CN110128596A - A kind of stretchable self-healing ionic conduction Nanometer composite hydrogel of high transparency and preparation method thereof - Google Patents
A kind of stretchable self-healing ionic conduction Nanometer composite hydrogel of high transparency and preparation method thereof Download PDFInfo
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- CN110128596A CN110128596A CN201910375865.9A CN201910375865A CN110128596A CN 110128596 A CN110128596 A CN 110128596A CN 201910375865 A CN201910375865 A CN 201910375865A CN 110128596 A CN110128596 A CN 110128596A
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- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 229920002678 cellulose Polymers 0.000 claims abstract description 26
- 239000001913 cellulose Substances 0.000 claims abstract description 26
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 25
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 25
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- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 25
- 229940033123 tannic acid Drugs 0.000 claims abstract description 25
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 25
- -1 methylacryloyl Chemical group 0.000 claims abstract description 21
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims abstract description 16
- 235000013824 polyphenols Nutrition 0.000 claims abstract description 13
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- 239000000499 gel Substances 0.000 claims description 11
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- 238000005352 clarification Methods 0.000 claims description 9
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- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical group CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 4
- KPGXRSRHYNQIFN-UHFFFAOYSA-N 2-oxoglutaric acid Chemical compound OC(=O)CCC(=O)C(O)=O KPGXRSRHYNQIFN-UHFFFAOYSA-N 0.000 claims description 3
- KDNYCTPSPZHJQF-UHFFFAOYSA-N 3-phenylbutan-2-ol Chemical compound CC(O)C(C)C1=CC=CC=C1 KDNYCTPSPZHJQF-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229930014669 anthocyanidin Natural products 0.000 claims description 3
- 235000008758 anthocyanidins Nutrition 0.000 claims description 3
- 229960003638 dopamine Drugs 0.000 claims description 3
- IPMYMEWFZKHGAX-UHFFFAOYSA-N Isotheaflavin Natural products OC1CC2=C(O)C=C(O)C=C2OC1C(C1=C2)=CC(O)=C(O)C1=C(O)C(=O)C=C2C1C(O)CC2=C(O)C=C(O)C=C2O1 IPMYMEWFZKHGAX-UHFFFAOYSA-N 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 2
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- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001452 anthocyanidin derivatives Chemical class 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000009738 saturating Methods 0.000 claims description 2
- IPMYMEWFZKHGAX-ZKSIBHASSA-N theaflavin Chemical compound C1=C2C([C@H]3OC4=CC(O)=CC(O)=C4C[C@H]3O)=CC(O)=C(O)C2=C(O)C(=O)C=C1[C@@H]1[C@H](O)CC2=C(O)C=C(O)C=C2O1 IPMYMEWFZKHGAX-ZKSIBHASSA-N 0.000 claims description 2
- 229940026509 theaflavin Drugs 0.000 claims description 2
- 235000014620 theaflavin Nutrition 0.000 claims description 2
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 claims 1
- 244000080767 Areca catechu Species 0.000 claims 1
- 235000006226 Areca catechu Nutrition 0.000 claims 1
- VJCSKFITHRWHAG-UHFFFAOYSA-N [OH-].[NH4+].C(C)CC(CC)(S(=O)(=O)O)C Chemical compound [OH-].[NH4+].C(C)CC(CC)(S(=O)(=O)O)C VJCSKFITHRWHAG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000033001 locomotion Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
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- 238000000034 method Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
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- 125000003368 amide group Chemical group 0.000 description 2
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- 238000012544 monitoring process Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
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- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
Abstract
The invention belongs to high molecular materials and advanced intelligent Material Field, it is related to a kind of stretchable self-healing ionic conduction Nanometer composite hydrogel of high transparency and preparation method thereof, i.e. using the Cellulose nanocrystal body of poly- tannic acid cladding as Physical crosslinking agent and reinforcing agent, hydrogen bond is formed by polyphenol hydroxyl and ionic bond is bonded the copolymer of 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide and acrylamide, regulate and control the feed ratio of 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide and acrylamide, light-initiated hydrogel is obtained through ultraviolet.The stretchable self-healing ionic conduction Nanometer composite hydrogel of high transparency of the present invention has height adhesion, the transparency, self-healing, strain-resistance sensitivities, can have broad application prospects in fields such as human body wearable device, elastic electroluminescent, artificial skins.
Description
Technical field
The invention belongs to high molecular materials and smart electronics field, and in particular to a kind of stretchable self-healing ion of high transparency
Electrical-conductive nanometer composite hydrogel and preparation method thereof.
Background technique
In recent years, stretchable self-healing hydrogel sensor causes people greatly to pay close attention to for the wearable sensing of intelligence.
Outer signals can be converted to electric signal output by the sensor, to detect physiology signal and limb motion.As a new generation
Flexible wearable sensor, property requirements include high sensitivity, high stretch, and the consistent good adhesive property of arbitrary surfaces,
Self-healing, low-power consumption, biocompatibility etc..And the mechanical strength of usually self-healing hydrogel is low, limits it in practical application
Tolerance in environment.Wherein natural polymer based aquagel sensor is because of its excellent biocompatibility, environment friendly tool
There is unique advantage.Tannic acid is a kind of natural polyphenol compound, phenolic hydroxyl group and pyrogallol group rich in side group,
It is easily formed intermolecular hydrogen bonding, can assign material excellent tack.Using tannic acid covered fiber element nanocrystal, with both sexes
The amino and sulfonic acid of the poly- 2- of ionomer (methylacryloyl oxygroup) ethyl-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide
Group forms a large amount of hydrogen bond, generates physical cross-linked network.At the same time, tannic acid, poly- 2- (methylacryloyl oxygroup) second
The multiple weak dynamic networks formed between base-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide, polyacrylamide three, make water-setting
Glue has high resiliency, high stretch, low modulus and self-healing property.Its dynamic physical key can be rebuild after being destroyed by external force, assign material
Excellent self-healing performance.The electric conductivity of ionic conduction gel is by poly- 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3-
Propyl sulfonic acid) ammonium hydroxide offer, it is a kind of biodegradable biocompatible natural polyelectrolyte, a large amount of conductions is provided
Ion ensures the high sensitivity of aqueous ionomer gel.Therefore, sensor may be implemented to the obvious limb motion of human body and subtle muscle
The real-time monitoring of movement has highly sensitive and good repeatability, has broad application prospects in biologic medical field.
Chinese invention patent (application number: 201811116179.1 patent names: stretchable self-healing hydrogel flexibility strain
Sensor and preparation method thereof) a kind of stretchable self-healing hydrogel flexibility strain transducer is disclosed, it is solidifying by a step colloidal sol-
The self-healing hydrogel with high stretch is prepared in glue method, and multifunction flexible strain is obtained after encapsulating using adhesive tape and is passed
Sensor.The water-setting matrix flexibility strain transducer has the high sensitive factor, can be used for the detection of elongation strain, compression stress；
Its high tensility and low lag behavior, may be implemented the real-time detection of small and violent human motion.Meanwhile in hydrogel
Unique coordinate bond and interaction of hydrogen bond, make that its self-healing time is short, self-healing is high-efficient, solve flexible sensor reality
Rear irreclaimable problem is broken in the breakage present in.The flexible device preparation process simple process that the present invention designs saves
Shi Shengli is had excellent performance, and can be widely applied to real time health monitoring, flexible robot, clinical diagnosis, flexible electronic skin and intelligence
The fields such as energy household.
United States Patent (USP) (the patent No.: 9976051 patent names: Self healing polymer compositions self-healing
Close polymer composites) a kind of component of polymer, including first polymer stage and second polymer stage are disclosed, wherein
First stage is a kind of adhesive of functional group by thermoplastic polymer polymer substrate modified adhesive functional group or one group；
The second polymer stage includes potentially acting as the chemical reaction of the thermoplastic polymer and polymer composition of self-regeneration agent more
It closes.
United States Patent (USP) (application number: 20150274805 patent names: Elastic Hydrogel elastic hydrogel) discloses
A kind of composition, the composition include a kind of handling a kind of troposphere elastin by a kind of compound containing acrylate group
And the troposphere elastin of the acroleic acid esterification formed, condition is that the acrylate group of the compound is attached to the convection current
On the amine of layer elastin.This troposphere elastin, the acrylic acid being connected including at least one amido with troposphere elastin
Ester group, troposphere elastin monomer are crosslinkings, and troposphere elastin monomer is by being present in the troposphere elastin monomer
Covalent bond between amino amino is connected with each other, and formation condition is that the acrylic of the compound is attached to the troposphere bullet
On the amido of power element.
Technology is the problem is that tensility can be insufficient at present, and electric conductivity is short of, and self-healing is poor, it is difficult to which being used for can only
Garments worn etc. has the environment more than sensing demand and fold.
Summary of the invention
To solve the above problems, the purpose of the present invention is to provide a kind of stretchable self-healing ionic conduction nanometers of high transparency
The preparation method of composite hydrogel.
Using the Cellulose nanocrystal body of poly- tannic acid cladding as Physical crosslinking agent and reinforcing agent, hydrogen is formed by polyphenol hydroxyl
Key and ionic bond bonding 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide and acrylamide
Copolymer, pass through regulation 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide and acryloyl
Through ultraviolet light-initiated final product hydrogel quickly is prepared in the feed ratio of amine.
A kind of stretchable self-healing ionic conduction Nanometer composite hydrogel of high transparency, it is characterised in that by tannic acid cladding
Cellulose nanocrystal and macromolecular chain combination of polymers form, the mass ratio of the tannic acid and Cellulose nanocrystal be 5:1 ~
1:1 is the Physical crosslinking agent and reinforcing agent of hydrogel；The macromolecular chain polymer is 2- (methylacryloyl oxygroup) second
The copolymer of base-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide and acrylamide.
The present invention also provides a kind of preparation methods of above-mentioned hydrogel, it is characterised in that including following steps in sequence:
(1) in deionized water by the dissolution of Cellulose nanocrystal body, magnetic agitation is to evenly dispersed at room temperature；Trihydroxy methyl is added dropwise
Aminomethane and hydrochloric acid adjust the pH of Cellulose nanocrystal dispersion liquid to alkalinity；Natural polyphenol is added into solution, at room temperature
Light yellow clarification mixed liquor is stirred to get, poly- tannic acid is reduced to for tannic acid and is coated on Cellulose nanocrystal body surface face；
(2) by a certain amount of acrylamide and 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- propyl sulfonic acid) hydroxide
Ammonium is added in step (1) acquired solution, is transferred into ice-water bath, and magnetic agitation makes solution viscosity be lower, saturating in clarification
Photoinitiator and conduction liquid and crosslinking agent N, N'- methylene-bis-acrylamide, shading magnetic agitation are added when bright into solution
Obtain pre-polymerization liquid；
(3) step (2) products therefrom continuously vacuumizes logical nitrogen, then is poured into molding die, is then placed in mold
Cured gel final product is irradiated under ultraviolet lamp.
Preparation method kind of the present invention, the natural polyphenol are tannic acid, in dopamine, catechol, anthocyanidin, theaflavin
One or more；Photoinitiator is 2- hydroxy-2-methyl propiophenone, 2- hydroxy-methyl phenyl-propane -1- ketone, 2- hydroxyl -2-
Methyl-1-phenyl-1- acetone, one or more of 2-oxoglutaric acid.
Beneficial effect
Compared with prior art, the beneficial effects of the present invention are: (i) easy one kettle way and low cost (ii) widely may be used
Tonality matter, and (iii) biocompatibility and nontoxicity.Obtained ion conductor shows high sensitivity, has under small strain
Close to 2.0 sensitivity coefficient of hydrogel theoretical value, extremely low operation voltage, wide strain window, strong tack and self-healing
Property is closed, will be had broad application prospects in fields such as wearable sensing, smart electronics, artificial skins.
Detailed description of the invention:
A kind of Fig. 1: the adhesion of the stretchable self-healing ionic conduction Nanometer composite hydrogel of high transparency prepared by embodiment 1.
Fig. 2: a kind of stretching of the stretchable self-healing ionic conduction Nanometer composite hydrogel of high transparency prepared by embodiment 1 is strong
Degree.
Specific embodiment
The following examples are further illustrations of the invention, it is not intended to limit the scope of the invention.
Embodiment 1:
(1) Cellulose nanocrystal body 10mg is dissolved in 10ml deionized water, magnetic agitation 2h is to evenly dispersed at room temperature；Drop
Adding concentration is the trishydroxymethylaminomethane and hydrochloric acid of 1M, adjusts the pH to 8.0 of Cellulose nanocrystal dispersion liquid；Into solution
The natural polyphenol tannic acid of 0.03mg is added, stirs 4h at room temperature, obtains light yellow clarification mixed liquor, is reduced to gather for tannic acid
Tannic acid is coated on Cellulose nanocrystal body surface face；
(2) 0.67g acrylamide and 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- sulfonic acid of 0.98g are weighed respectively
Propyl) ammonium hydroxide is added in step (1) acquired solution, is transferred into ice-water bath, magnetic agitation 1h, and solution viscosity becomes
It is low, it is in clear；The photoinitiator 2- hydroxy-2-methyl propiophenone and 0.1wt% of 0.05mol% monomer are added into solution
Conduction liquid and 0.01wt% crosslinking agent N, N'- methylene-bis-acrylamide, shading magnetic agitation 0.5h obtains pre-polymerization
Liquid；
(3) step (2) products therefrom continuously vacuumizes logical nitrogen 10min, is transferred in molding die with syringe, then by mould
Tool is placed in ultraviolet lamp (365nm, 22.4mW/cm2) under irradiate 6min, obtain cured gel final product.
The present invention according to the stretchable self-healing ionic conduction Nanometer composite hydrogel of high transparency that above-mentioned preparation method obtains,
Adhesion is as shown in Figure 1, the gel can have excellent adhesion with various materials plates such as PP, PC, ABS and POM.Gel
Mechanics is as shown in Fig. 2, fracture tensile strength 157KPa, breaking strain 1080%.
Embodiment 2:
(1) Cellulose nanocrystal body 40mg is dissolved in 12ml deionized water, magnetic agitation 2h is to evenly dispersed at room temperature；Drop
Adding concentration is the trishydroxymethylaminomethane and hydrochloric acid of 1M, adjusts the pH to 8.5 of Cellulose nanocrystal dispersion liquid；Into solution
The natural polyphenol dopamine of 0.1mg is added, stirs 5h at room temperature, obtains light yellow clarification mixed liquor, is reduced to gather for tannic acid
Tannic acid is coated on Cellulose nanocrystal body surface face；
(2) 0.8g acrylamide and 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- sulfonic acid of 0.12 g are weighed respectively
Propyl) ammonium hydroxide is added in step (1) acquired solution, is transferred into ice-water bath, magnetic agitation 1.5h, solution viscosity
It is lower, is in clear；The photoinitiator 2- hydroxy-methyl phenyl-propane -1- ketone of 0.06mol% monomer is added into solution, and
Crosslinking agent N, the N'- methylene-bis-acrylamide of 0.05wt%, shading magnetic agitation 1h obtain pre-polymerization liquid；
(3) step (2) products therefrom continuously vacuumizes logical nitrogen 15min, is transferred in molding die with syringe, then by mould
Tool is placed in ultraviolet lamp (365nm, 22.4mW/cm2) under irradiate 8min, obtain cured gel final product.
Embodiment 3:
(1) Cellulose nanocrystal body 60mg is dissolved in 13ml deionized water, magnetic agitation 2h is to evenly dispersed at room temperature；Drop
Adding concentration is the trishydroxymethylaminomethane and hydrochloric acid of 1M, adjusts the pH to 8.7 of Cellulose nanocrystal dispersion liquid；Into solution
The natural polyphenol catechol of 0.12mg is added, stirs 6h at room temperature, obtains light yellow clarification mixed liquor, is reduced to gather for tannic acid
Tannic acid is coated on Cellulose nanocrystal body surface face；
(2) 0.15g acrylamide and 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- sulfonic acid of 0.14g are weighed respectively
Propyl) ammonium hydroxide is added in step (1) acquired solution, is transferred into ice-water bath, magnetic agitation 1.5h, solution viscosity
It is lower, is in clear；The photoinitiator 2- hydroxy-2-methyl -1- phenyl -1- third of 0.08mol% monomer is added into solution
Crosslinking agent N, the N'- methylene-bis-acrylamide of ketone and 0.07wt%, shading magnetic agitation 1.5h obtain pre-polymerization liquid；
(3) step (2) products therefrom continuously vacuumizes logical nitrogen 20min, is transferred in molding die with syringe, then by mould
Tool is placed in ultraviolet lamp (365nm, 22.4mW/cm2) under irradiate 9min, obtain cured gel final product.
Embodiment 4:
(1) Cellulose nanocrystal body 80mg is dissolved in 14ml deionized water, magnetic agitation 2h is to evenly dispersed at room temperature；Drop
Adding concentration is the trishydroxymethylaminomethane and hydrochloric acid of 1M, adjusts the pH to 9.0 of Cellulose nanocrystal dispersion liquid；Into solution
The natural polyphenol A of 0.21mg is added, stirs 8h at room temperature, obtains light yellow clarification mixed liquor, is reduced to poly- tannin for tannic acid
Acid is coated on Cellulose nanocrystal body surface face；
(2) 1.67g acrylamide and 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- sulfonic acid of 2.25g are weighed respectively
Propyl) ammonium hydroxide is added in step (1) acquired solution, is transferred into ice-water bath, magnetic agitation 3h, and solution viscosity becomes
It is low, it is in clear；The photoinitiator 2-oxoglutaric acid of 0.09mol% monomer and the crosslinking agent of 0.09wt% are added into solution
N, N'- methylene-bis-acrylamide, shading magnetic agitation 2h, obtain pre-polymerization liquid；
(3) step (2) products therefrom continuously vacuumizes logical nitrogen 30min, is transferred in molding die with syringe, then by mould
Tool is placed in ultraviolet lamp (365nm, 22.4mW/cm2) under irradiate 15min, obtain cured gel final product.
Embodiment 5:
(1) Cellulose nanocrystal body 120mg is dissolved in 20ml deionized water, magnetic agitation 2h is to evenly dispersed at room temperature；
The trishydroxymethylaminomethane and hydrochloric acid that concentration is 1M is added dropwise, adjusts the pH to 10.0 of Cellulose nanocrystal dispersion liquid；Xiang Rong
The natural polyphenol anthocyanidin of 0.36mg is added in liquid, stirs 12h at room temperature, obtains light yellow clarification mixed liquor, also for tannic acid
It originally was that poly- tannic acid is coated on Cellulose nanocrystal body surface face；
(2) 2.0g acrylamide and 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- sulfonic acid third of 2.56g are weighed respectively
Base) ammonium hydroxide is added in step (1) acquired solution, is transferred into ice-water bath, magnetic agitation 4h, and solution viscosity becomes
It is low, it is in clear；The photoinitiator 2- hydroxy-2-methyl propiophenone and 0.1wt% of 0.1mol% monomer are added into solution
Crosslinking agent N, N'- methylene-bis-acrylamide, shading magnetic agitation 2.5h obtain pre-polymerization liquid；
(3) step (2) products therefrom continuously vacuumizes logical nitrogen 40min, is transferred in molding die with syringe, then by mould
Tool is placed in ultraviolet lamp (365nm, 22.4mW/cm2) under irradiate 20min, obtain cured gel final product.
Foregoing description is only the description to present pre-ferred embodiments, is not any restriction to the scope of the invention.Appoint
Any change or modification what those skilled in the art makes according to the technology contents of the disclosure above should all regard
For equivalent effective embodiment, the range of technical solution of the present invention protection is belonged to.
Claims (3)
1. a kind of stretchable self-healing ionic conduction Nanometer composite hydrogel of high transparency, it is characterised in that the fibre coated by tannic acid
Dimension element is nanocrystalline and macromolecular chain combination of polymers forms, and the mass ratio of the tannic acid and Cellulose nanocrystal is 5:1 ~ 1:
1, it is the Physical crosslinking agent and reinforcing agent of hydrogel；The macromolecular chain polymer is 2- (methylacryloyl oxygroup) second
The copolymer of base-dimethyl-(3- propyl sulfonic acid) ammonium hydroxide and acrylamide.
2. a kind of preparation method of the stretchable self-healing ionic conduction Nanometer composite hydrogel of high transparency, it is characterised in that including such as
The step of lower sequence:
(1) in deionized water by the dissolution of Cellulose nanocrystal body, magnetic agitation is to evenly dispersed at room temperature；Trihydroxy methyl is added dropwise
Aminomethane and hydrochloric acid adjust the pH of Cellulose nanocrystal dispersion liquid to alkalinity；Natural polyphenol is added into solution, at room temperature
Light yellow clarification mixed liquor is stirred to get, poly- tannic acid is reduced to for tannic acid and is coated on Cellulose nanocrystal body surface face；
(2) by a certain amount of acrylamide and 2- (methylacryloyl oxygroup) ethyl-dimethyl-(3- propyl sulfonic acid) hydroxide
Ammonium is added in step (1) acquired solution, is transferred into ice-water bath, and magnetic agitation makes solution viscosity be lower, saturating in clarification
Photoinitiator and conduction liquid and crosslinking agent N, N'- methylene-bis-acrylamide, shading magnetic agitation are added when bright into solution
Obtain pre-polymerization liquid；
(3) step (2) products therefrom continuously vacuumizes logical nitrogen, then is poured into molding die, is then placed in mold
Cured gel final product is irradiated under ultraviolet lamp.
3. preparation method according to claim 2, it is characterised in that the natural polyphenol is tannic acid, dopamine, catechu
One or more of phenol, anthocyanidin, theaflavin；Photoinitiator is 2- hydroxy-2-methyl propiophenone, 2- hydroxy-methyl phenyl
Propane -1- ketone, 2- hydroxy-2-methyl -1- phenyl -1- acetone, one or more of 2-oxoglutaric acid.
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Application publication date: 20190816 |