CN104861112A - Shape memory anti-tear hydrogel with carbon dioxide responsibility, as well as preparation method and application of shape memory anti-tear hydrogel - Google Patents
Shape memory anti-tear hydrogel with carbon dioxide responsibility, as well as preparation method and application of shape memory anti-tear hydrogel Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title abstract 8
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 18
- ZXLYUNPVVODNRE-UHFFFAOYSA-N 6-ethenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=C)=N1 ZXLYUNPVVODNRE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000006386 memory function Effects 0.000 claims abstract description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 claims description 17
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000004971 Cross linker Substances 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 125000004386 diacrylate group Chemical group 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- 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 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 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
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 2
- 230000006835 compression Effects 0.000 abstract description 4
- 238000007906 compression Methods 0.000 abstract description 4
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 abstract 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 abstract 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 230000000638 stimulation Effects 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003254 radicals Chemical class 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000000243 solution Substances 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 101000663001 Mus musculus TNFAIP3-interacting protein 1 Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 108091027981 Response element Proteins 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
- 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
- 239000002612 dispersion medium Substances 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
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- 125000003827 glycol group Chemical group 0.000 description 1
- 238000000892 gravimetry Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003960 organic solvent Substances 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
- -1 polyoxyethylene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009736 wetting Methods 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
- 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
Abstract
The invention discloses a shape memory anti-tear hydrogel with carbon dioxide responsibility and a preparation method. The preparation method comprises the following steps: taking 2-vinyl-4,6-diamino-1,3,5-triazine and N,N-dimethyl acrylamide as monomers, taking polyethylene glycol acrylate as a cross-linking agent, and preparing the shape memory anti-tear hydrogel through copolymerization under an initiator, wherein the mass ratio of 2-vinyl-4,6-diamino-1,3,5-triazine to N,N-dimethyl acrylamide is (3:2)to(3:1). The hydrogel has strong stretch resistance, compression resistance, tearing resistance and notching resistance, meanwhile, the hydrogel has stimulative-responsibility on CO2, and has a shape memory function under the stimulation of CO2. The preparation method is simple, and the shape memory anti-tear hydrogel is easy to store for a long time and transport for a long distance.
Description
Technical field
The present invention relates to a kind of hydrogel and preparation method, more particularly, relate to a kind of 2-vinyl-4,6-diamino-1,3,5-triazines, N, N-DMAA multipolymer (PVDT-co-PDMA) hydrogel and preparation method thereof, has high strength, anti tear, CO
2responsiveness and shape memory function.
Background technology
Hydrogel take water as dispersion medium, wetting ability and water-fast and can absorb the macromolecule polymer material that large quantity of moisture (usual water content is greater than 50% of total mass) has crosslinking structure.Environment sensitive type hydrogel or intelligent aqueous gel capable refer to (as pH value, temperature, light, electricity, magnetic field, biomolecules etc.) its volume and mechanical property when the change being subject to external environment can there is corresponding change.Intelligent aqueous gel capable is used for biological medicine material, soft wet driving mechanism and pharmaceutical carrier by exploitation widely.But the mechanical property of traditional environment sensitive type hydrogel is very weak very crisp, and the tearing energy of typical hydrogels is 10
-1-100J/m
2.Although recently have remarkable progress for acquisition high strength intelligent aqueous gel capable, obtaining the environment sensitive type hydrogel with anti tear is still a challenge.
In order to improve the lear energy of gel, by research, scientists thinks that obtaining anti tear hydrogel must meet two conditions: 1. when gel is subject to tearing effect, and needing can the mechanism of energy dispersive; 2. gel is when being out of shape, and needs the ability keeping original configuration.Can draw a kind of method improving the tearing toughness of gel by this, sacrifice network or reversible weak physical cross-linked network namely by introducing easy fracture in gel network improve the lear energy of gel.2-vinyl-4,6-diamino-1,3,5-triazines (VDT), due in the strong molecule in its polymer molecular chain between amino and intermolecular hydrogen bond action make it be used widely in highstrenghtpiston.But strong hydrogen bond action makes water molecules be difficult to enter in crosslinked pure poly-2-vinyl-4,6-diamino-1,3,5-triazines network, thus the water content of gel is extremely low.So 2-vinyl-4,6-diamino-1,3,5-triazines is not usually used in the preparation of hydrogel in traditional sense.N,N-DMAA, due to its intermolecular weak hydrogen bond action, makes it have good toughening effect for material.
Summary of the invention
The object of the invention is to overcome 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, is specially 2-vinyl-4,6-diaminostilbene, 3,5-triazine, N,N-DMAA multipolymer (PVDT-co-PVDT), this multipolymer is except the natural characteristics showing hydrogel, also there is very strong stretch-proof and resistance to compression, excellent tear strength, CO
2stimulating responsive and shape memory function.
Object 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-triazine, N, N-DMAA and linking agent are formed by radical polymerization copolymerization, and the molecular chain two ends of described cross-linker molecules are with the backbone structure i.e. (CH in the middle of carbon-carbon double bond, molecular chain being peg molecule
2cH
2o) n.
Prepare the method for subject hydrogel, carry out according to following step:
By 2-vinyl-4,6-diaminostilbene, 3,5-triazine, N,N-DMAA, linking agent and initiator dissolve in a solvent, 2-vinyl-4 is caused by initiator, 6-diamino-1,3,5-triazines, N, unsaturated link(age) in N-DMAA and cross-linker molecules, prepares the high intensity hydrogel with shape memory function under the condition of anoxybiotic by Raolical polymerizable.
In the inventive solutions, with 2-vinyl-4, 6-diaminostilbene, 3, 5-triazine and N, N-DMAA is as comonomer, with cross-linking agents comonomer, the molecular chain two ends of cross-linker molecules are with double bond, it is skeleton structure (the i.e. backbone structure of peg molecule that " oxygen-carbon-to-carbon-oxygen " singly-bound is connected in the middle of molecular chain, (CH2CH2O) n), thermal source or light source is adopted to make initiator provide free radical, 2-vinyl-4 is caused again by free radical, 6-diaminostilbene, 3, 5-triazine, N, N-DMAA and linking agent are (as the polyethyleneglycol diacrylate of different number-average molecular weight, Mn is 2000-6000) in double bond, three is almost caused simultaneously, polymerization reaction take place, in the hydrogel material of final preparation, there is poly-2-vinyl-4, 6-diaminostilbene, 3, 5-triazine, N, the segment of N-DMAA and linking agent three kinds of materials, wherein 2-vinyl-4, 6-diaminostilbene, 3, 5-triazine provides the rigid nature in skeleton, N, N-DMAA provides the toughness properties in skeleton, polyethylene glycol structures in linking agent provides soft segment, above-mentioned three part synergies, whole hydrogel material is made to embody high strength, anti tear and shape memory function.
The free radical utilizing initiator to provide causes 2-vinyl-4,6-diamino-1,3,5-triazines, N,N-DMAA and linking agent and reacts.Wherein initiator can select thermal initiator conventional in field of macromolecule polymerization, as Diisopropyl azodicarboxylate (ABIN), benzoyl peroxide (BPO), or light trigger, as 1-[4-(2-hydroxy ethoxy)-phenylene]-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone (Irgacure 2959), methyl vinyl ketone, st-yrax.If selection thermal initiator, then need first to utilize rare gas element (as nitrogen, argon gas or helium) to get rid of oxygen in reaction system, to avoid its inhibition, then according to activity and the consumption of initiator, keep considerable time on kick off temperature reaction system being heated to initiator used, as more than 1h or longer (1-5h), abundant free radical can be produced for a long time to impel initiator, initiation reaction system continues Raolical polymerizable occurs, final preparation hydrogel of the present invention.If selective light initiator, then can select transparent airtight reaction vessel, radical polymerization is caused under the condition of UV-irradiation, because light-initiated efficiency is higher than thermal initiation, because of during according to the activity of selected initiator and consumption adjustment irradiation time, irradiation time can be shorter than the heat-up time of thermal initiation, as 20 minutes or longer (30min-1h).
In the inventive solutions, should according to 2-vinyl-4,6-diaminostilbene, 3,5-triazine, N, the initiator of N-DMAA choice for use, the solvability of linking agent, select the solvent that can dissolve above-mentioned four kinds of materials completely or can dissolve each other completely with above-mentioned four kinds of materials, to mix reaction system.Due to 2-vinyl-4,6-diaminostilbene, 3,5-triazine has polarity, initiator and linking agent are also wanted can be dissolved in polar solvent, therefore can select the polar solvent in organic solvent, as dimethyl formamide, N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO).
In preparation scheme, the mass ratio of monomer 2-vinyl-4,6-diamino-1,3,5-triazines, N,N-DMAA is 3:(2-1).The quality of linking agent quality and two kinds of monomers (2-vinyl-4,6-diamino-1,3,5-triazines, N,N-DMAA) and ratio be 1:(5-20), preferred 1:(10-20).The quality of initiator is 3-5% of monomer and linking agent total mass.After the completion of reaction, multipolymer is taken out from reaction vessel, after removing monomer, initiator, linking agent and the solvent not participating in reaction, be immersed in phosphate buffered saline(PBS) (PBS) until reach swelling equilibrium (as soaked 3 days, change a water every 12h, reach swelling equilibrium).
A kind of high strength PVDT-co-PDMA hydrogel provided by the invention is with 2-vinyl-4,6-diaminostilbene, 3,5-triazine, N,N-DMAA are raw material, and under linking agent and initiator exist, copolymerization is made, realize 2-vinyl-4, the intermolecular strong hydrogen bonding of 6-diamino-1,3,5-triazines and N, the weak hydrogen bond synergy that N-DMAA is formed, combine the character of polyoxyethylene glycol simultaneously, there is very strong stretch-proof and resistance to compression, excellent tear strength.Simultaneously when the mass ratio of 2-vinyl-4,6-diamino-1,3,5-triazines, N,N-DMAA is 3:2, gel is for CO
2there is responsiveness and realize shape memory based on this.This gel process for preparing is simple, and product is easy to long-term and preserves and long-distance transport.
Accompanying drawing explanation
Fig. 1 is the FTIR technique figure of subject hydrogel, and in figure, A is PVD-71.4-10, B be PVD-60-10, C is the infrared absorpting light spectra that PVD-0-10 hydrogel is corresponding.
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 that hydrogel of the present invention is at CO
2the process schematic (1) of shape memory is realized under effect.
Fig. 4 is that hydrogel of the present invention is at CO
2the process schematic (2) of shape memory is realized under effect.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with specific embodiment.
By monomer 2-vinyl-4, 6-diaminostilbene, 3, 5-triazine (100mg, Tokyo Kasei Kogyo), N, N-DMAA (40mg, about 40 μ l, sigma), with linking agent polyethyleneglycol diacrylate (14mg, number-average molecular weight 4000, sigma) join in 1.5ml centrifuge tube, after dimethyl sulfoxide (DMSO) (DMSO) dissolved monomer of 611 μ l and linking agent, add light trigger Irgacure2959 (4.6mg, 1-[4-(2-hydroxy ethoxy)-phenylene]-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone, sigma).Will containing monomer, the solvent of linking agent and initiator injects closed mold, and mould irradiates 40min in ultra-violet curing case (XL-1000UV, Spectronics Corporation), fully to cause radical polymerization.Open mould subsequently and take out gel, repeatedly rinse for several times with phosphate buffer soln, and soak 3 days, change above-mentioned phosphate buffer soln every 12h.Prepare gel flap by same steps, carry out the experiment of mechanical property, tear resistance and shape memory.This gel sample called after PVD-71.4-10.The sample wherein carrying out stretching mechanical property testing is of a size of 20mm × 10mm, and thick is 500 μm.The sample size of Compressive Mechanical Properties test is the cylinder of diameter 10mm, 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-diaminostilbene, 3, 5-triazine, N, the quality of N-DMAA, the consumption of linking agent polyethyleneglycol diacrylate (number-average molecular weight 4000), the consumption of fixed light initiator Irgacure 2959 is about 3% of total mass, be prepared as follows 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 and test 2-vinyl-4 of the present invention with the following method, 6-diaminostilbene, 3,5-triazine, N,N-DMAA (PVDT-co-PDMA) hydrogel tear resistance: by wide 7.5mm, long 50mm, the pants type sample fixture of notch length 20mm, thickness 0.5mm 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 terminated when tearing energy is expanded by breach.
Profit detects 2-vinyl-4,6-diamino-1,3,5-triazines of the present invention with the following method, the shape memory function of N,N-DMAA (PVDT-co-PDMA) hydrogel: a. by sheet-like hydrous gel slitting, long 95mm, wide 5mm, thickness 0.5mm, is placed on and passes through CO
2deionized water in 1 hour fully softening gel, gel batten is manually wound up as spirrillum and is positioned over without CO
28 hours are fixed in the deionized water of process.Then in deionized water, CO is passed into
2, after can finding 1 hour, gel recovers again original vertical bar state.B. by sheet-like hydrous gel slitting, long 60mm, wide 12mm, thickness 0.5mm, is placed on and passes through CO
2deionized water in 1 hour fully softening gel, gel batten is manually stretched 1.5 times along its length and is positioned over without CO
28 hours are fixed in the deionized water of process.Then in deionized water, CO is passed into
2can find that gel can recover original state in 2 hours, refer to Figure of description 3 and 4, illustrate that the application in photosynthesis-carbon dioxide response element prepared by hydrogel of the present invention.
The testing method of water content: water content is measured by gravimetry under room temperature 20-25 degrees Celsius.Gel sample immerses 0.1M PBS (c (PO
4 3-)=0.1M, pH=7.4) in, until swelling equilibrium.The hydrogel of complete swelling sops up the PBS solution on its surface gently by filter paper after, survey its mass M by microbalance
1.Then gel puts into the baking oven oven dry of 50 DEG C until mass conservation is M
2.Equilibrium moisture content is defined as: M
1and M
2of poor quality/M
1, M
1and M
2represent weight in wet base and the dry weight of gel respectively, the determination of each gel water content at least needs the water content measuring 5 samples, then gets its mean value.The water content of subject hydrogel is advisable 70%-76%.
Hydrogel sample performance perameter prepared by each different components refers to following table.Visible PVDT-co-PDMA hydrogel provided by the invention has very strong stretch-proof, resistance to compression and lear energy on the whole, has CO under certain proportion simultaneously
2responsiveness 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 compresses, so using the stress of 90% strain place as intensity.
PVD-a-b:a represents that monomer 2-vinyl-4,6-diamino-1,3,5-triazines accounts for the massfraction of all monomers (two kinds of monomer mass sums), and b represents that linking agent accounts for the massfraction of all monomers (two kinds of monomer mass sums).
According to the scheme described in summary of the invention, adjust the processing parameter of hydrogel preparation process, sample base table prepared by hydrogel and the embodiment of preparation reveals identical character.
Above to invention has been exemplary description; should be noted that; when not departing from core of the present invention, any simple distortion, amendment or other those skilled in the art can not spend the equivalent replacement of creative work all to fall into protection scope of the present invention.
Claims (8)
1. one kind has the shape memory anti tear hydrogel of photosynthesis-carbon dioxide response, it is characterized in that, by 2-vinyl-4,6-diaminostilbene, 3,5-triazine, N,N-DMAA and linking agent are formed by radical polymerization copolymerization, and the molecular chain two ends of described cross-linker molecules are with the backbone structure in the middle of carbon-carbon double bond, molecular chain being peg molecule.
2. a kind of shape memory anti tear hydrogel with photosynthesis-carbon dioxide response according to claim 1, it is characterized in that, described linking agent is polyethyleneglycol diacrylate, and Mn is 2000-6000.
3. one kind has the preparation method of the shape memory anti tear hydrogel of photosynthesis-carbon dioxide response, it is characterized in that, by 2-vinyl-4, 6-diaminostilbene, 3, 5-triazine, N, N-DMAA, linking agent and initiator dissolve in a solvent, 2-vinyl-4 is caused by initiator, 6-diaminostilbene, 3, 5-triazine, N, unsaturated link(age) in N-DMAA and cross-linker molecules, prepared the high intensity hydrogel with shape memory function by Raolical polymerizable under the condition of anoxybiotic, the molecular chain two ends of wherein said cross-linker molecules are with carbon-carbon double bond, it is the backbone structure of peg molecule in the middle of molecular chain, the mass ratio of monomer 2-vinyl-4,6-diamino-1,3,5-triazines, N,N-DMAA is 3:(2-1), the quality of linking agent quality and two kinds of monomers and ratio be 1:(5-20), the quality of initiator is 3-5% of monomer and linking agent total mass.
4. preparation method according to claim 3, is characterized in that, described linking agent is polyethyleneglycol diacrylate, and Mn is 2000-6000.
5. preparation method according to claim 3, is characterized in that, the quality of linking agent quality and two kinds of monomers and ratio be 1:(10-20).
6. preparation method according to claim 3, is characterized in that, described initiator is thermal initiator Diisopropyl azodicarboxylate or benzoyl peroxide, keeps 1-5h on kick off temperature reaction system being heated to initiator used.
7. preparation method according to claim 3, it is characterized in that, described initiator be light trigger 1-[4-(2-hydroxy ethoxy)-phenylene]-2-hydroxyl-2 ', 2 '-dimethyl ethyl ketone, methyl vinyl ketone or st-yrax, select transparent airtight reaction vessel, under the condition of UV-irradiation, cause radical polymerization, irradiation time is 20min or 30min-1h.
8. the application in photosynthesis-carbon dioxide response device prepared by hydrogel as described in claim 1 or 2.
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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 |
| CN113637182A (en) * | 2021-08-10 | 2021-11-12 | 四川大学 | CO based on dynamic covalent bond2Responsive intelligent hydrogel and preparation method and application thereof |
| CN114395078A (en) * | 2021-12-27 | 2022-04-26 | 宁波捷傲创益新材料有限公司 | Humidity control material and preparation method thereof |
| CN116023917A (en) * | 2021-10-26 | 2023-04-28 | 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 |
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| CN116023917A (en) * | 2021-10-26 | 2023-04-28 | 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 |
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| CN114395078A (en) * | 2021-12-27 | 2022-04-26 | 宁波捷傲创益新材料有限公司 | Humidity control material and preparation method thereof |
| 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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| Publication number | Publication date |
|---|---|
| CN106279551A (en) | 2017-01-04 |
| CN104861112B (en) | 2017-03-08 |
| CN106279551B (en) | 2018-09-14 |
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