawn mixture into particles. Adding 60 g of blending particles into a blending solvent composed of 150 g of deionized water and 150 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 mold to be cooled to obtain the polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 5.3MPa, and the elongation at break was 420%.
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 polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel is characterized by comprising the following steps:
(1) plasticizing modification of polyvinyl alcohol: 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) preparation of blend particles: putting plasticized polyvinyl alcohol particles and polylactic acid into a mixer, uniformly mixing at 50-70 ℃, adding into a double-screw extruder, melting, blending and extruding at 170-190 ℃, stretching by 4-12 times by a traction device, and then granulating stretched blending extrusion materials to obtain blending particles;
(3) preparation of composite hydrogel: 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 polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel;
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 polylactic acid in the step (2) is (16-19): (1-4), the polylactic acid is particles for conventional melt spinning;
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 |
|---|---|---|---|
| CN201810594156.5A CN108794769B (en) | 2018-06-11 | 2018-06-11 | Preparation method of polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810594156.5A CN108794769B (en) | 2018-06-11 | 2018-06-11 | Preparation method of polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108794769A CN108794769A (en) | 2018-11-13 |
| CN108794769B true CN108794769B (en) | 2020-12-25 |
Family
ID=64088260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810594156.5A Expired - Fee Related CN108794769B (en) | 2018-06-11 | 2018-06-11 | Preparation method of polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108794769B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912911B (en) * | 2019-03-05 | 2021-10-29 | 中原工学院 | Preparation method of polymer micro-nanofiber reinforced polyvinyl alcohol foam material |
| CN109912834A (en) * | 2019-03-05 | 2019-06-21 | 中原工学院 | A kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel |
| CN109897315B (en) * | 2019-03-05 | 2021-10-29 | 中原工学院 | Preparation method of maleic anhydride polypropylene micro-nanofiber/polyvinyl alcohol foam material |
| CN109876186B (en) * | 2019-03-21 | 2021-09-28 | 福州大学 | Biomedical degradable double-layer stent for nerve repair and preparation method thereof |
| CN115926122B (en) * | 2022-12-23 | 2024-05-14 | 浙江海正生物材料股份有限公司 | Method for preparing polylactic acid-polyvinyl alcohol graft copolymer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004285279A (en) * | 2003-03-24 | 2004-10-14 | Aichi Prefecture | Polymeric hydrogel composite, its preparing process, and gel porous body |
| CN103147159A (en) * | 2013-03-12 | 2013-06-12 | 中原工学院 | Preparation method of polylactic acid nanofiber |
| CN106188795A (en) * | 2016-07-08 | 2016-12-07 | 贵州省材料产业技术研究院 | In-situ fibrillation strengthens thermoplastic elastomer films material and preparation method thereof |
-
2018
- 2018-06-11 CN CN201810594156.5A patent/CN108794769B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004285279A (en) * | 2003-03-24 | 2004-10-14 | Aichi Prefecture | Polymeric hydrogel composite, its preparing process, and gel porous body |
| CN103147159A (en) * | 2013-03-12 | 2013-06-12 | 中原工学院 | Preparation method of polylactic acid nanofiber |
| CN106188795A (en) * | 2016-07-08 | 2016-12-07 | 贵州省材料产业技术研究院 | In-situ fibrillation strengthens thermoplastic elastomer films material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| "Facile preparation of hydrogen-bonded supramolecular polyvinyl alcohol-glycerol gels with excellent thermoplasticity and mechanical properties";Shengjie Shi等;《Polymer》;20170224;第111卷(第24期);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;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20180415(第04期);B020-146 * |
| "原位成纤技术研究进展";董珈豪等;《现代化工》;20150228;第35卷(第2期);第23-26页 * |
| "基于聚乙烯醇水凝胶的复合载体构建及性能研究";尹郅祺;《中国优秀硕士学位论文全文数据库 医药卫生科技辑》;20150715(第07期);E080-32 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108794769A (en) | 2018-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108794769B (en) | Preparation method of polylactic acid micro-nanofiber/polyvinyl alcohol composite hydrogel | |
| CN108727752B (en) | Method for preparing high-strength polyvinyl alcohol composite hydrogel by utilizing in-situ fiber forming | |
| CN109111581B (en) | Preparation method of high-strength conductive polyvinyl alcohol composite hydrogel | |
| 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 | |
| JP6351574B2 (en) | Foam molding | |
| JP2017031246A (en) | Foamed molded article | |
| 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 | |
| CN106750271A (en) | The preparation method of nano silicon reinforced nylon 6 composite | |
| CN109021257B (en) | Preparation method of PBAT micro-nanofiber/polyvinyl alcohol in-situ composite hydrogel | |
| CN111269510A (en) | Compatible ethylene-tetrafluoroethylene copolymer nano composite material and preparation method thereof | |
| CN113603993B (en) | Preparation method of self-healing polymer-nano composite material | |
| CN111040138A (en) | Preparation method of polycaprolactone stent material based on extrusion technology | |
| 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 | |
| CN108822457B (en) | Preparation method of carboxylated multi-walled carbon nanotube/PBS (poly (butylene succinate)) micro-nanofiber/polyvinyl alcohol composite conductive hydrogel | |
| CN102797050A (en) | Melt spinning method for high-strength high-modulus polyvinyl alcohol fiber | |
| CN111704790A (en) | Preparation method of polylactic acid-based composite wire for 3D printing | |
| CN111484666A (en) | Modified powdered rubber toughened polypropylene composite material and preparation method thereof | |
| CN115322405A (en) | Graphene-polylactic acid antibacterial master batch and preparation method and application thereof | |
| CN111234471A (en) | PBT composite material with low linear thermal expansion coefficient and preparation method thereof | |
| CN108794770B (en) | Preparation method of silver nanowire/PBAT nanofiber/polyvinyl alcohol composite conductive hydrogel | |
| CN111286164B (en) | Biodegradable plastic and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| 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 |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201225 |