CN108727753B - Preparation method of thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel - Google Patents
Preparation method of thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel Download PDFInfo
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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
- C08J3/02—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
The invention belongs to the field of hydrogel preparation, and particularly relates to a preparation method of thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel. The invention uses a glycerol-water binary mixed solvent to replace a single water solvent in the traditional hydrogel, and uses polyurethane 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 polyurethane micro-nanofiber/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 thermoplastic polyurethane 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.
Polyurethane is a generic name of polymers containing repeated carbamate groups (-NHCO-) in the structure, and the physical and chemical properties of the polyurethane can be greatly adjusted by designing the proportion of soft segments and hard segments. Thermoplastic Polyurethane (TPU) materials have excellent mechanical strength, high elasticity, wear resistance, lubricity, fatigue resistance, biocompatibility, processability, etc. and are widely used in the biomedical field, as well as good biocompatibility and anticoagulation properties, and are called "ideal biomaterials". 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 polyurethane micro-nanofiber reinforced polyvinyl alcohol hydrogel is prepared by using an in-situ fiber forming technology, and the method is not reported in domestic and foreign documents.
Disclosure of Invention
The invention provides a preparation method of thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel, which solves the problems of long preparation period and low mechanical strength of polyvinyl alcohol hydrogel. The invention uses a glycerol-water binary mixed solvent to replace a single water solvent in the traditional hydrogel, and uses polyurethane 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 polyurethane micro-nanofiber/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:
a preparation method of thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel 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 polyurethane 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 strips 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 mold to be cooled to obtain the polyurethane 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 polyurethanes used are conventional melt-spinning particles.
The invention has the beneficial effects that:
firstly, polyurethane and plasticized polyvinyl alcohol are used as raw materials, a composite material which takes PVA as a matrix and TPU as a disperse phase is prepared by twin-screw extrusion and stretching, and in the process, the TPU forms in-situ microfiber in the PVA matrix due to the shearing, stretching and other effects exerted by a continuous phase; and then, putting the TPU/PVA composite material into a glycerol-water binary mixed solvent, heating and dissolving to prepare the TPU/PVA composite hydrogel, wherein the PVA is dissolved in the mixed solvent and the TPU is not dissolved in the mixed solvent in the process, so that the micro-nano fiber structure of the dispersed phase TPU is maintained to achieve the purpose of in-situ reinforcement.
The polyvinyl alcohol and the polyurethane in the hydrogel prepared by the invention have hydrogen bond action, so that the compatibility between the polyvinyl alcohol and the polyurethane is improved, the polyurethane microfiber can be uniformly dispersed in a polyvinyl alcohol matrix, the diameter of the microfiber can reach a nanometer level, and the mechanical property of the polyvinyl alcohol is effectively improved.
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 thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel of the embodiment 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 polyurethane 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 the blended 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 thermoplastic polyurethane micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 3.4MPa and the elongation at break was 450%.
Example 2
The preparation method of the thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel of the embodiment comprises the following steps:
the preparation method of the thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel of the embodiment 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 polyurethane 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 the blended 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 thermoplastic polyurethane micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 2.5MPa, and the elongation at break was 630%.
Example 3
The preparation method of the thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel of the embodiment 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 polyurethane 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 thermoplastic polyurethane micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 2.9MPa, and the elongation at break was 540%.
Example 4
The preparation method of the thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel of the embodiment 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 polyurethane 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 the blended 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 thermoplastic polyurethane micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 4.0MPa, and the elongation at break was 490%.
Example 5
The preparation method of the thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel of the embodiment 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 polyurethane 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 thermoplastic polyurethane micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 2.9MPa, and the elongation at break was 560%.
Example 6
The preparation method of the thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel of the embodiment 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 polyurethane 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 mold to be cooled to obtain the thermoplastic polyurethane micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 4.1MPa, and the elongation at break was 450%.
Example 7
The preparation method of the thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel of the embodiment 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 polyurethane 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 thermoplastic polyurethane micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 4.6MPa, and the elongation at break was 380%.
Example 8
The preparation method of the thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel of the embodiment 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 820 g of plasticized polyvinyl alcohol and 180 g of polyurethane 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 9 times of stretching by a traction device, and then pelletizing the stretched blend strands. And adding 30 g of the blended particles into a blending solvent composed of 100 g of deionized water and 100 g of glycerol, stirring for 3.5 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 thermoplastic polyurethane micro-nanofiber/polyvinyl alcohol composite hydrogel. The tensile strength of this hydrogel was 3.2MPa and the elongation at break was 530%.
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 thermoplastic polyurethane 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 polyurethane 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 the temperature of 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 thermoplastic polyurethane nanofiber/polyvinyl alcohol composite hydrogel;
the mass ratio of the plasticized polyvinyl alcohol particles to the polyurethane in the step (2) is (16-19): (1-4), the polyurethane is thermoplastic polyurethane, and the thermoplastic polyurethane is particles for conventional melt spinning;
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 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).
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| 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 |
| CN110396771B (en) * | 2019-07-05 | 2020-09-01 | 武汉纺织大学 | Preparation method of nanofiber non-woven fabric |
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