CN108822457A - A kind of preparation method of functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel - Google Patents
A kind of preparation method of functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel Download PDFInfo
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
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- 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
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The present invention proposes a kind of preparation method of functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel, solves the problems, such as existing conductive polyvinyl alcohol composite hydrogel long preparation period and mechanical strength is low.The present invention prepares polyvinyl alcohol composite hydrogel using multi-walled carbon nanotube and PBS micro nanometer fiber as reinforcing material with the single aqueous solvent in glycerol-water binary mixed solvent substitution conventional hydrogels.The manufacturing cycle for the polyvinyl alcohol conductive hydrogel that method of the invention greatly shortens, and the polyvinyl alcohol composite conducting hydrogel prepared has many advantages, such as good mechanical performance, good biocompatibility, biodegradable.
Description
Technical field
The invention belongs to hydrogel preparation fields, particularly relate to a kind of micro-nano fibre of functionalized multi-wall carbonnanotubes/PBS
Dimension/polyvinyl alcohol composite conducting hydrogel preparation method.
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 PVA hydrogel is applied to tissue engineering material, there is also many power
Learn various problems such as performance, biocompatibility.
In recent years conductive hydrogel as multifunctional intellectual hydrogel family newcomer and receive much attention, conductive hydrogel
It is generally made of conductive material and hydrogel matrix two parts and enumerates its two-component respectively unique performance.Conductive material is logical
It crosses crosslinking copolymerization or graft reaction and is embedded into gel three-dimensional network only by it while keeping hydrogel good characteristic
Carrier transition performance caused by special electron-conjugated system assigns hydrogel electron transport ability, according to its distribution of conductivity
Range conductive hydrogel is expected to all applied to conductive film electric transducer electro photoluminescence drug delivery system and biological fuel cell etc.
It is multi-field, but most of conductive hydrogel mechanical strengths are weaker at present, viscoelasticity is insufficient and electric conductivity is poor is difficult to meet reality
The needs of border application.
It is the important method for improving its mechanical property and realizing functionalization simultaneously that nano material is introduced in hydrogel matrix,
Such as Cellulose nanocrystal body, graphene, nano TiO 2 etc. as enhancing are added in aquogel system and enhance water-setting with this
Mechanical property hot property of glue etc., therefore the research hotspot for being selected to expand plural gel application of reinforcing material.Carbon nanometer
Pipe CNTs have unique one-dimensional nano structure and excellent mechanics electricity thermal stability and magnetic performance in recent years its in high score
The fields such as sub- Material reinforcement functional material preparation and biomedicine show that tempting application prospect is paid close attention to by researcher.
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.In situ in the research at fine enhancing technology, there is presently no adopt
With the correlative study report of in-situ fibrillation enhancing polyvinyl alcohol hydrogel.
Contain the ester bond of a large amount of facile hydrolysis in aliphatic polyester main chain, and main chain is submissive, ester bond be easy with microorganism, enzyme with
And hydrone interacts and degrades, and the hot spot researched and developed in world wide is had become as green environment friendly materials.
Poly butylene succinate（PBS）As a kind of typical aliphatic polyester, have many advantages, such as：PBS excellent in mechanical performance, with
General-purpose plastics PE, PP mechanical property is close；Heat resistance is good, and processing performance is good, can be on existing plastic processing common apparatus
Processing is formed, is that processing performance is best in existing degradation plastic.This patent use first melting extrusion, stretch
Method makes PBS form in-situ micro-fibril in PVA, and system is then blended with multi-walled carbon nanotube using this in-situ micro-fibril composite material
Standby hydrogel, microfibrillar structure cooperates with multi-walled carbon nanotube and plays humidification to matrix in hydrogel.
Summary of the invention
The present invention proposes a kind of functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel
Preparation method, solve the problems, such as existing conductive polyvinyl alcohol composite hydrogel long preparation period and mechanical strength be low.This hair
The bright single aqueous solvent in glycerol-water binary mixed solvent substitution conventional hydrogels, with multi-walled carbon nanotube and PBS micro-nano
Rice fiber is that reinforcing material prepares polyvinyl alcohol composite hydrogel.The polyvinyl alcohol conduction water-setting that method of the invention greatly shortens
The manufacturing cycle of glue, and prepare polyvinyl alcohol composite conducting hydrogel have good mechanical performance, good biocompatibility, can
The advantages that biodegradable.
The technical proposal of the invention is realized in this way：
A kind of preparation method of functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel, packet
Include following steps（In terms of mass fraction）：
（1）It by 50-70 parts of polyvinyl alcohol, 30-50 parts of glycerine, puts into high-speed mixer, controls mixing temperature 50
It DEG C -70 DEG C, is uniformly mixed；It with double screw extruder melt blending and is granulated, is increased at 150 DEG C -180 DEG C using conventional method
Mould granule of polyvinyl alcohol；
（2）By step（1）80-95 parts of obtained plasticised polyvinyl alcohol are put into high-speed mixer with PBS 5-20 parts, are controlled
Mixing temperature is uniformly mixed at 50 DEG C -70 DEG C；It is squeezed out at 160 DEG C -180 DEG C with double screw extruder melt blending, is passed through simultaneously
Traction equipment carries out 6-12 times and stretches, and the blending material strip pelletizing that then will be stretched obtains PBS micro nanometer fiber/polyvinyl alcohol
Composite granule；
（3）By step（2）Obtained PBS micro nanometer fiber/polyvinyl alcohol composite material is added to by deionized water and glycerine
In the blend solvent collectively constituted, wherein PBS micro nanometer fiber/15-20 parts of polyvinyl alcohol composite material, deionized water 40-
42.5 parts, 40-42.5 parts of glycerine, the mass ratio of deionized water and glycerine is 1：1；2-4 is stirred at a temperature of 80 DEG C -95 DEG C
Hour is completely dissolved until polyvinyl alcohol, obtains PBS micro nanometer fiber/poly-vinyl alcohol solution；
（4）Functionalized multi-wall carbonnanotubes are added in the blend solvent collectively constituted by deionized water and glycerine, wherein
1-2 parts of functionalized multi-wall carbonnanotubes, 49-49.5 parts of deionized water, 49-49.5 parts of glycerine, deionized water and glycerine
Mass ratio is 1：1；Ultrasonic disperse 1-4 hours is uniformly dispersed until functionalized multi-wall carbonnanotubes, obtains carboxylated multi wall carbon and receives
Mitron dispersion liquid；
（5）By PBS micro nanometer fiber/poly-vinyl alcohol solution and functionalized multi-wall carbonnanotubes dispersion liquid in 80 DEG C of -95 DEG C of temperature
It is lower to be uniformly mixed, then solution is poured into mold and is cooled to room temperature to obtain the micro-nano fibre of functionalized multi-wall carbonnanotubes/PBS
Dimension/polyvinyl alcohol composite conducting hydrogel, wherein PBS micro nanometer fiber/poly-vinyl alcohol solution and functionalized multi-wall carbonnanotubes
The mass ratio of dispersion liquid is 1：1-2.
Polyvinyl alcohol used herein is selected from PVA1799（The degree of polymerization 1700, alcoholysis degree 99%）And PVA1797（The degree of polymerization
1700, alcoholysis degree 97%）Or their mixture；Used PBS is commercially available blown film grade particles；Used carboxylated is more
Wall carbon nano tube caliber 10-20nm, length 10-30um, carboxyl-content 2%.
The beneficial effects of the present invention are：
One, the present invention is with PVA by twin-screw extrusion, stretching preparation using the PVA first using PBS and by plasticising as raw material
Matrix, PBS be dispersed phase composite material, in the process due to applied by continuous phase shearing, stretch the effects of, PBS
In-situ micro-fibril is formed in PVA matrix；Then it is molten PBS/PVA composite material to be placed in the heating of glycerol-water binary mixed solvent
It solves and prepares PBS/PVA composite hydrogel, PVA is dissolved in mixed solvent in the process and PBS is insoluble, this makes dispersed phase
The micro/nano fiber structure of PBS is maintained and achievees the purpose that In-sltu reinforcement.Meanwhile having hydrogen bond action between PVA and PBS,
Compatibility between the two is increased, PBS fento can be made to be uniformly dispersed in polyvinyl alcohol matrix, and fento diameter can be with
Reach Nano grade, effectively raises the mechanical performance of polyvinyl alcohol hydrogel.
Two, the present invention introduces PBS micro nanometer fiber and functionalized multi-wall carbonnanotubes simultaneously, is carried using micro nanometer fiber
Carbon nanotube forms micro nanometer fiber-carbon mano-tube composite, realizes carboxylic carbon nano-tube in polyvinyl alcohol gel matrix
It is evenly dispersed, assign its electric conductivity while improving polyvinyl alcohol hydrogel mechanical strength.
Three, the present invention is with the single aqueous solvent in glycerol-water binary mixed solvent substitution conventional hydrogels, relative to biography
The freeze-thaw round-robin method of system, it is multiple that the present invention need to only can be prepared by high strength poly vinyl alcohol conduction by way of natural cooling
Heshui gel can significantly shorten preparation time, improve production efficiency；Meanwhile the glycerine in mixed gel network and water it
Between powerful hydrogen bond action be firmly anchored to hydrone in polymer network so that the alcohol/water mixed gel have it is long-term
Stability.
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
The functionalized multi-wall carbonnanotubes of the present embodiment/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel preparation side
Method includes the following steps：
By 550 grams of polyvinyl alcohol（PVA1797）, 450 grams of glycerine put into high-speed mixer, control mixing temperature 60
DEG C, it is uniformly mixed；It with double screw extruder melt blending and is granulated using conventional method at 150 DEG C, obtains plasticised polyvinyl alcohol
Particle.It takes 875 grams of plasticised polyvinyl alcohols and 125 grams of PBS to put into high-speed mixer, controls mixing temperature at 70 DEG C, mix
Uniformly；It is squeezed out at 180 DEG C with double screw extruder melt blending, while 8 times of stretchings is carried out by traction equipment, then will stretched
The blending material strip pelletizing crossed.
It takes 200 grams of PBS/PVA blended particles to be added to be total to by what 400 grams of deionized waters and 400 grams of glycerine collectively constituted
In miscible agent, stir 4 hours to form homogeneous solution until polyvinyl alcohol is completely dissolved at a temperature of 80 DEG C；Take carboxylated multi wall carbon
20 grams of nanotube be added to 490 grams of deionized waters and blend solvent that 490 grams of glycerine collectively constitute in, make carboxylic using ultrasonic wave
Base multi-walled carbon nano-tube is uniformly dispersed, and obtains functionalized multi-wall carbonnanotubes dispersion liquid；Take 200 grams of PBS/ poly-vinyl alcohol solutions
And 400 grams of functionalized multi-wall carbonnanotubes dispersion liquids are uniformly mixed at 80 DEG C, are then poured into mold solution and are cooled to room temperature
Obtain functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel.The stretching of this hydrogel is strong
Degree is 0.92MPa, and elongation at break 410%, conductivity is 1.8 × 10-1S/cm。
Embodiment 2
The functionalized multi-wall carbonnanotubes of the present embodiment/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel preparation side
Method includes the following steps：
By 550 grams of polyvinyl alcohol（PVA1797）, 450 grams of glycerine put into high-speed mixer, control mixing temperature 60
DEG C, it is uniformly mixed；It with double screw extruder melt blending and is granulated using conventional method at 150 DEG C, obtains plasticised polyvinyl alcohol
Particle.It takes 875 grams of plasticised polyvinyl alcohols and 125 grams of PBS to put into high-speed mixer, controls mixing temperature at 70 DEG C, mix
Uniformly；It is squeezed out at 180 DEG C with double screw extruder melt blending, while 8 times of stretchings is carried out by traction equipment, then will stretched
The blending material strip pelletizing crossed.
It takes 150 grams of PBS/PVA blended particles to be added to be total to by what 425 grams of deionized waters and 425 grams of glycerine collectively constituted
In miscible agent, stir 3 hours to form homogeneous solution until polyvinyl alcohol is completely dissolved at a temperature of 90 DEG C；Take carboxylated multi wall carbon
10 grams of nanotube be added to 495 grams of deionized waters and blend solvent that 495 grams of glycerine collectively constitute in, make carboxylic using ultrasonic wave
Base multi-walled carbon nano-tube is uniformly dispersed, and obtains functionalized multi-wall carbonnanotubes dispersion liquid；Take 200 grams of PBS/ poly-vinyl alcohol solutions
And 300 grams of functionalized multi-wall carbonnanotubes dispersion liquids are uniformly mixed at 90 DEG C, are then poured into mold solution and are cooled to room temperature
Obtain functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel.The stretching of this hydrogel is strong
Degree is 1.3MPa, and elongation at break 300%, conductivity is 3.5 × 10-3S/cm。
Embodiment 3
The functionalized multi-wall carbonnanotubes of the present embodiment/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel preparation side
Method includes the following steps：
By 700 grams of polyvinyl alcohol（PVA1799）, 300 grams of glycerine put into high-speed mixer, control mixing temperature 70
DEG C, it is uniformly mixed；It with double screw extruder melt blending and is granulated at 180 DEG C, obtains plasticised polyvinyl alcohol particle.Take 900 grams
PVA and 100 gram of PBS of plasticising is put into high-speed mixer, is controlled mixing temperature at 70 DEG C, is uniformly mixed；At 180 DEG C with double spiral shells
Bar extruder melt blending squeezes out, while carrying out 6 times of stretchings, the blending material strip pelletizing that then will be stretched by traction equipment.
It takes 200 grams of PBS/PVA blended particles to be added to be total to by what 400 grams of deionized waters and 400 grams of glycerine collectively constituted
In miscible agent, stir 4 hours to form homogeneous solution until polyvinyl alcohol is completely dissolved at a temperature of 80 DEG C；Take carboxylated multi wall carbon
20 grams of nanotube be added to 490 grams of deionized waters and blend solvent that 490 grams of glycerine collectively constitute in, make carboxylic using ultrasonic wave
Base multi-walled carbon nano-tube is uniformly dispersed, and obtains functionalized multi-wall carbonnanotubes dispersion liquid；Take 200 grams of PBS/ poly-vinyl alcohol solutions
And 200 grams of functionalized multi-wall carbonnanotubes dispersion liquids are uniformly mixed at 80 DEG C, are then poured into mold solution and are cooled to room temperature
Obtain functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel.The stretching of this hydrogel is strong
Degree is 2.7MPa, and elongation at break 350%, conductivity is 4.7 × 10-3S/cm。
Embodiment 4
The functionalized multi-wall carbonnanotubes of the present embodiment/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel preparation side
Method includes the following steps：
By 700 grams of polyvinyl alcohol（PVA1799）, 300 grams of glycerine put into high-speed mixer, control mixing temperature 70
DEG C, it is uniformly mixed；It with double screw extruder melt blending and is granulated at 180 DEG C, obtains plasticised polyvinyl alcohol particle.Take 800 grams
PVA and 200 gram of PBS of plasticising is put into high-speed mixer, is controlled mixing temperature at 70 DEG C, is uniformly mixed；At 180 DEG C with double spiral shells
Bar 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 200 grams of PBS/PVA blended particles to be added to be total to by what 400 grams of deionized waters and 400 grams of glycerine collectively constituted
In miscible agent, stir 4 hours to form homogeneous solution until polyvinyl alcohol is completely dissolved at a temperature of 80 DEG C；Take carboxylated multi wall carbon
20 grams of nanotube be added to 490 grams of deionized waters and blend solvent that 490 grams of glycerine collectively constitute in, make carboxylic using ultrasonic wave
Base multi-walled carbon nano-tube is uniformly dispersed, and obtains functionalized multi-wall carbonnanotubes dispersion liquid；Take 200 grams of PBS/ poly-vinyl alcohol solutions
And 200 grams of functionalized multi-wall carbonnanotubes dispersion liquids are uniformly mixed at 80 DEG C, are then poured into mold solution and are cooled to room temperature
Obtain functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel.The stretching of this hydrogel is strong
Degree is 2.8MPa, and elongation at break 260%, conductivity is 8.1 × 10-3S/cm。
Embodiment 5
The functionalized multi-wall carbonnanotubes of the present embodiment/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel preparation side
Method includes the following steps：
By 500 grams of polyvinyl alcohol（PVA1799）, 500 grams of glycerine put into high-speed mixer, control mixing temperature 50
DEG C, it is uniformly mixed；It with double screw extruder melt blending and is granulated using conventional method at 160 DEG C, obtains plasticised polyvinyl alcohol
Particle.It takes 950 grams of plasticised polyvinyl alcohols and 50 grams of PBS to put into high-speed mixer, controls mixing temperature at 70 DEG C, mixing is equal
It is even；It is squeezed out at 160 DEG C with double screw extruder melt blending, while 10 times of stretchings is carried out by traction equipment, then will stretched
The blending material strip pelletizing crossed.
It takes 160 grams of PBS/PVA blended particles to be added to be total to by what 420 grams of deionized waters and 420 grams of glycerine collectively constituted
In miscible agent, stir 3 hours to form homogeneous solution until polyvinyl alcohol is completely dissolved at a temperature of 85 DEG C；Take carboxylated multi wall carbon
15 grams of nanotube be added to 492.5 grams of deionized waters and blend solvent that 492.5 grams of glycerine collectively constitute in, use ultrasonic wave
So that functionalized multi-wall carbonnanotubes is uniformly dispersed, obtains functionalized multi-wall carbonnanotubes dispersion liquid；Take 200 grams of PBS/ polyvinyl alcohol
Solution and 250 grams of functionalized multi-wall carbonnanotubes dispersion liquids are uniformly mixed at 95 DEG C, are then poured into mold solution and are cooled to
Room temperature obtains functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel.The drawing of this hydrogel
Stretching intensity is 1.5MPa, and elongation at break 230%, conductivity is 5.7 × 10-3S/cm。
Embodiment 6
The functionalized multi-wall carbonnanotubes of the present embodiment/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel preparation side
Method includes the following steps：
By 500 grams of polyvinyl alcohol（PVA1797）, 500 grams of glycerine put into high-speed mixer, control mixing temperature 50
DEG C, it is uniformly mixed；It with double screw extruder melt blending and is granulated using conventional method at 160 DEG C, obtains plasticised polyvinyl alcohol
Particle.It takes 820 grams of plasticised polyvinyl alcohols and 180 grams of PBS to put into high-speed mixer, controls mixing temperature at 70 DEG C, mix
Uniformly；It is squeezed out at 160 DEG C with double screw extruder melt blending, while 9 times of stretchings is carried out by traction equipment, then will stretched
The blending material strip pelletizing crossed.
It takes 170 grams of PBS/PVA blended particles to be added to be total to by what 415 grams of deionized waters and 415 grams of glycerine collectively constituted
In miscible agent, stir 2 hours to form homogeneous solution until polyvinyl alcohol is completely dissolved at a temperature of 95 DEG C；Take carboxylated multi wall carbon
19 grams of nanotube be added to 490.5 grams of deionized waters and blend solvent that 490.5 grams of glycerine collectively constitute in, use ultrasonic wave
So that functionalized multi-wall carbonnanotubes is uniformly dispersed, obtains functionalized multi-wall carbonnanotubes dispersion liquid；Take 200 grams of PBS/ polyvinyl alcohol
Solution and 380 grams of functionalized multi-wall carbonnanotubes dispersion liquids are uniformly mixed at 90 DEG C, are then poured into mold solution and are cooled to
Room temperature obtains functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel.The drawing of this hydrogel
Stretching intensity is 0.86MPa, and elongation at break 410%, conductivity is 8.7 × 10-1S/cm。
Embodiment 7
The functionalized multi-wall carbonnanotubes of the present embodiment/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel preparation side
Method includes the following steps：
By 300 grams of polyvinyl alcohol（PVA1797）, by 300 grams of polyvinyl alcohol（PVA1799）, 400 grams of glycerine, 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.820 grams of plasticised polyvinyl alcohols and 180 grams of PBS are taken to put into high-speed mixer
In, mixing temperature is controlled at 70 DEG C, is uniformly mixed；It is squeezed out at 165 DEG C with double screw extruder melt blending, while passing through traction
Equipment carries out 10 times of stretchings, the blending material strip pelletizing that then will be stretched.
It takes 160 grams of PBS/PVA blended particles to be added to be total to by what 420 grams of deionized waters and 420 grams of glycerine collectively constituted
In miscible agent, stir 3.5 hours to form homogeneous solution until polyvinyl alcohol is completely dissolved at a temperature of 87 DEG C；Take carboxylated multi wall
17 grams of carbon nanotube be added to 491.5 grams of deionized waters and blend solvent that 491.5 grams of glycerine collectively constitute in, use ultrasound
Wave makes functionalized multi-wall carbonnanotubes be uniformly dispersed, and obtains functionalized multi-wall carbonnanotubes dispersion liquid；Take 200 grams of PBS/ polyethylene
Alcoholic solution and 280 grams of functionalized multi-wall carbonnanotubes dispersion liquids are uniformly mixed at 90 DEG C, are then poured into solution cooling in mold
Functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel is obtained to room temperature.This hydrogel
Tensile strength is 0.94MPa, and elongation at break 330%, conductivity is 2.6 × 10-2S/cm。
Embodiment 8
The functionalized multi-wall carbonnanotubes of the present embodiment/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel preparation side
Method includes the following steps：
By 500 grams of polyvinyl alcohol（PVA1797）, by 50 grams of polyvinyl alcohol（PVA1799）, it is mixed to put into high speed 450 grams of glycerine
In conjunction machine, mixing temperature is controlled at 75 DEG C, is uniformly mixed；Using conventional method at 165 DEG C with double screw extruder melt blending
And be granulated, obtain plasticised polyvinyl alcohol particle.880 grams of plasticised polyvinyl alcohols and 120 grams of PBS are taken to put into high-speed mixer,
Mixing temperature is controlled at 75 DEG C, is uniformly mixed；It is squeezed out at 178 DEG C with double screw extruder melt blending, while passing through traction dress
It is standby to carry out 9 times of stretchings, the blending material strip pelletizing that then stretched.
It takes 150 grams of PBS/PVA blended particles to be added to be total to by what 425 grams of deionized waters and 425 grams of glycerine collectively constituted
In miscible agent, stir 3 hours to form homogeneous solution until polyvinyl alcohol is completely dissolved at a temperature of 92 DEG C；Take carboxylated multi wall carbon
10 grams of nanotube be added to 495 grams of deionized waters and blend solvent that 495 grams of glycerine collectively constitute in, make carboxylic using ultrasonic wave
Base multi-walled carbon nano-tube is uniformly dispersed, and obtains functionalized multi-wall carbonnanotubes dispersion liquid；Take 200 grams of PBS/ poly-vinyl alcohol solutions
And 200 grams of functionalized multi-wall carbonnanotubes dispersion liquids are uniformly mixed at 80 DEG C, are then poured into mold solution and are cooled to room temperature
Obtain functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel.The stretching of this hydrogel is strong
Degree is 1.1MPa, and elongation at break 330%, conductivity is 5.2 × 10-4S/cm.
Embodiment 9
The functionalized multi-wall carbonnanotubes of the present embodiment/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel preparation side
Method includes the following steps：
By 550 grams of polyvinyl alcohol（PVA1797）, 450 grams of glycerine put into high-speed mixer, control mixing temperature 55
DEG C, it is uniformly mixed；It with double screw extruder melt blending and is granulated using conventional method at 165 DEG C, obtains plasticised polyvinyl alcohol
Particle.It takes 850 grams of plasticised polyvinyl alcohols and 150 grams of PBS to put into high-speed mixer, controls mixing temperature at 65 DEG C, mix
Uniformly；It is squeezed out at 175 DEG C with double screw extruder melt blending, while 11 times of stretchings is carried out by traction equipment, then will drawn
The blending material strip pelletizing extended through.
It takes 170 grams of PBS/PVA blended particles to be added to be total to by what 415 grams of deionized waters and 415 grams of glycerine collectively constituted
In miscible agent, stir 2 hours to form homogeneous solution until polyvinyl alcohol is completely dissolved at a temperature of 95 DEG C；Take carboxylated multi wall carbon
17 grams of nanotube be added to 491.5 grams of deionized waters and blend solvent that 491.5 grams of glycerine collectively constitute in, use ultrasonic wave
So that functionalized multi-wall carbonnanotubes is uniformly dispersed, obtains functionalized multi-wall carbonnanotubes dispersion liquid；Take 200 grams of PBS/ polyvinyl alcohol
Solution and 340 grams of functionalized multi-wall carbonnanotubes dispersion liquids are uniformly mixed at 90 DEG C, are then poured into mold solution and are cooled to
Room temperature obtains functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel.The drawing of this hydrogel
Stretching intensity is 0.86MPa, and elongation at break 320%, conductivity is 3.2 × 10-2S/cm。
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 (7)
1. a kind of functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyvinyl alcohol composite conducting hydrogel preparation method,
Characterized by the following steps：
（1）By in polyvinyl alcohol and glycerine investment mixing machine, control mixing temperature is 50 DEG C -70 DEG C, is uniformly mixed, and is added double
Melt blending is granulated under the conditions of 150 DEG C -180 DEG C in screw extruder, obtains plasticised polyvinyl alcohol particle；
（2）Plasticised polyvinyl alcohol particle and PBS are put into mixing machine, in 50 DEG C -70 DEG C, are uniformly mixed, double spiral shells are added to
In bar extruder, melt blending is squeezed out under the conditions of 160 DEG C -180 DEG C, is stretched 6-12 times through traction device, then will be stretched
Blending extrusion material pelletizing, obtain PBS micro nanometer fiber/polyvinyl alcohol composite granule；
（3）PBS micro nanometer fiber/polyvinyl alcohol composite granule is added in blend solvent, 2- is stirred under the conditions of 80-95 DEG C
It is completely dissolved until polyvinyl alcohol within 4 hours, obtains PBS micro nanometer fiber/poly-vinyl alcohol solution；
（4）Functionalized multi-wall carbonnanotubes are added in blend solvent, ultrasonic disperse 1-4 hours to carboxylated multi-wall carbon nano-tube
Pipe is uniformly dispersed, and obtains functionalized multi-wall carbonnanotubes dispersion liquid；
（5）By PBS micro nanometer fiber/poly-vinyl alcohol solution and functionalized multi-wall carbonnanotubes dispersion liquid in 80 DEG C of -95 DEG C of conditions
It is lower to be uniformly mixed, it is subsequently poured into room temperature cooling in mold, obtains functionalized multi-wall carbonnanotubes/PBS micro nanometer fiber/polyethylene
Alcohol composite conducting hydrogel.
2. functionalized multi-wall carbonnanotubes as described in claim 1/PBS micro nanometer fiber/polyvinyl alcohol composite conducting water-setting
The preparation method of glue, it is characterised in that：The step（1）The mass ratio of middle polyvinyl alcohol and glycerine is（5-7）：（3-5）, gather
Vinyl alcohol is the mixture of PVA1799, PVA1797 or both.
3. functionalized multi-wall carbonnanotubes as described in claim 1/PBS micro nanometer fiber/polyvinyl alcohol composite conducting water-setting
The preparation method of glue, it is characterised in that：The step（2）The mass ratio of middle plasticised polyvinyl alcohol particle and PBS is（16-19）：
（1-4）, PBS is commercially available blown film grade particles.
4. functionalized multi-wall carbonnanotubes as described in claim 1/PBS micro nanometer fiber/polyvinyl alcohol composite conducting water-setting
The preparation method of glue, it is characterised in that：The step（3）Middle blend solvent is made of deionized water and glycerine, wherein go from
The mass ratio of sub- water and glycerine is 1:The mass ratio of 1, PBS micro nanometer fiber/polyvinyl alcohol composite granule and blend solvent is
（3-4）：（16-17）.
5. functionalized multi-wall carbonnanotubes as described in claim 1/PBS micro nanometer fiber/polyvinyl alcohol composite conducting water-setting
The preparation method of glue, it is characterised in that：The step（4）Middle blend solvent is made of deionized water and glycerine, wherein go from
The mass ratio of sub- water and glycerine is 1:1.
6. functionalized multi-wall carbonnanotubes as described in claim 1/PBS micro nanometer fiber/polyvinyl alcohol composite conducting water-setting
The preparation method of glue, it is characterised in that：The step（4）The mass ratio of middle functionalized multi-wall carbonnanotubes and blend solvent is
（1-2）：（98-99）, wherein functionalized multi-wall carbonnanotubes caliber 10-20nm, length 10-30um, carboxyl-content 2%.
7. functionalized multi-wall carbonnanotubes as described in claim 1/PBS micro nanometer fiber/polyvinyl alcohol composite conducting water-setting
The preparation method of glue, it is characterised in that：The step（5）Middle PBS micro nanometer fiber/poly-vinyl alcohol solution and carboxylated multi wall carbon
The mass ratio of nanotube dispersion liquid is 1:（1-2）.
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