CN104861112B - A kind of have shape memory anti tear hydrogel of photosynthesis-carbon dioxide response and its preparation method and application - Google Patents
A kind of have shape memory anti tear hydrogel of photosynthesis-carbon dioxide response and its preparation method and application Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 43
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000004044 response Effects 0.000 title claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 230000006386 memory function Effects 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 125000004386 diacrylate group Chemical group 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 claims description 13
- WWEWYHLJEWDHLY-UHFFFAOYSA-N C(=C)C1=C(C(=CC(=C1)N)N)C=CC1=CC=CC=C1 Chemical compound C(=C)C1=C(C(=CC(=C1)N)N)C=CC1=CC=CC=C1 WWEWYHLJEWDHLY-UHFFFAOYSA-N 0.000 claims description 13
- ZXLYUNPVVODNRE-UHFFFAOYSA-N 6-ethenyl-1,3,5-triazine-2,4-diamine Chemical class NC1=NC(N)=NC(C=C)=N1 ZXLYUNPVVODNRE-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000004971 Cross linker Substances 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- -1 2- hydroxy ethoxy Chemical group 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims 2
- 150000002118 epoxides Chemical class 0.000 claims 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 claims 1
- 239000000499 gel Substances 0.000 abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 12
- 229920002554 vinyl polymer Polymers 0.000 abstract description 8
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 abstract 2
- GMISHZVPHINJPA-UHFFFAOYSA-N N1=CN=CN=C1.NNC(NN)=O Chemical class N1=CN=CN=C1.NNC(NN)=O GMISHZVPHINJPA-UHFFFAOYSA-N 0.000 abstract 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 2
- 230000004936 stimulating effect Effects 0.000 abstract 1
- 230000000638 stimulation Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002953 phosphate buffered saline Substances 0.000 description 5
- 229920002939 poly(N,N-dimethylacrylamides) Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 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 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000008366 buffered solution Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000000892 gravimetry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 150000002835 noble gases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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Classifications
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- 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
- C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
- C08F267/06—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of esters
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Medical Uses (AREA)
- Medicinal Preparation (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention discloses a kind of has shape memory anti tear hydrogel of photosynthesis-carbon dioxide response and preparation method thereof, with 2 vinyl 4,6 diaminourea 1,3,5 triazines, N, N DMAA is monomer, and the copolymerization in the presence of initiator with polyethyleneglycol diacrylate by cross-linking agent is made.2 vinyl, 4,6 diaminourea 1,3,5 triazine, N, the mass ratio of N DMAA is (3：2)‑(3：1).Gel has very strong stretch-proof, incompressible, and anti tear, resistance to breach ability, simultaneously to CO2There is stimulating responsive, and under its stimulation, there is shape memory function.Its preparation method is simple, and product is easy to preserve for a long time and transport for long-distance.
Description
Technical field
The present invention relates to a kind of hydrogel and preparation method, more particularly, it relates to a kind of 2- vinyl -4,6- diamino
Base -1,3,5-triazines, N,N-DMAA copolymer (PVDT-co-PDMA) hydrogel and preparation method thereof, have height
Intensity, anti tear, CO2Response and shape memory function.
Background technology
Hydrogel is with water as disperse medium, hydrophilic and water-fast and can absorb large quantity of moisture and (generally contain
The water yield is more than the 50% of gross mass) there is the macromolecule polymer material of cross-linked structure.Environment sensitive type hydrogel or intelligence
Hydrogel refer to when being changed by external environment (such as pH value, temperature, light, electricity, magnetic field, biomolecule etc.) its volume with
And mechanical property can occur to change accordingly.Intelligent aqueous gel capable is widely developed for biological medicine material, soft wet driver
And pharmaceutical carrier.However, the mechanical property of traditional environment sensitive type hydrogel is very weak very crisp, the tearing energy of typical hydrogels
10-1-100J/m2.Although recently there is remarkable progress for acquisition high intensity intelligent aqueous gel capable, obtaining and there is anti tear
Environment sensitive type hydrogel be still one challenge.
In order to improve the lear energy of gel, scientists think that by research obtaining anti tear hydrogel must is fulfilled for
Two conditions：1. when gel is subject to tear to act on, it is desirable to have can be with the mechanism of energy dispersive；2. gel, in deformation, needs
There is the ability keeping original configuration.A kind of method of the tearing toughness improving gel can be drawn by this, that is, pass through solidifying
Introduce easy fracture in glue network sacrifices the network or reversible weak physical cross-linked network lear energy to improve gel.2-
Vinyl -4,6- diamino-1,3,5-triazines (VDT), due in its polymer molecular chain the strong intramolecular between amino and
Intermolecular hydrogen bond action makes it be used widely in highstrenghtpiston.But strong hydrogen bond action make hydrone be difficult to into
Enter to crosslinked pure poly- 2- vinyl -4, in 6- diamino-1,3,5-triazines network, thus the water content of gel is extremely low.So,
2- vinyl -4,6- diaminostilbene in traditional sense, 3,5- triazine is not usually used in the preparation of hydrogel.N, N- dimethyl allene
Amide is because its intermolecular weak hydrogen bond action is so that it has good toughening effect for material.
Content of the invention
It is an object of the invention to overcoming the deficiencies in the prior art, provide a kind of with 2- vinyl -4,6- diaminostilbene, 3,
5- triazine is the hydrogel of main body, specially 2- vinyl -4,6- diamino-1,3,5-triazines, N,N-DMAA
Copolymer (PVDT-co-PVDT), this copolymer removes the inherent character showing hydrogel, also has very strong stretch-proof and resists
Compressed capability, excellent tear resistance, CO2Stimulating responsive and shape memory function.
The purpose of the present invention is achieved by following technical proposals：
A kind of shape memory anti tear hydrogel with photosynthesis-carbon dioxide response, by 2- vinyl -4,6- diaminostilbene,
3,5- triazines, N,N-DMAA and cross-linking agent are formed by radical polymerization copolymerization, described cross-linker molecules point
Subchain two ends carry carbon-carbon double bond, the middle backbone structure for peg molecule of strand is (CH2CH2O)n.
The method preparing subject hydrogel, is carried out as steps described below：
By 2- vinyl -4,6- diaminostilbene, 3,5- triazine, N, N- DMAA, cross-linking agent and initiator are molten
Solution in a solvent, by initiator cause 2- vinyl -4,6- diamino-1,3,5-triazines, N,N-DMAA and
Unsaturated bond in cross-linker molecules, is prepared with shape memory function by Raolical polymerizable under conditions of anoxybiotic
High intensity hydrogel.
In the inventive solutions, with 2- vinyl -4,6- diamino-1,3,5-triazines and N, N- dimethyl allene
, as comonomer, with cross-linking agents comonomer, the strand two ends of cross-linker molecules are with double bond, strand for amide
Between for " oxygen-carbon-to-carbon-oxygen " singly-bound be connected framing structure (i.e. the backbone structure of peg molecule, (CH2CH2O) n), adopt
Thermal source or light source make initiator provide free radical, then cause 2- vinyl -4 by free radical, 6- diamino-1,3,5-triazines,
(such as the polyethyleneglycol diacrylate of different number-average molecular weights, Mn is 2000 for N,N-DMAA and cross-linking agent
6000) double bond in, makes three almost cause simultaneously, polyreaction occurs, in the hydrogel material of final preparation, has poly- 2-
Vinyl -4, the segment of 6- diamino-1,3,5-triazines, N,N-DMAA and three kinds of materials of cross-linking agent, wherein 2-
Vinyl -4,6- diamino-1,3,5-triazines provides the rigid nature in skeleton, and N,N-DMAA is provided in skeleton
Toughness properties, polyethylene glycol structures in cross-linking agent provide soft segment, above-mentioned three part synergism, make whole hydrogel
Material embodies high intensity, anti tear and shape memory function.
Cause 2- vinyl -4,6- diaminostilbene, 3,5- triazine, N, N- dimethyl propylene using the free radical that initiator provides
Acrylamide and cross-linking agent react.Wherein initiator can select conventional thermal initiator in field of macromolecule polymerization, such as even
Nitrogen bis-isobutyronitrile (ABIN), benzoyl peroxide (BPO), or light trigger, such as 1- [4- (2- hydroxy ethoxy)-phenylene]-
2- hydroxyl -2 ', 2 '-dimethyl ethyl ketone (Irgacure 2959), methyl vinyl ketone, Benzoinum.If selection thermal initiator,
Then need to exclude the oxygen in reaction system first with noble gases (as nitrogen, argon or helium), to avoid its inhibition
Effect, the then activity according to initiator and consumption, reaction system is heated on the initiation temperature of initiator used and protects
Hold considerable time, such as more than 1h or longer (1-5h), to promote initiator can produce enough freedom for a long time
Base, persistently Raolical polymerizable in initiation reaction system, the final hydrogel preparing the present invention there is.If selecting light-initiated
Agent, then can select transparent airtight reaction vessel, causes radical polymerization, due to light-initiated under conditions of ultraviolet light
Efficiency is higher than thermal initiation, and during because of the activity according to selected initiator and consumption adjustment irradiation time, irradiation time can be shorter than heat and draw
The heat time heating time sent out, as 20 minutes or longer (30min-1h).
In the inventive solutions it should according to 2- vinyl -4,6- diamino-1,3,5-triazines, N, N- diformazan
Base acrylamide selects initiator, the dissolubility of cross-linking agent using, and is selected to be completely dissolved above-mentioned four kinds of materials or energy
Enough solvents dissolving each other completely with above-mentioned four kinds of materials, with mix homogeneously reaction system.Due to 2- vinyl -4,6- diaminostilbene,
3,5- triazine polarized, initiator and cross-linking agent also will can be dissolved in polar solvent, therefore may be selected in organic solvent
Polar solvent, such as dimethylformamide, dimethyl acetylamide, oxolane, dimethyl sulfoxide.
In preparation scheme, monomer 2- vinyl -4,6- diamino-1,3,5-triazines, N,N-DMAA
Mass ratio is 3：(2—1).Cross-linking agent quality and two kinds of monomers (2- vinyl -4,6- diaminostilbene, 3,5- triazine, N, N- diformazans
Base acrylamide) quality sum ratio be 1：(5 20), preferably 1：(10—20).The quality of initiator is monomer and cross-linking agent
The 3 5% of gross mass.After the completion of reaction, take out copolymer from reaction vessel, remove monomer, the initiation not participating in reaction
After agent, cross-linking agent and solvent, be immersed in phosphate buffered saline(PBS) (PBS) until reach swelling equilibrium (as soak 3 days, every
12h changes a water, reaches swelling equilibrium).
A kind of high intensity PVDT-co-PDMA hydrogel that the present invention provides is with 2- vinyl -4,6- diaminostilbene 3,
5- triazine, N,N-DMAA are raw material, and copolymerization in the presence of cross-linking agent and initiator is made, and realizes 2- ethylene
Base -4,6- diaminostilbene, the intermolecular strong hydrogen bonding of 3,5- triazine and N, the weak hydrogen bond that N- DMAA is formed is worked in coordination with and is made
With, combine the property of Polyethylene Glycol simultaneously, there is very strong stretch-proof and resistance to compression, excellent tear resistance.Simultaneously
In 2- vinyl -4,6- diaminostilbene, 3,5- triazine, N, the mass ratio of N- DMAA is 3:When 2, gel for
CO2There is response and shape memory is realized based on this.This gel process for preparing is simple, product be easy to preserve for a long time and
Long-distance transport.
Brief description
Fig. 1 is the FTIR technique figure of subject hydrogel, and in figure A is PVD-71.4-10, and B is
PVD-60-10, C are the corresponding infrared absorpting light spectra of PVD-0-10 hydrogel.
Fig. 2 is the anti tear test pictorial diagram of the PVD-71.4-10 hydrogel pants type sample of subject hydrogel.
Fig. 3 is the hydrogel of the present invention in CO2The process schematic (1) of shape memory is realized under effect.
Fig. 4 is the hydrogel of the present invention in CO2The process schematic (2) of shape memory is realized under effect.
Specific embodiment
Further illustrate technical scheme with reference to specific embodiment.
By monomer 2- vinyl -4,6- diamino-1,3,5-triazines (100mg, Tokyo Kasei Kogyo), N, N- bis-
Methacrylamide (40mg, about 40 μ l, sigma), and cross-linking agent polyethyleneglycol diacrylate (14mg, number-average molecular weight
4000, sigma) it is added in 1.5ml centrifuge tube, dissolved after monomer and cross-linking agent with the dimethyl sulfoxide (DMSO) of 611 μ l, plus
Enter light trigger Irgacure2959 (4.6mg, 1- [4- (2- hydroxy ethoxy)-phenylene] -2- hydroxyl -2 ', 2 '-dimethyl second
Ketone, sigma).Monomer will be contained, in the solvent injection closed mold of cross-linking agent and initiator, mould is in ultra-violet curing case (XL-
1000UV, Spectronics Corporation) middle irradiation 40min, causes radical polymerization with abundant.Then turn on mould
Take out gel, repeatedly rinsed for several times with phosphate buffered solution, and soak 3 days, change above-mentioned phosphate-buffered every 12h molten
Liquid.Prepare gel tablet by same steps, carry out mechanical property, tear resistance and shape memory experiment.This gel sample is ordered
Entitled PVD-71.4-10.The size wherein carrying out the sample of stretching mechanical property testing is 20mm × 10mm, and thickness is 500 μm.Pressure
The sample size of contracting Mechanics Performance Testing is diameter 10mm, the cylinder of high 8mm.Tear resistance test sample size is according to 1/
2GBT 529-2008 A size (wide 7.5mm, long 50mm, notch length 20mm, thickness 0.5mm).
Change monomer 2- vinyl -4,6- diamino-1,3,5-triazines, the quality of N,N-DMAA, crosslinking
The consumption of agent polyethyleneglycol diacrylate (number-average molecular weight 4000), the consumption of fixing light trigger Irgacure 2959 is about
For the 3% of gross mass, prepare following hydrogel sample PVD-60-10, PVD-66.7-10, PVD-69-10, PVD-71.4-10,
PVD-73.2-10, PVD-75-10, PVD-71.4-5, PVD-71.4-6, PVD-71.4-7, PVD-71.4-8, PVD-71.4-9,
PVD-71.4-10, PVD-71.4-12, PVD-71.4-14, PVD-71.4-16, PVD-71.4-18, PVD-71.4-20.
Adopt 2- vinyl -4 testing the present invention with the following method, 6- diamino-1,3,5-triazines, N, N- dimethyl allene
Amide (PVDT-co-PDMA) hydrogel tear resistance：By wide 7.5mm, long 50mm, notch length 20mm, thickness 0.5mm's
Pants type sample fixture is fixed on electronic universal tester (Jinan epoch ensaying company limited), and rate of extension is 50mm/min
(as shown in Figure of description 2).Drawing divided by thickness of sample to the mean force terminating when tearing energy extends by breach.
Profit detects 2- vinyl -4 of the present invention, 6- diamino-1,3,5-triazines, N, N- dimethyl allene with the following method
The shape memory function of amide (PVDT-co-PDMA) hydrogel：A. by sheet-like hydrous gel cutting, long 95mm, wide 5mm, thickness
0.5mm, is placed on by CO2Deionized water in fully soften gel within 1 hour, gel batten is wound up as helical form manually and puts
It is placed in without CO28 hours are fixed in the deionized water processing.Then it is passed through CO toward in deionized water2, it can be found that 1 hour
Gel recovers original vertical bar state again afterwards.B. by sheet-like hydrous gel cutting, long 60mm, wide 12mm, thickness 0.5mm, it is placed on
By CO2Deionized water in fully soften gel within 1 hour, by gel batten, 1.5 times of stretching along its length is positioned over manually
Without CO28 hours are fixed in the deionized water processing.Then it is passed through CO toward in deionized water2It can be found that gel can be
Recover original state in 2 hours, refer to Figure of description 3 and 4, illustrate that photosynthesis-carbon dioxide response prepared by the hydrogel of the present invention
Application in element.
The method of testing of water content：Water content is measured by gravimetry under 20 25 degrees Celsius of room temperature.Solidifying
Glue sample immerses 0.1M PBS (c (PO4 3-)=0.1M, pH=7.4) in, until swelling equilibrium.The hydrogel of complete swelling passes through
After filter paper gently sops up the PBS solution on its surface, its mass M is surveyed by microbalance1.Then gel is put in 50 DEG C of baking oven
Drying until mass conservation is M2.Equilibrium moisture content is defined as：M1And M2Of poor quality/M1, M1And M2Represent gel respectively
Weight in wet base and dry weight, the determination of each gel water content at least needs to measure the water content of 5 samples, then takes its meansigma methods.This
The water content of invention hydrogel is advisable 70% 76%.
The hydrogel sample performance parameter of each different component preparation refers to following table.It can be seen that the PVDT-co- that the present invention provides
PDMA hydrogel has very strong stretch-proof, resistance to compression and lear energy on the whole, has under certain proportion simultaneously
CO2Response and corresponding shape memory function.
The various performance parameters of table 1 hydrogel sample
Compressive strength：During measurement, gel is compressed to machine maximum range and also cannot compress, so with answering at 90% strain
Masterpiece is intensity.
PVD-a-b：A represents monomer 2- vinyl -4,6- diaminostilbene, and 3,5- triazine accounts for all monomers (two kinds of monomer matter
Amount sum) mass fraction, b represents that cross-linking agent accounts for the mass fraction of all monomers (two kinds of monomer mass sums).
According to the scheme described in content of the invention, the technological parameter of hydrogel preparation process is adjusted, the water-setting of preparation
Glue reveals identical property with the sample base table of embodiment preparation.
Above the present invention is done with exemplary description it should illustrate, in the situation of the core without departing from the present invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent of creative work equal
Fall into protection scope of the present invention.
Claims (9)
1. a kind of shape memory anti tear hydrogel with photosynthesis-carbon dioxide response is it is characterised in that by 2- vinyl -4,6-
Diamino-1,3,5-triazines, N,N-DMAA and cross-linking agent are formed by radical polymerization copolymerization, described cross-linking agent
The strand two ends of molecule carry carbon-carbon double bond, the middle backbone structure for peg molecule of strand；Monomer 2- vinyl-
4,6- diaminostilbene, 3,5- triazine, N, the mass ratio of N- DMAA is 3：(2—1)；Cross-linking agent quality and two kinds of lists
The ratio of the quality sum of body is 1：(5 20), the quality of initiator is the 3 5% of monomer and cross-linking agent gross mass.
2. a kind of shape memory anti tear hydrogel with photosynthesis-carbon dioxide response according to claim 1, its feature
It is, described cross-linking agent is polyethyleneglycol diacrylate, Mn is 2,000 6000.
3. a kind of shape memory anti tear hydrogel with photosynthesis-carbon dioxide response according to claim 1, its feature
It is, described initiator is thermal initiator azodiisobutyronitrile or benzoyl peroxide.
4. a kind of shape memory anti tear hydrogel with photosynthesis-carbon dioxide response according to claim 1, its feature
Be, described initiator be light trigger 1- [4- (2- hydroxy ethoxy)-phenylene] -2- hydroxyl -2 ', 2 '-dimethyl ethyl ketone, first
Base vinyl ketone or Benzoinum.
5. a kind of preparation method of the shape memory anti tear hydrogel with photosynthesis-carbon dioxide response is it is characterised in that by 2-
Vinyl -4,6- diamino-1,3,5-triazines, N,N-DMAA, cross-linking agent and initiator dissolve in a solvent, lead to
Cross initiator and cause 2- vinyl -4,6- diaminostilbene, 3,5- triazine, N, on N- DMAA and cross-linker molecules
Unsaturated bond, prepares the high intensity water-setting with shape memory function under conditions of anoxybiotic by Raolical polymerizable
Glue, the strand two ends of wherein said cross-linker molecules carry carbon-carbon double bond, the middle main chain for peg molecule of strand
Structure；Monomer 2- vinyl -4,6- diaminostilbene, 3,5- triazine, N, the mass ratio of N- DMAA is 3：(2—1)；
The quality of cross-linking agent quality and two kinds of monomers and ratio be 1：(5 20), the quality of initiator is monomer and cross-linking agent gross mass
3 5%.
6. preparation method according to claim 5 it is characterised in that described cross-linking agent be polyethyleneglycol diacrylate,
Mn is 2,000 6000.
7. preparation method according to claim 5 it is characterised in that the quality of cross-linking agent quality and two kinds of monomers and ratio
For 1：(10—20).
8. preparation method according to claim 5 is it is characterised in that described initiator is thermal initiator azodiisobutyronitrile
Or benzoyl peroxide, reaction system is heated on the initiation temperature of initiator used and keeps 1-5h.
9. preparation method according to claim 5 is it is characterised in that described initiator is light trigger 1- [4- (2- hydroxyl second
Epoxide)-phenylene] -2- hydroxyl -2 ', 2 '-dimethyl ethyl ketone, methyl vinyl ketone or Benzoinum, from transparent airtight anti-
Answer container, cause radical polymerization under conditions of ultraviolet light, irradiation time is 20min or 30min 1h.
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| CN201510289511.4A CN104861112B (en) | 2015-05-29 | 2015-05-29 | A kind of have shape memory anti tear hydrogel of photosynthesis-carbon dioxide response and its preparation method and application |
| CN201610702562.XA CN106279551B (en) | 2015-05-29 | 2015-05-29 | Application of the tear-proof hydrogel in preparing photosynthesis-carbon dioxide response device |
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| CN105585653A (en) * | 2016-02-27 | 2016-05-18 | 北京化工大学 | Reversible CO2-cured photosensitive oligomer and application thereof |
| CN109822702A (en) * | 2019-02-25 | 2019-05-31 | 王金华 | A kind of high steady wood fire retardant |
| CN113637182B (en) * | 2021-08-10 | 2022-10-18 | 四川大学 | CO based on dynamic covalent bond 2 Responsive intelligent hydrogel and preparation method and application thereof |
| CN116023917B (en) * | 2021-10-26 | 2024-03-26 | 中国石油化工股份有限公司 | CO (carbon monoxide) 2 Responsive gel system, preparation method thereof and oil reservoir CO prevention 2 Leakage method |
| CN114395078B (en) * | 2021-12-27 | 2024-01-23 | 宁波捷傲创益新材料有限公司 | Humidity control material and preparation method thereof |
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|---|---|---|---|---|
| US4492776A (en) * | 1983-04-29 | 1985-01-08 | Coopervision, Inc. | Hydrogel contact lenses for permanent wear |
| CN101824123A (en) * | 2009-12-23 | 2010-09-08 | 天津大学 | High-strength temperature-sensitive hydrogel as well as preparation method and application thereof |
| CN102675562A (en) * | 2012-05-16 | 2012-09-19 | 天津大学 | Polyethylene glycol macromonomer cross-linked high-strength hydrogel and photo-initiation radical polymerization process thereof |
| CN103570872A (en) * | 2013-10-11 | 2014-02-12 | 天津大学 | High-strength photosensitive hydrogel as well as preparation method and application thereof |
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| GB0623043D0 (en) * | 2006-11-18 | 2006-12-27 | Univ Sheffield | Sensor devices |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4492776A (en) * | 1983-04-29 | 1985-01-08 | Coopervision, Inc. | Hydrogel contact lenses for permanent wear |
| CN101824123A (en) * | 2009-12-23 | 2010-09-08 | 天津大学 | High-strength temperature-sensitive hydrogel as well as preparation method and application thereof |
| CN102675562A (en) * | 2012-05-16 | 2012-09-19 | 天津大学 | Polyethylene glycol macromonomer cross-linked high-strength hydrogel and photo-initiation radical polymerization process thereof |
| CN103570872A (en) * | 2013-10-11 | 2014-02-12 | 天津大学 | High-strength photosensitive hydrogel as well as preparation method and application thereof |
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