CN107163185B - It is a kind of can spontaneous driving dopamine gel driver and preparation method thereof and driving method - Google Patents
It is a kind of can spontaneous driving dopamine gel driver and preparation method thereof and driving method Download PDFInfo
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- CN107163185B CN107163185B CN201710376981.3A CN201710376981A CN107163185B CN 107163185 B CN107163185 B CN 107163185B CN 201710376981 A CN201710376981 A CN 201710376981A CN 107163185 B CN107163185 B CN 107163185B
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- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 title claims abstract description 242
- 229960003638 dopamine Drugs 0.000 title claims abstract description 121
- 230000002269 spontaneous effect Effects 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 144
- NQIMONOHVBBZKE-UHFFFAOYSA-N n-[2-(3,4-dihydroxyphenyl)ethyl]-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCCC1=CC=C(O)C(O)=C1 NQIMONOHVBBZKE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007654 immersion Methods 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000003431 cross linking reagent Substances 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 21
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 239000000499 gel Substances 0.000 abstract 3
- 239000000017 hydrogel Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 230000008569 process Effects 0.000 description 16
- 238000010382 chemical cross-linking Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000006392 deoxygenation reaction Methods 0.000 description 15
- 239000003643 water by type Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 10
- -1 N, N'Methylene Chemical group 0.000 description 9
- 150000003926 acrylamides Chemical class 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 5
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 5
- 239000003292 glue Substances 0.000 description 4
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 3
- GILDFPGOCAQXOP-UHFFFAOYSA-N azanium;2-methylprop-2-enimidate Chemical compound N.CC(=C)C(N)=O GILDFPGOCAQXOP-UHFFFAOYSA-N 0.000 description 3
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229960004502 levodopa Drugs 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000006399 behavior Effects 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Dental Preparations (AREA)
Abstract
The invention discloses it is a kind of can spontaneous driving dopamine gel driver and preparation method thereof and driving method, the gel which is copolymerized by dopamine Methacrylamide and acrylamide monomers is using Fe3+Fixed temporary shapes are obtained after solution immersion treatment in alkaline solution to be prepared；The driving function that the dopamine gel driver can make hydrogel realize that spontaneous shape changes in the solution by changing the method for solution ph.
Description
Technical field
The present invention relates to the intellectual material fields of functional dopamine polymer, and in particular to it is a kind of can spontaneous driving it is more
Bar amine gel driver and preparation method thereof and driving method.
Background technique
Gel assigns the characteristic of its soft substance due to containing a large amount of solvent, and with perfect three-dimensional net structure,
Have many advantages, such as that the strong response of weak stimulation-, the big effect of few addition-, drive condition are mild；And soft substance driver especially gel flooding
Dynamic development of the device in intelligent device field is of increasing concern.
In the research of gel driver, shape memory gel driver can be returned to original-shape from temporary shapes,
To study a kind of rather extensive gel driver at present.But each driving for the shape memory gel driver reported at present
Period require first with external force by gel be fixed as a temporary shapes (ACS Appl. Mater. Interfaces 2016,
8, 12384−12392；Macromol. Mater. Eng. 2017,302,1600359), and it is spontaneous to cannot achieve gel
It is converted between temporary shapes and original-shape, therefore the mode of operation of gel driver is more complicated.Meanwhile reporting at present
Dopamine gel mechanical strength is lower, and it is solidifying to constrain dopamine significantly for unbearable biggish stretching, compression or repeated deformation etc.
Application of the glue in field of drivers.
From dopamine and Fe3+Complexing inspired, based on shape memory gel driver, we are creative
Ground devise it is a kind of can spontaneous driving dopamine gel driver, i.e., dopamine Methacrylamide and hydrophilic monomer are total to
It is poly- to obtain gel, then by gel in Fe3+Immersion treatment in solution, reusing external force makes the gel obtain temporary shapes, by it
It is put into alkaline solution and fixes this temporary shapes；The gel with temporary shapes is put into acid solution again, temporary shapes can
Original-shape is reverted to get dopamine gel driver is arrived.The driver can make it in temporary shapes by controlling pH value of solution
Spontaneous variation is between original-shape to generate driving, and this process may be repeated.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides it is a kind of can spontaneous driving dopamine gel driver and its system
Preparation Method and driving method.
Dopamine gel driver of the invention is total to by dopamine Methacrylamide and hydrophilic acrylamide class monomer
Poly- obtained gel, in Fe3+Enable the temporary shapes become by external force solid in solution after immersion treatment in alkaline solution
It is fixed, dopamine gel driver is obtained, which can not apply external force by controlling solution ph
In the case where, drive its spontaneous variation between temporary shapes and original-shape to generate, and this process may be repeated.
The purpose of the present invention is achieved through the following technical solutions.
It is a kind of can spontaneous driving dopamine gel driver preparation method, include the following steps:
(1) dopamine gel is prepared: acrylamide monomers and crosslinking agent are soluble in water, obtain mixed liquor a；By dopamine
Methacrylamide and initiator are dissolved in organic solvent, obtain mixed liquor b；Mixed liquor a and mixed liquor b are mixed again and remove institute
The oxygen in mixed liquor is obtained, is then injected into mold, is polymerize under ultraviolet lighting, obtain dopamine gel；
(2) it prepares dopamine gel driver: the dopamine gel of step (1) preparation is used into Fe3+Solution immersion treatment,
It obtains containing Fe3+Gel；Made using external force containing Fe3+Gel obtain temporary shapes, the gel with temporary shapes is put
Enter to fix this temporary shapes in alkaline solution to get dopamine gel driver is arrived.
Further, step (1) described acrylamide monomers areN, N-In dimethylacrylamide and acrylamide
More than one, concentration of the acrylamide monomers in mixed liquor is 2 ~ 6 mol/L；The crosslinking agent isN, N'It is sub-
Bisacrylamide, concentration of the crosslinking agent in mixed liquor are 0.2 ~ 1 mmol/L.
Further, concentration of step (1) the dopamine Methacrylamide in mixed liquor is 0.2 ~ 0.8
mol/L；The initiator is photoinitiator Irgacure-2959, and the dosage of the initiator is acrylamide monomers and more
The 0.2 ~ 0.4% of bar amine Methacrylamide integral molar quantity.
Further, the wave-length coverage of step (1) described ultraviolet lighting is 300 ~ 380nm, and power is 10 ~ 50W；It is described poly-
The time of conjunction is 2 ~ 20 h.
Further, step (1) described organic solvent is organic solvent miscible with water, preferably methanol, ethyl alcohol, diformazan
Base sulfoxide, acetone, tetrahydrofuran orN, N-Dimethylformamide.
Further, step (2) Fe3+Solution is FeCl3Solution, Fe2(SO4)3Solution and Fe (NO3)3In solution
More than one, concentration is 0.01 ~ 0.5 mol/L；The time of the immersion treatment is 10 ~ 60 s.
Further, step (2) alkaline solution is NaOH solution, the KOH solution, Ca (OH) of pH > 92Solution or
Ba(OH)2Solution；The temporary shapes are the shapes different from gel original-shape；The regular time is 10 ~ 60 s.
One kind as made from above-described preparation method can spontaneous driving dopamine gel driver.
Above-described one kind can spontaneous driving dopamine gel driver driving method, comprising the following steps:
(1) dopamine gel driver is put into acid solution and is impregnated, temporary shapes can revert to original-shape；
(2) the dopamine gel driver for reverting to original-shape is placed into alkaline solution and is impregnated, the dopamine
Gel driver can in the case where no external force it is spontaneous become again before temporary shapes；
(3) the dopamine gel driver with temporary shapes is carried out to the operation of step (1), the dopamine gel again
Driver can revert to original-shape, and the dopamine gel driver for reverting to original-shape is carried out to the behaviour of step (2) again
Make, the dopamine gel driver in the case where no external force it is spontaneous become again before temporary shapes；That is, passing through
Step (1) and step (2) continuously repeat operation, may be implemented by controlling solution ph, in the feelings for not applying external force
Under condition, making the dopamine gel driver, spontaneous variation is driven between temporary shapes and original-shape with generating in the solution
It is dynamic.
Further, step (1) acid solution is HCl solution, the H of pH < 52SO4Solution or HNO3Solution；It is described
The time of immersion is 10 ~ 60 s.
Further, step (2) alkaline solution is NaOH solution, the KOH solution, Ca (OH) of pH > 92Solution or
Ba(OH)2Solution；The time of the immersion is 1 ~ 20 min；The temporary shapes are and the original shape of dopamine gel driver
The different shape of shape.
Compared with prior art, the present invention has the advantage that and technical effect:
1. dopamine gel driver provided by the invention, can be by controlling pH value of solution, in the feelings for not applying external force
Under condition, making gel, spontaneous variation is driven between temporary shapes and original-shape with generating in the solution, and this process is repeatable
It carries out, overcoming conventional shape-memory gel driver each shape memory period must be by external force acquisition temporary shapes
Defect.
2 it is provided by the present invention can the dopamine gel driver of continuous spontaneous driving can be used for designing spontaneous driving
The Intelligent Drive Electronics such as flexible robot.
3. the present invention uses " one-step method ", dopamine gel driver is prepared by the method for shape memory gel, is made
Preparation method is easy, easy to operate, can be directly used for preparing gel driver.
4. the dopamine gel driver of spontaneous driving prepared by the present invention has higher than traditional dopamine gel good
Mechanical strength overcomes the low disadvantage of traditional dopamine gel mechanical strength.
It, can be according to using 5. the present invention can adjust the mechanical strength of gel by the content of control monomer or crosslinking agent
Environment difference provides the dopamine gel driver of varying strength and different driving rate.
Specific embodiment
Further detailed description is done to the present invention below with reference to embodiment.To gel obtained in embodiment, use
The measurement of method disclosed in 2016,8,12384 12392 document of the ACS Appl. Mater. such as Huang Interfaces is mechanical
Performance, these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
Embodiment 1
At room temperature by 1.03 mLN, NDimethylacrylamide and 15.417 μ L chemical cross-linking agentsN, N'Methylene
Base bisacrylamide aqueous solution (concentration is 20 mg/mL) is dissolved in 3 mL deoxygenation deionized waters, and 1 mL is then added and contains 0.55
The dimethyl sulphoxide solution of g dopamine Methacrylamide and 8.35 mg initiator Irgacure-2959, leads to after mixing evenly
Enter nitrogen and remove oxygen therein, finally reaction solution is added in mold and is sealed, is at room temperature 300nm, power in wavelength
To polymerize 2 h under the ultraviolet lighting of 50W into gel.The tensile break strength of gained dopamine gel is 30 kPa；By what is obtained
Dopamine gel is in 0.01 mol/L FeCl330 s are impregnated in solution, will contain Fe3+Dopamine gel twist into it is spiral-shaped
20 s are fixed in the NaOH solution of pH=12 afterwards to get dopamine gel driver, HCl solution of the driver in pH=1 is arrived
Uncoiling can be realized in 10 s of middle immersion, and being then immersed in 2 min in the NaOH solution of pH=12 can be realized spiral again, this
Process is 8 times repeatable.
Embodiment 2
At room temperature by 2.06 mLN, NDimethylacrylamide and 15.417 μ L chemical cross-linking agentsN, N'Methylene
Base bisacrylamide aqueous solution (concentration is 20 mg/mL) is dissolved in 2 mL deoxygenation deionized waters, and 1 mL is then added and contains
The methanol solution of 0.55 g dopamine Methacrylamide and 10.1 mg initiator Irgacure-2959, leads to after mixing evenly
Enter nitrogen and remove oxygen therein, finally reaction solution is added in mold and is sealed, is at room temperature 380nm, power in wavelength
To polymerize 5 h under the ultraviolet lighting of 30W into gel.The tensile break strength of gained dopamine gel is 110 kPa；By what is obtained
Dopamine gel is in 0.2 mol/L FeCl310 s are impregnated in solution, will contain Fe3+Dopamine gel twist into it is spiral-shaped after
60 s are fixed in the KOH solution of pH=9.5 to get to dopamine gel driver, the driver is in the HCl solution of pH=2
Impregnating 20 s can be realized uncoiling, and being then immersed in 20 min in the KOH solution of pH=9.5 can be realized spiral again, this mistake
Journey is 8 times repeatable.
Embodiment 3
At room temperature by 3.09 mLN, NDimethylacrylamide and 15.417 μ L chemical cross-linking agentsN, N'Methylene
Base bisacrylamide aqueous solution (concentration is 20 mg/mL) is dissolved in 1 mL deoxygenation deionized water, and 1 mL is then added and contains
The ethanol solution of 0.55 g dopamine Methacrylamide and 25 mg initiator Irgacure-2959, is passed through after mixing evenly
Nitrogen removes oxygen therein, and finally reaction solution is added in mold and is sealed, and is at room temperature 360nm in wavelength, power is
Polyase 13 h is at gel under the ultraviolet lighting of 40W.The tensile break strength of gained dopamine gel is 160 kPa；It is more by what is obtained
Bar amine gel is in 0.03 mol/L Fe2(SO4)325 s are impregnated in solution, and the dopamine gel containing iron ion is twisted into spiral
In the Ca (OH) of pH=10 after shape250 s are fixed in solution to get to dopamine gel driver, the driver is in pH=3
30 s are impregnated in HCl solution can be realized uncoiling, then be immersed in the Ca (OH) of pH=10215 min can be realized in solution
Again spiral, this process are 9 times repeatable.
Embodiment 4
At room temperature by 2.06 mLN, NDimethylacrylamide and 15.417 μ L chemical cross-linking agentsN, N'Methylene
Base bisacrylamide aqueous solution (concentration is 20 mg/mL) is dissolved in 2 mL deoxygenation deionized waters, and 1 mL is then added and contains
The acetone soln of 0.22 g dopamine Methacrylamide and 16.7 mg initiator Irgacure-2959, leads to after mixing evenly
Enter nitrogen and remove oxygen therein, finally reaction solution is added in mold and is sealed, is at room temperature 330nm, power in wavelength
To polymerize 10 h under the ultraviolet lighting of 20W into gel.The tensile break strength of gained dopamine gel is 100 kPa；It will obtain
Dopamine gel in 0.5 mol/L FeCl360 s are impregnated in solution, will contain Fe3+Dopamine gel twist into it is spiral-shaped
Afterwards in the Ba (OH) of pH ~ 13210 s are fixed in solution to get to dopamine gel driver, the driver is in pH=4.5
H2SO460 s are impregnated in solution can be realized uncoiling, then be immersed in the Ba (OH) of pH=1325 min can be realized in solution
Again spiral, this process are 7 times repeatable.
Embodiment 5
At room temperature by 2.06 mLN, NDimethylacrylamide and 15.417 μ L chemical cross-linking agentsN, N'Methylene
Base bisacrylamide aqueous solution (concentration is 20 mg/mL) is dissolved in 1 mL deoxygenation deionized water, and 2 mL are then added and contain
The tetrahydrofuran solution of 0.88 g dopamine Methacrylamide and 16.7 mg initiator Irgacure-2959, stirs evenly
After be passed through nitrogen and remove oxygen therein, finally reaction solution is added in mold and is sealed, is at room temperature 350nm in wavelength,
It polymerize 20 h into gel under the ultraviolet lighting that power is 10W.The tensile break strength of gained dopamine gel is 120 kPa；It will
Obtained dopamine gel is in 0.2 mol/L Fe (NO3)330 s are impregnated in solution, will contain Fe3+Dopamine gel twist into
30 s are fixed after arc in the NaOH solution of pH=13 to get to dopamine gel driver, the driver is in pH=1.5
HNO310 s are impregnated in solution can be realized radian reduction, and being then immersed in 2 min in the NaOH solution of pH=13 can be realized weight
Radian is newly increased, this process is 5 times repeatable.
Embodiment 6
At room temperature by 2.06 mLN, NDimethylacrylamide and 7.78 μ L chemical cross-linking agentsN, N'Methylene
Bisacrylamide aqueous solution (concentration is 20 mg/mL) is dissolved in 2 mL deoxygenation deionized waters, and 1 mL is then added and contains 0.55
The dimethyl sulphoxide solution of g dopamine Methacrylamide and 16.7 mg initiator Irgacure-2959, after mixing evenly
It is passed through nitrogen and removes oxygen therein, finally reaction solution is added in mold and is sealed, be at room temperature 370nm, function in wavelength
It polymerize 5 h into gel under the ultraviolet lighting that rate is 45W.The tensile break strength of gained dopamine gel is 100 kPa；It will obtain
Dopamine gel in 0.5 mol/L Fe (NO3)330 s are impregnated in solution, will contain Fe3+Dopamine gel twist into spiral
20 s are fixed after shape in the NaOH solution of pH=12 to get dopamine gel driver, H of the driver in pH=1 is arrived2SO4
20 s are impregnated in solution can be realized uncoiling, and being then immersed in 2 min in the NaOH solution of pH=12 can be realized spiral shell again
Rotation, this process are 8 times repeatable.
Embodiment 7
At room temperature by 2.06 mLN, NDimethylacrylamide and 23.13 μ L chemical cross-linking agentsN, N'Methylene
Bisacrylamide aqueous solution (concentration is 20 mg/mL) is dissolved in 2 mL deoxygenation deionized waters, and 1 mL is then added and contains 0.55
G dopamine Methacrylamide and 16.7 mg initiator Irgacure-2959'sN, N-Dimethyl formamide solution, stirring
It is passed through nitrogen after uniformly and removes oxygen therein, finally reaction solution is added in mold and is sealed, is in wavelength at room temperature
350nm, power be 25W ultraviolet light irradiation under polymerize 15 h into gel.The tensile break strength of gained dopamine gel is 150
kPa；By obtained dopamine gel in 0.5 mol/L Fe (NO3)320 s are impregnated in solution, will contain Fe3+Dopamine it is solidifying
Glue twist into it is spiral-shaped after 20 s are fixed in the NaOH solution of pH=14 to get to dopamine gel driver, which exists
25 s are impregnated in the HCl solution of pH=1 can be realized uncoiling, and being then immersed in 1 min in the NaOH solution of pH=14 can be real
Now spiral, this process are 8 times repeatable again.
Embodiment 8
At room temperature by 2.06 mLN, NDimethylacrylamide and 38.55 μ L chemical cross-linking agentsN, N'Methylene
Bisacrylamide aqueous solution (concentration is 20 mg/mL) is dissolved in 2 mL deoxygenation deionized waters, and 1 mL is then added and contains 0.55
The dimethyl sulphoxide solution of g dopamine Methacrylamide and 16.7 mg initiator Irgacure-2959, after mixing evenly
It is passed through nitrogen and removes oxygen therein, finally reaction solution is added in mold and is sealed, be at room temperature 360nm, function in wavelength
It polymerize 6 h into gel under the ultraviolet lighting that rate is 40W.The tensile break strength of gained dopamine gel is 150 kPa；It will obtain
Dopamine gel in 0.1 mol/L Fe2(SO4)340 s are impregnated in solution, will contain Fe3+Dopamine gel twist into spiral
In the Ba (OH) of pH=12 after shape220 s are fixed in solution to get to dopamine gel driver, the driver is in pH=1
HNO340 s are impregnated in solution can be realized uncoiling, then be immersed in the Ba (OH) of pH=12210 min can be realized in solution
Again spiral, this process are 8 times repeatable.
Embodiment 9
At room temperature by 2.13 g acrylamides and 57.78 μ L chemical cross-linking agentsN, N'Methylene-bisacrylamide water
Solution (concentration is 20 mg/mL) is dissolved in 12.942 mL deoxygenation deionized waters, and 2 mL are then added and contain 0.66 g DOPA
The dimethyl sulphoxide solution of amine Methacrylamide and 20 mg initiator Irgacure-2959, is passed through nitrogen after mixing evenly
Oxygen therein is removed, finally reaction solution is added in mold and is sealed, is at room temperature 365nm in wavelength, power is 45W's
Polyase 13 h is at gel under ultraviolet lighting.The tensile break strength of gained dopamine gel is 50 kPa；Obtained dopamine is coagulated
Glue is in 0.1 mol/L FeCl320 s are impregnated in solution, will contain Fe3+Dopamine gel twist into it is spiral-shaped after in pH=12
NaOH solution in fix 20 s to get to dopamine gel driver, which impregnates 60 s in the HCl solution of pH=3
Uncoiling can be realized, being then immersed in 2 min in the NaOH solution of pH=12 can be realized spiral again, this process is repeatable
10 times.
Embodiment 10
At room temperature by 3.195 g acrylamides and 57.78 μ L chemical cross-linking agentsN, N'Methylene-bisacrylamide water
Solution (concentration is 20 mg/mL) is dissolved in 12.942 mL deoxygenation deionized waters, and 2 mL are then added and contain 0.66 g DOPA
Amine Methacrylamide and 40 mg initiator Irgacure-2959'sN, N-Dimethyl formamide solution leads to after mixing evenly
Enter nitrogen and remove oxygen therein, finally reaction solution is added in mold and is sealed, is at room temperature 360nm, power in wavelength
To polymerize 2 h under the ultraviolet lighting of 50W into gel.The tensile break strength of gained dopamine gel is 100 kPa；By what is obtained
Dopamine gel is in 0.1 mol/L FeCl320 s are impregnated in solution, will contain Fe3+Dopamine gel twist into it is spiral-shaped after
20 s are fixed in the KOH solution of pH=12 to get to dopamine gel driver, the driver is in the HCl solution of pH=1.5
Impregnating 10 s can be realized uncoiling, and being then immersed in 2 min in the KOH solution of pH=12 can be realized spiral again, this process
It is 10 times repeatable.
Embodiment 11
At room temperature by 6.39 g acrylamides and 57.78 μ L chemical cross-linking agentsN, N'Methylene-bisacrylamide water
Solution (concentration is 20 mg/mL) is dissolved in 9.942 mL deoxygenation deionized waters, and 5 mL are then added and contain 0.66 g dopamine
The tetrahydrofuran solution of Methacrylamide and 45 mg initiator Irgacure-2959 is passed through nitrogen removing after mixing evenly
Reaction solution is finally added in mold and is sealed by oxygen therein, is at room temperature 340nm in wavelength, power is the ultraviolet of 40W
It polymerize 5 h under illumination into gel.The tensile break strength of gained dopamine gel is 150 kPa；The dopamine gel that will be obtained
In 0.01 mol/L Fe2(SO4)330 s are impregnated in solution, will contain Fe3+Dopamine gel twist into after curved shape pH=
20 s are fixed in 14 KOH solution to get dopamine gel driver, H of the driver in pH=4 is arrived2SO430 are impregnated in solution
S can become vertical bar shaped again, and curved shape can be become again by being then immersed in 1 min in the KOH solution of pH=14, this process can
It is repeated 9 times.
Embodiment 12
At room temperature by 3.195 g acrylamides and 57.78 μ L chemical cross-linking agentsN, N'Methylene-bisacrylamide water
Solution (concentration is 20 mg/mL) is dissolved in 11.942 mL deoxygenation deionized waters, and 3 mL are then added and contain 1.32 g DOPA
The methanol solution of amine Methacrylamide and 45.747 mg initiator Irgacure-2959, is passed through nitrogen after mixing evenly and removes
Oxygen therein is removed, finally reaction solution is added in mold and is sealed, is at room temperature 365nm in wavelength, power is the purple of 20W
It polymerize 10 h under outer illumination into gel.The tensile break strength of gained dopamine gel is 110 kPa；Obtained dopamine is coagulated
Glue is in 0.01 mol/L Fe (NO3)340 s are impregnated in solution, will contain Fe3+Dopamine gel twist into it is spiral-shaped after in pH
=13 Ba (OH)220 s are fixed in solution to get dopamine gel driver, HNO of the driver in pH=1 is arrived3It is soaked in solution
Steeping 10 s can be realized uncoiling, then be immersed in the Ba (OH) of pH=132Spiral again can be realized in 2 min in solution, this mistake
Journey is 10 times repeatable.
Embodiment 13
At room temperature by 3.195 g acrylamides and 57.78 μ L chemical cross-linking agentsN, N'Methylene-bisacrylamide water
Solution (concentration is 20 mg/mL) is dissolved in 9.942 mL deoxygenation deionized waters, and 5 mL are then added and contain 2.64 g dopamines
The ethanol solution of Methacrylamide and 30 mg initiator Irgacure-2959 is passed through nitrogen after mixing evenly and removes wherein
Oxygen, finally reaction solution is added in mold and is sealed, at room temperature wavelength be 360nm, power be 25W ultraviolet lighting
15 h are at gel for lower polymerization.The tensile break strength of gained dopamine gel is 120 kPa；Obtained dopamine gel is existed
0.2 mol/L Fe(NO3)310 s are impregnated in solution, will contain Fe3+Dopamine gel twist into it is spiral-shaped after in pH=10
Ca(OH)260 s are fixed in solution to get dopamine gel driver, H of the driver in pH=1.5 is arrived2SO4It is impregnated in solution
Uncoiling can be realized in 20 s, is then immersed in the Ca (OH) of pH=102Spiral again can be realized in 8 min in solution, this process
It is 12 times repeatable.
Embodiment 14
At room temperature by 3.195 g acrylamides and 23.112 μ L chemical cross-linking agentsN, N'Methylene-bisacrylamide
Aqueous solution (concentration be 20 mg/mL) is dissolved in 11.976 mL deoxygenation deionized waters, and 3 mL are then added, and to contain 1.32 g more
The acetone soln of bar amine Methacrylamide and 22.87 mg initiator Irgacure-2959, is passed through nitrogen after mixing evenly and removes
Oxygen therein is removed, finally reaction solution is added in mold and is sealed, is at room temperature 310nm in wavelength, power is the purple of 40W
It polymerize 8 h under outer illumination into gel.The tensile break strength of gained dopamine gel is 80 kPa；The dopamine gel that will be obtained
In 0.03 mol/L Fe2(SO4)360 s are impregnated in solution, will contain Fe3+Dopamine gel twist into it is spiral-shaped after pH=
50 s are fixed in 11 NaOH solution to get dopamine gel driver is arrived, which impregnates 20 in the HCl solution of pH=2
Uncoiling can be realized in s, and being then immersed in 5 min in the NaOH solution of pH=11 can be realized spiral again, this process is repeatable
10 times.
Embodiment 15
At room temperature by 3.195 g acrylamides and 115.56 μ L chemical cross-linking agentsN, N'Methylene-bisacrylamide
Aqueous solution (concentration be 20 mg/mL) is dissolved in 11.942 mL deoxygenation deionized waters, and 3 mL are then added, and to contain 1.32 g more
The dimethyl sulphoxide solution of bar amine Methacrylamide and 34.31 mg initiator Irgacure-2959, is passed through after mixing evenly
Nitrogen removes oxygen therein, and finally reaction solution is added in mold and is sealed, and is at room temperature 350nm in wavelength, power is
It polymerize 20 h under the ultraviolet lighting of 20W into gel.The tensile break strength of gained dopamine gel is 120 kPa；By what is obtained
Dopamine gel is in 0.5 mol/L FeCl340 s are impregnated in solution, will contain Fe3+Dopamine gel twist into it is spiral-shaped after
Ba (OH) in pH=9.5260 s are fixed in solution to get dopamine gel driver, HNO of the driver in pH=3 is arrived3It is molten
40 s are impregnated in liquid can be realized uncoiling, then be immersed in the Ba (OH) of pH=9.5220 min can be realized again in solution
Spiral, this process are 9 times repeatable.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes made without departing from the spirit and principles of the present invention, modification, substitution, combination, should be
Equivalent substitute mode, is included within the scope of the present invention.
Claims (9)
1. one kind can spontaneous driving dopamine gel driver preparation method, which comprises the steps of:
(1) dopamine gel is prepared: acrylamide monomers and crosslinking agent are soluble in water, obtain mixed liquor a；By dopamine methyl
Acrylamide and initiator are dissolved in organic solvent, obtain mixed liquor b；Mixed liquor a and mixed liquor b are mixed again and remove gained and is mixed
The oxygen in liquid is closed, is then injected into mold, is polymerize under ultraviolet lighting, obtain dopamine gel；
(2) it prepares dopamine gel driver: the dopamine gel of step (1) preparation is used into Fe3+Solution immersion treatment, obtains
Contain Fe3+Gel；Made using external force containing Fe3+Gel obtain temporary shapes, the gel with temporary shapes is put into alkali
Property solution in fix this temporary shapes to get to dopamine gel driver；Step (1) described acrylamide monomers areN, N-One or more of dimethylacrylamide and acrylamide, concentration of the acrylamide monomers in mixed liquor are 2
~ 6 mol/L；The crosslinking agent isN, N'Methylene-bisacrylamide, concentration of the crosslinking agent in mixed liquor are 0.2
~ 1 mmol/L；Concentration of the dopamine Methacrylamide in mixed liquor is 0.2 ~ 0.8 mol/L；The initiator
For photoinitiator Irgacure-2959, the dosage of the initiator is acrylamide monomers and dopamine Methacrylamide
The 0.2 ~ 0.4% of integral molar quantity.
2. one kind as described in claim 1 can spontaneous driving dopamine gel driver preparation method, which is characterized in that
The wave-length coverage of step (1) described ultraviolet lighting is 300 ~ 380nm, and power is 10 ~ 50W；The time of the polymerization is 2 ~ 20
h。
3. one kind as described in claim 1 can spontaneous driving dopamine gel driver preparation method, which is characterized in that
Step (1) organic solvent be methanol, ethyl alcohol, dimethyl sulfoxide, acetone, tetrahydrofuran orN, N-Dimethylformamide.
4. one kind as described in claim 1 can spontaneous driving dopamine gel driver preparation method, which is characterized in that
Step (2) described Fe3+Solution is FeCl3Solution, Fe2(SO4)3Solution and Fe (NO3)3One or more of solution, concentration are
0.01 ~ 0.5 mol/L；The time of the immersion treatment is 10 ~ 60 s.
5. one kind as described in claim 1 can spontaneous driving dopamine gel driver preparation method, which is characterized in that
Step (2) alkaline solution is NaOH solution, the KOH solution, Ca (OH) of pH > 92Solution or Ba (OH)2Solution；It is described to face
When shape be the shape different from gel original-shape；The regular time is 10 ~ 60 s.
6. one kind as made from claim 1 ~ 5 described in any item preparation methods can spontaneous driving dopamine gel driving
Device.
7. one kind as claimed in claim 6 can spontaneous driving dopamine gel driver driving method, which is characterized in that packet
Include following steps:
(1) dopamine gel driver is put into acid solution and is impregnated, temporary shapes can revert to original-shape；
(2) the dopamine gel driver for reverting to original-shape is placed into alkaline solution and is impregnated, the dopamine gel
Driver can in the case where no external force it is spontaneous become again before temporary shapes；
(3) the dopamine gel driver with temporary shapes is carried out to the operation of step (1), the dopamine gel driving again
Device can revert to original-shape, and the dopamine gel driver for reverting to original-shape is carried out to the operation of step (2), institute again
State dopamine gel driver in the case where no external force it is spontaneous become again before temporary shapes；That is, passing through step
(1) and step (2) continuously repeats operation, may be implemented by controlling solution ph, in the case where not applying external force,
Making the dopamine gel driver, spontaneous variation is driven between temporary shapes and original-shape with generating in the solution.
8. one kind as claimed in claim 7 can spontaneous driving dopamine gel driver driving method, which is characterized in that
Step (1) acid solution is HCl solution, the H of pH < 52SO4Solution or HNO3Solution；The time of the immersion is 10 ~ 60
s。
9. one kind as claimed in claim 7 can spontaneous driving dopamine gel driver driving method, which is characterized in that
Step (2) alkaline solution is NaOH solution, the KOH solution, Ca (OH) of pH > 92Solution or Ba (OH)2Solution；The leaching
The time of bubble is 1 ~ 20 min；The temporary shapes are the shapes different from dopamine gel driver original-shape.
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