CN109912834A - A kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel - Google Patents
A kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel Download PDFInfo
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- CN109912834A CN109912834A CN201910163977.8A CN201910163977A CN109912834A CN 109912834 A CN109912834 A CN 109912834A CN 201910163977 A CN201910163977 A CN 201910163977A CN 109912834 A CN109912834 A CN 109912834A
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Abstract
The present invention relates to composite material or high-molecular porous hydrogel fields, particularly relate to a kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel.Disclose a kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel, for the low problem of existing polyvinyl alcohol cellular hydrogel mechanical strength, the present invention using in polyvinyl alcohol the glyceral methacrylate grafted polyethylene micro nanometer fiber of shaped in situ and polyvinyl alcohol as chief component, using glycerol and polyethylene glycol as composite pore-forming, polyvinyl alcohol foam composite material is prepared, can be made up for each other's deficiencies and learn from each other using composite material, generate the mechanical performance that the advantages of synergistic effect effectively raises porous aquagel.The polymer nanofiber that the present invention is prepared with melt-blending process, have many advantages, such as at low cost, mild condition is easily controllable, raw material is easy to get, it is environmentally protective, can industrialization large-scale production.
Description
Technical field
The present invention relates to composite material or high-molecular porous hydrogel fields, particularly relate to a kind of polymer micro-nanometer fiber
Enhance the preparation method of polyvinyl alcohol cellular hydrogel.
Background technique
Hydrogel is a kind of functional polymer material, by three-dimensional net structure macromolecule and fill in its network chain gap
Hydrone medium is constituted.Hydrogel is soft and flexible, can be swollen in water, and can generate to extraneous small stimulation significant
Response, there is intelligence, therefore cause extensive research in recent years.Research is concentrated mainly on the preparation of novel hydrogels and new
Hydrogel application field.Hydrogel is widely used, and can be used as drug controlled release material, tissue bulking material, artificial cartilage, change
Scholar-tyrant, light control material, biosensor, tissue cultures etc..Polyvinyl alcohol is one kind as made of polyvinyl acetate ester hydrolysis, and
Contain the water-soluble polymer of a large amount of polar hydroxyl groups on strand.Polyvinyl alcohol (PVA) hydrogel has good lubrication, rubs
Wipe, elastomeric property, good biocompatibility, chemical stability, biodegradability, is had in biomedical and organizational project
The tissue substitute and repair materials of development prospect.But when one pack system PVA hydrogel is used for the materials such as artificial cartilage reparation,
Many properties such as its mechanical property, swelling behavior, biocompatibility are not met by the requirement of medical material.PVA hydrogel can
To do pore former with water, without having to worry about residue problem, but the PVA aqueous solution of only low concentration is by the preparation of freeze-thaw method
PVA hydrogel has pore structure, and aperture is small (generally there was only several microns), and the water in the PVA aqueous solution of high concentration is in refrigerating process
In tend to generate super cold water, generated in manufactured PVA hydrogel without hole, so that the high intensity of PVA hydrogel and porous knot
Structure is incompatible.
The compound developing direction for having become new biomaterial of two or more polymer phases, composite material are past at present
Toward possessing excellent performance not available for single polymers material.High molecular blending and alloy are the effective of improvement plastics performance
One of method, dispersed phase morphology is an important factor for influencing material final mechanical property again in blend, and the form of fiber is more
Be conducive to disperse to achieve the purpose that enhancing to transmitting load.When the diameter of fiber is small arrives sub-micron or nanometer scale, fiber is just
A series of unusual characteristics are shown, such as: there is very big large specific surface area, cause surface that can increase with activity, to produce
Skin effect, quantum size effect, small-size effect etc..In addition, nanofiber it is flexible and in terms of also have
Surprising characteristic.Since nanofiber shows the application in specific and multi-field, more and more researchers in various aspects
Begin to focus on and study nanofiber.Nano-composite gel is the composite material for forming nano-size dispersion in hydrogel.
Because it not only maintains the functional character of nano material itself, but also by be obviously improved hydrogel physical mechanical property,
Thermal stability.
In-situ fibrillation be it is a kind of in process, the incompatible and polymer with different melting points of two kinds of thermodynamics is at it
It is stretched at a temperature of more than fusing point, dispersed phase is formed under the collective effect of elongation flow field and Shearing Flow has certain draw ratio
Fento, a kind of method that fibre reinforced materials is formed in situ.Polyethylene (PE) is excellent due at low cost, easy processing, mechanical performance
The features such as good, occupies highly important status in high molecular material, but its nonpolarity and surface inertness limit its application model
It encloses.Graft modification is carried out to polyethylene, polarity or functional form group are introduced on nonpolar strand, is conducive to improve high score
The interface affinity of sub- material and polar material, thus the high polymer alloy that processability is excellent.It contracts when using methacrylic acid
When water glyceride (GMA) graft modification PE, strongly active group is contained in GMA molecule, grafting can be improved in co-mixing system
The compatibility of object and polar polymer.The method that this patent uses melting extrusion, stretching first connects glyceral methacrylate
Branch polyethylene forms in-situ micro-fibril in PVA, then prepares polyvinyl alcohol cellular water-setting using this in-situ micro-fibril composite material
Glue, microfibrillar structure, which obtains retaining, in porous aquagel plays humidification to matrix.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of high intensity PVA porous aquagel, disclose a kind of polymerization
Object micro nanometer fiber enhances the preparation method of polyvinyl alcohol cellular hydrogel, mechanical strong for existing polyvinyl alcohol cellular hydrogel
Low problem is spent, the present invention is with the glyceral methacrylate grafted polyethylene micro nanometer fiber of the shaped in situ in polyvinyl alcohol
Polyvinyl alcohol foam composite wood is prepared using glycerol and polyethylene glycol as composite pore-forming with polyvinyl alcohol for chief component
Material can be made up for each other's deficiencies and learn from each other using composite material, generate the machine that the advantages of synergistic effect effectively raises porous aquagel
Tool performance.
The technical scheme of the present invention is realized as follows:
A kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel, comprising the following steps:
(1) it weighs by weight in PVA, glycerine and polyethylene glycol investment high-speed mixer, control mixing temperature is 50 DEG C ~ 70
DEG C, plasticising PVA particle is obtained with double screw extruder melt blending and granulation at 150 DEG C ~ 180 DEG C after mixing；
(2) the plasticising PVA particle that step (1) obtains is put by weight with glyceral methacrylate grafted polyethylene particle
In high-speed mixer, control mixing temperature is 50 DEG C ~ 70 DEG C, after mixing, at 160 DEG C~180 DEG C with double screw extruder
Melt blending squeezes out, while carrying out 4~12 times of stretchings by traction equipment, and the blending material strip pelletizing that then will be stretched obtains
Blended particles；
(3) blended particles that step (2) obtains are add to deionized water, are stirred 2~4 hours at a temperature of 85 DEG C~95 DEG C
Uniform mixed solution is formed until blended particles are completely dissolved；
(4) mixed solution for obtaining step (3) is prepared into water by circulating frozen/fusion method in 1~1.5 h of room temperature
Then hydrogel is placed in deionized water and removes polyethylene glycol and glycerine by gel, obtain porous polyethylene alcohol hydrogel.
The parts by weight of PVA, glycerine and polyethylene glycol are followed successively by 50~70 parts, 15~25 parts and 15 in the step (1)
~25 parts.
PVA is PVA1799 or PVA1797 in the step (1), wherein the degree of polymerization 1700 of PVA1799, alcoholysis degree 99%,
The degree of polymerization 1700 of PVA1797, alcoholysis degree 97%；The molecular weight of polyethylene glycol is 2000,4000 or 6000.
The parts by weight of the middle plasticising PVA particle of the step (2) and glyceral methacrylate grafted polyethylene particle are successively
For 70~95 parts and 5~30 parts, wherein glyceral methacrylate grafted polyethylene is that glyceral methacrylate grafting is highly dense
Polyethylene or glyceral methacrylate grafted linear low-density polyethylene are spent, grafting rate is 0.5~1.2%.
The parts by weight of blended particles and deionized water are followed successively by 1 ~ 2.5 part, 7.5~9 parts in the step (3).
For the cryogenic temperature that circulating frozen/fusion method uses in the step (4) for -18 DEG C to -20 DEG C, melting temperature is room
Temperature, cycle-index 3 ~ 7 times.
The beneficial effects of the present invention are:
1. the present invention passes through double spiral shells using the PVA first using glyceral methacrylate grafted polyethylene and by plasticising as raw material
Bar squeezes out, stretches preparation using PVA as matrix, and glyceral methacrylate grafted polyethylene is the composite material of dispersed phase, herein
In the process due to applied by continuous phase shearing, stretch the effects of, glyceral methacrylate grafted polyethylene is in PVA matrix
Middle formation in-situ micro-fibril；Then by glyceral methacrylate grafted polyethylene/PVA composite material, dissolution prepares methyl in water
Glycerol acrylate grafted polyethylene/compound porous the hydrogel of PVA, PVA is dissolved in water and metering system acid glycerol in the process
Ester grafted polyethylene is insoluble, this enables the micro/nano fiber structure of dispersed phase glyceral methacrylate grafted polyethylene to protect
It holds and achievees the purpose that In-sltu reinforcement.Meanwhile having hydrogen bond action between PVA and glyceral methacrylate grafted polyethylene, increase
Compatibility between the two is added, glyceral methacrylate grafted polyethylene fento can be made to disperse in polyvinyl alcohol matrix
Uniformly, and fento diameter can achieve Nano grade, effectively raise the mechanical performance of polyvinyl alcohol cellular hydrogel.This
Kind porous aquagel can be applied to the industries such as drink, food, brewing, pharmacy, chemical, sewage treatment, environmental protection, full
Foot clarification purifies, is separated by solid-liquid separation, being recovered by filtration the requirement of more high-technology condition in system.
There is the polymer nanofiber that the present invention is prepared with melt-blending process at low cost, mild condition to be easy to
Control, raw material be easy to get, be environmentally protective, can industrialization large-scale production the advantages that.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
A kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel of the present embodiment, including following step
It is rapid:
770 grams of polyvinyl alcohol (PVA1797), 180 grams of glycerine, 50 grams of polyethylene glycol (molecular weight 6000) are put into high speed
In mixing machine, mixing temperature is controlled at 70 DEG C, is uniformly mixed；It is melted altogether at 175 DEG C with double screw extruder using conventional method
It mixes and is granulated, obtain plasticised polyvinyl alcohol particle.750 grams of plasticised polyvinyl alcohols and 250 grams of glyceral methacrylates are taken to be grafted
High density polyethylene (HDPE) is put into high-speed mixer, is controlled mixing temperature at 70 DEG C, is uniformly mixed；It is squeezed at 190 DEG C with twin-screw
Machine melt blending squeezes out out, while carrying out 9 times of stretchings, the blending material strip pelletizing that then will be stretched by traction equipment.
Blended particles are add to deionized water, wherein 10 grams of blended particles, 90 grams of deionized water, at a temperature of 85 DEG C
Stirring to form homogeneous solution until blended particles are completely dissolved in 4 hours.Mixed solution is in room temperature 1h；By circulating frozen/
Fusion method prepares plastic, and wherein cryogenic temperature is -20 DEG C, and melting temperature is room temperature, and cycle-index 3 times；The water-setting that will be prepared
Glue removes polyethylene glycol and glycerine in deionized water, and it is multiple to obtain glyceral methacrylate grafted polyethylene nanofiber/PVA
Close porous aquagel.The tensile strength of this porous aquagel is 1.1 MPa.
Embodiment 2
A kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel of the present embodiment, including following step
It is rapid:
790 grams of polyvinyl alcohol (PVA1797), 150 grams of glycerine, 60 grams of polyethylene glycol (molecular weight 4000) are put into high speed
In mixing machine, mixing temperature is controlled at 70 DEG C, is uniformly mixed；It is melted altogether at 164 DEG C with double screw extruder using conventional method
It mixes and is granulated, obtain plasticised polyvinyl alcohol particle.870 grams of plasticised polyvinyl alcohols and 130 grams of glyceral methacrylates are taken to be grafted
High density polyethylene (HDPE) is put into high-speed mixer, is controlled mixing temperature at 70 DEG C, is uniformly mixed；It is squeezed at 185 DEG C with twin-screw
Machine melt blending squeezes out out, while carrying out 10 times of stretchings, the blending material strip pelletizing that then will be stretched by traction equipment.
It takes 12 grams of blended particles to be added in 88 grams of deionized waters, 3.5 hours is stirred at a temperature of 88 DEG C until polyethylene
Alcohol is completely dissolved to form homogeneous solution, and mixed solution is in 1.5 h of room temperature；Plastic is prepared by circulating frozen/fusion method,
Middle cryogenic temperature is -18 DEG C, and melting temperature is room temperature, cycle-index 4 times；The hydrogel prepared is removed in deionized water
Polyethylene glycol and glycerine obtain glyceral methacrylate grafted polyethylene nanofiber/compound porous hydrogel of PVA.This is more
The tensile strength of hole hydrogel is 1.4 MPa.
Embodiment 3
A kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel of the present embodiment, including following step
It is rapid:
By 740 grams of polyvinyl alcohol (PVA1799), 200 grams of glycerine, 60 grams of polyethylene glycol (molecular weight 2000) put into high speed
In mixing machine, mixing temperature is controlled at 55 DEG C, is uniformly mixed；It with double screw extruder melt blending and is granulated, obtains at 170 DEG C
Plasticised polyvinyl alcohol particle.PVA and 160 gram of glyceral methacrylate grafted linear low-density polyethylene of 840 grams of plasticising is taken to throw
Enter into high-speed mixer, controls mixing temperature at 70 DEG C, be uniformly mixed；It is squeezed at 184 DEG C with double screw extruder melt blending
Out, while by traction equipment 7 times of stretchings, the blending material strip pelletizing that then will be stretched are carried out.
It takes 15 grams of blended particles to be added in 85 grams of deionized waters, 4 hours is stirred at a temperature of 87 DEG C until polyvinyl alcohol
It is completely dissolved to form homogeneous solution, mixed solution is in 1.2 h of room temperature；Plastic is prepared by circulating frozen/fusion method, wherein
Cryogenic temperature is -19 DEG C, and melting temperature is room temperature, cycle-index 7 times；The hydrogel prepared is removed in deionized water poly-
Ethylene glycol and glycerine obtain glyceral methacrylate grafted polyethylene nanofiber/compound porous hydrogel of PVA.This is porous
The tensile strength of hydrogel is 2.1MPa.
Embodiment 4
A kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel of the present embodiment, including following step
It is rapid:
By 700 grams of polyvinyl alcohol (PVA1799), 200 grams of glycerine, 100 grams of polyethylene glycol (molecular weight 6000) put into height
In fast mixing machine, mixing temperature is controlled at 70 DEG C, is uniformly mixed；It with double screw extruder melt blending and is granulated, obtains at 180 DEG C
To plasticised polyvinyl alcohol particle.Take PVA and 100 gram of glyceral methacrylate grafted high density polyethylene investment of 900 grams of plasticising
Into high-speed mixer, mixing temperature is controlled at 70 DEG C, is uniformly mixed；It is squeezed out at 180 DEG C with double screw extruder melt blending,
6 times of stretchings, the blending material strip pelletizing that then will be stretched are carried out by traction equipment simultaneously.
It takes 17 grams of blended particles to be added in 83 grams of deionized waters, 2 hours is stirred at a temperature of 95 DEG C until polyvinyl alcohol
It is completely dissolved to form homogeneous solution；Mixed solution is in 1.3 h of room temperature；Plastic is prepared by circulating frozen/fusion method, wherein
Cryogenic temperature is -20 DEG C, and melting temperature is room temperature, cycle-index 7 times；The hydrogel prepared is removed in deionized water poly-
Ethylene glycol and glycerine obtain glyceral methacrylate grafted polyethylene nanofiber/compound porous hydrogel of PVA.This is porous
The tensile strength of hydrogel is 2.0MPa.
Embodiment 5
A kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel of the present embodiment, including following step
It is rapid:
By 800 grams of polyvinyl alcohol (PVA1797), 150 grams of glycerine, 50 grams of polyethylene glycol (molecular weight 4000) put into high speed
In mixing machine, mixing temperature is controlled at 70 DEG C, is uniformly mixed；It is melted altogether at 165 DEG C with double screw extruder using conventional method
It mixes and is granulated, obtain plasticised polyvinyl alcohol particle.850 grams of plasticised polyvinyl alcohols and 150 grams of glyceral methacrylates are taken to be grafted
High density polyethylene (HDPE) is put into high-speed mixer, is controlled mixing temperature at 70 DEG C, is uniformly mixed；It is squeezed at 180 DEG C with twin-screw
Machine melt blending squeezes out out, while carrying out 8 times of stretchings, the blending material strip pelletizing that then will be stretched by traction equipment.
It takes 25 grams of blended particles to be added in 75 grams of deionized waters, 4 hours is stirred at a temperature of 95 DEG C until polyvinyl alcohol
It is completely dissolved to form homogeneous solution, mixed solution is in 1.3 h of room temperature；Plastic is prepared by circulating frozen/fusion method, wherein
Cryogenic temperature is -20 DEG C, and melting temperature is room temperature, cycle-index 7 times；The hydrogel prepared is removed in deionized water poly-
Ethylene glycol and glycerine obtain glyceral methacrylate grafted polyethylene nanofiber/compound porous hydrogel of PVA.This is porous
The tensile strength of hydrogel is 2.4MPa.
Embodiment 6
A kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel of the present embodiment, including following step
It is rapid:
By 750 grams of polyvinyl alcohol (PVA1797), 150 grams of glycerine, 100 grams of polyethylene glycol (molecular weight 6000) put into high speed
In mixing machine, mixing temperature is controlled at 50 DEG C, is uniformly mixed；It is melted altogether at 170 DEG C with double screw extruder using conventional method
It mixes and is granulated, obtain plasticised polyvinyl alcohol particle.Take 850 grams of plasticising PVA low with 150 grams of glyceral methacrylate grafted linears
Density polyethylene is put into high-speed mixer, is controlled mixing temperature at 50 DEG C, is uniformly mixed；At 180 DEG C with twin-screw extrusion
Machine melt blending squeezes out, while carrying out 10 times of stretchings, the blending material strip pelletizing that then will be stretched by traction equipment.
It takes 16 grams of blended particles to be added in 84 grams of deionized waters, 3 hours is stirred at a temperature of 92 DEG C until polyvinyl alcohol
It is completely dissolved to form homogeneous solution.Mixed solution is in 1.4 h of room temperature；Plastic is prepared by circulating frozen/fusion method, wherein
Cryogenic temperature is -20 DEG C, and melting temperature is room temperature, cycle-index 6 times；The hydrogel prepared is removed in deionized water poly-
Ethylene glycol and glycerine obtain glyceral methacrylate grafted polyethylene nanofiber/compound porous hydrogel of PVA.This is porous
The tensile strength of hydrogel is 1.9MPa.
Embodiment 7
A kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel of the present embodiment, including following step
It is rapid:
By 720 grams of polyvinyl alcohol (PVA1799), 200 grams of glycerine, it is mixed that 80 grams of polyethylene glycol (molecular weight 4000) put into high speed
In conjunction machine, mixing temperature is controlled at 70 DEG C, is uniformly mixed；Using conventional method at 160 DEG C with double screw extruder melt blending
And be granulated, obtain plasticised polyvinyl alcohol particle.Take 950 grams of plasticised polyvinyl alcohols and 50 grams of glyceral methacrylate grafting highly dense
Degree polyethylene is put into high-speed mixer, is controlled mixing temperature at 70 DEG C, is uniformly mixed；At 170 DEG C with double screw extruder
Melt blending squeezes out, while carrying out 4 times of stretchings, the blending material strip pelletizing that then will be stretched by traction equipment.
It takes 11 grams of blended particles to be added in 89 grams of deionized waters, 4 hours is stirred at a temperature of 88 DEG C until polyvinyl alcohol
It is completely dissolved to form homogeneous solution；Mixed solution is in 1.3 h of room temperature；Plastic is prepared by circulating frozen/fusion method, wherein
Cryogenic temperature is -20 DEG C, and melting temperature is room temperature, cycle-index 5 times；The hydrogel prepared is removed in deionized water poly-
Ethylene glycol and glycerine obtain glyceral methacrylate grafted polyethylene nanofiber/compound porous hydrogel of PVA.This is porous
The tensile strength of hydrogel is 1.7MPa.
Embodiment 8
A kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel of the present embodiment, including following step
It is rapid:
By 760 grams of polyvinyl alcohol (PVA1797), 180 grams of glycerine, it is mixed that 60 grams of polyethylene glycol (molecular weight 2000) put into high speed
In conjunction machine, mixing temperature is controlled at 60 DEG C, is uniformly mixed；Using conventional method at 170 DEG C with double screw extruder melt blending
And be granulated, obtain plasticised polyvinyl alcohol particle.Take 700 grams of plasticised polyvinyl alcohols and 300 grams of glyceral methacrylate grafting lines
Property low density polyethylene (LDPE) put into high-speed mixer, control mixing temperature at 70 DEG C, be uniformly mixed；At 190 DEG C with twin-screw
Extruder melt blending squeezes out, while carrying out 12 times of stretchings, the blending material strip pelletizing that then will be stretched by traction equipment.
It takes 22 grams of blended particles to be added in 78 grams of deionized waters, 3.5 hours is stirred at a temperature of 92 DEG C until polyethylene
Alcohol is completely dissolved to form homogeneous solution, and mixed solution is in 1.5 h of room temperature；Plastic is prepared by circulating frozen/fusion method,
Middle cryogenic temperature is -20 DEG C, and melting temperature is room temperature, cycle-index 7 times；The hydrogel prepared is removed in deionized water
Polyethylene glycol and glycerine obtain glyceral methacrylate grafted polyethylene nanofiber/compound porous hydrogel of PVA.This is more
The tensile strength of hole hydrogel is 2.0MPa.
Embodiment 9
A kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel of the present embodiment, including following step
It is rapid:
By 730 grams of polyvinyl alcohol (PVA1799), 200 grams of glycerine, it is mixed that 70 grams of polyethylene glycol (molecular weight 4000) put into high speed
In conjunction machine, mixing temperature is controlled at 60 DEG C, is uniformly mixed；Using conventional method at 150 DEG C with double screw extruder melt blending
And be granulated, obtain plasticised polyvinyl alcohol particle.Take 875 grams of plasticised polyvinyl alcohols and 125 grams of glyceral methacrylate grafting high
Density polyethylene is put into high-speed mixer, is controlled mixing temperature at 70 DEG C, is uniformly mixed；At 180 DEG C with twin-screw extrusion
Machine melt blending squeezes out, while carrying out 7 times of stretchings, the blending material strip pelletizing that then will be stretched by traction equipment.
It takes 18 grams of blended particles to be added in 82 grams of deionized waters, 3 hours is stirred at a temperature of 92 DEG C until polyvinyl alcohol
It is completely dissolved to form homogeneous solution；Mixed solution is in 1.0 h of room temperature；Plastic is prepared by circulating frozen/fusion method, wherein
Cryogenic temperature is -20 DEG C, and melting temperature is room temperature, cycle-index 3 times；The hydrogel prepared is removed in deionized water poly-
Ethylene glycol and glycerine obtain glyceral methacrylate grafted polyethylene nanofiber/compound porous hydrogel of PVA.This is porous
The tensile strength of hydrogel is 1.3MPa.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel, it is characterised in that including following
Step:
(1) it weighs by weight in PVA, glycerine and polyethylene glycol investment high-speed mixer, control mixing temperature is 50 DEG C ~ 70
DEG C, plasticising PVA particle is obtained with double screw extruder melt blending and granulation at 150 DEG C ~ 180 DEG C after mixing；
(2) the plasticising PVA particle that step (1) obtains is put by weight with glyceral methacrylate grafted polyethylene particle
In high-speed mixer, control mixing temperature is 50 DEG C ~ 70 DEG C, after mixing, at 160 DEG C~180 DEG C with double screw extruder
Melt blending squeezes out, while carrying out 4~12 times of stretchings by traction equipment, and the blending material strip pelletizing that then will be stretched obtains
Blended particles；
(3) blended particles that step (2) obtains are add to deionized water, are stirred 2~4 hours at a temperature of 85 DEG C~95 DEG C
Uniform mixed solution is formed until blended particles are completely dissolved；
(4) mixed solution for obtaining step (3) is prepared into water by circulating frozen/fusion method in 1~1.5 h of room temperature
Then hydrogel is placed in deionized water and removes polyethylene glycol and glycerine by gel, obtain porous polyethylene alcohol hydrogel.
2. the preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel according to claim 1,
Be characterized in that: the parts by weight of PVA, glycerine and polyethylene glycol are followed successively by 50~70 parts, 15~25 parts and 15 in the step (1)
~25 parts.
3. the preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel according to claim 1,
Be characterized in that: PVA is PVA1799 or PVA1797 in the step (1), wherein the degree of polymerization 1700 of PVA1799, alcoholysis degree
The degree of polymerization 1700 of 99%, PVA1797, alcoholysis degree 97%；The molecular weight of polyethylene glycol is 2000,4000 or 6000.
4. the preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel according to claim 1,
Be characterized in that: the parts by weight of the middle plasticising PVA particle of the step (2) and glyceral methacrylate grafted polyethylene particle are successively
For 70~95 parts and 5~30 parts, wherein glyceral methacrylate grafted polyethylene is that glyceral methacrylate grafting is highly dense
Polyethylene or glyceral methacrylate grafted linear low-density polyethylene are spent, grafting rate is 0.5~1.2%.
5. the preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel according to claim 1,
Be characterized in that: the parts by weight of blended particles and deionized water are followed successively by 1 ~ 2.5 part, 7.5~9 parts in the step (3).
6. the preparation method of polymer micro-nanometer fiber enhancing polyvinyl alcohol cellular hydrogel according to claim 1,
Be characterized in that: the cryogenic temperature that circulating frozen/fusion method uses in the step (4) is for -18 DEG C to -20 DEG C, melting temperature
Room temperature, cycle-index 3 ~ 7 times.
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| WO2021002820A1 (en) * | 2019-07-01 | 2021-01-07 | Veri̇tas Teksti̇l Konfeksi̇yon Pazarlama Sanayi̇ Ve Ti̇caret Anoni̇m Şi̇rketi̇ | Method for production of poly-vinyl alcohol -filament fibre of high strength and elasticity |
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