CN108440696A - A kind of polyalcohol hydrogel and its preparation and application based on two-dimentional titanium carbide layer shape compound crosslink - Google Patents
A kind of polyalcohol hydrogel and its preparation and application based on two-dimentional titanium carbide layer shape compound crosslink Download PDFInfo
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- CN108440696A CN108440696A CN201810140608.2A CN201810140608A CN108440696A CN 108440696 A CN108440696 A CN 108440696A CN 201810140608 A CN201810140608 A CN 201810140608A CN 108440696 A CN108440696 A CN 108440696A
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 77
- 150000005846 sugar alcohols Polymers 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 31
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 7
- 150000003926 acrylamides Chemical class 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000009466 transformation Effects 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 7
- 229910052753 mercury Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052724 xenon Inorganic materials 0.000 claims description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical group CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 230000004298 light response Effects 0.000 claims description 3
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 229960002477 riboflavin Drugs 0.000 claims description 2
- 235000019192 riboflavin Nutrition 0.000 claims description 2
- 239000002151 riboflavin Substances 0.000 claims description 2
- MGMPGUIDKNPENO-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;iron Chemical compound [Fe].OC[C@H](O)[C@H]1OC(=O)C(O)=C1O MGMPGUIDKNPENO-RXSVEWSESA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000012782 phase change material Substances 0.000 claims 1
- 229920002401 polyacrylamide Polymers 0.000 claims 1
- 238000010382 chemical cross-linking Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract description 3
- 239000000499 gel Substances 0.000 description 14
- 239000000523 sample Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005286 illumination Methods 0.000 description 6
- -1 rare-earth hydroxide Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910009818 Ti3AlC2 Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- CGFPNELNAZZYQL-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;sulfuric acid Chemical compound OS(O)(=O)=O.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CGFPNELNAZZYQL-RXSVEWSESA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals 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
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
-
- 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
- C08K3/10—Metal compounds
- C08K3/14—Carbides
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Medicinal Preparation (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention belongs to organic/inorganic nano composite hydrogel fields, a kind of preparation method of the polyalcohol hydrogel based on two-dimentional titanium carbide layer shape compound crosslink are specifically disclosed, with Ti3C2Nanometer sheet is that crosslinking agent, acrylic compounds and/or acrylamides are monomer, carry out polymerisation to get.The invention also discloses polyalcohol hydrogel and the polyalcohol hydrogels made from the use preparation method as the application in temperature sensitive phase transformation and/or near-infrared optical-thermal conversion material.Preparation method of the present invention, the Ti3C2Nanometer sheet participates in polymerisation and adulterates in situ in obtained polymer network structure by way of physics and chemical crosslinking, can not only assign polyalcohol hydrogel new photoelectric characteristic, moreover it is possible to assign excellent mechanical property, such as self-healing performance, high tenacity etc..
Description
Technical field
The present invention relates to a kind of temperature sensitive polymer hydrogel based on two-dimentional titanium carbide layer shape compound crosslink and preparation sides
Method and application belong to organic/inorganic nano composite hydrogel field.
Background technology
Organic/inorganic nano composite hydrogel generally refers to inorganic nanoparticles and is dispersed in organic polymer composition
In cross-linked network, it can not only assign polyalcohol hydrogel new photoelectric characteristic, moreover it is possible to assign excellent mechanical property, such as self-healing
Performance, high tenacity etc. are closed, it is especially beneficial for the application for expanding hydrogel.The inorganic nano that the field is widely studied at present
Grain includes nanoclay (lithium diatomaceous earth etc.), graphene oxide, stratiform rare-earth hydroxide, C3N4Deng.
Existing composite hydrogel is generally required to be prepared by the way that the chemical crosslinking agent method containing multiple double bond is additionally added, and is commonly used
Chemical cross-linking agent there is N, N '-methylene diacrylamides, the poor biocompatibility of this crosslinking agent to limit composite hydrogel
Extensive use.
Two-dimentional titanium carbide layer shape compound is a kind of novel stratified nano materials, belong to two-dimentional transition metal carbide or
A member of carbonitride (MXene) has the two-dimensional structure metallic conductivity of similar graphene and excellent chemical property etc.,
It is all to enhance based composites etc. in energy storage, catalysis, absorption, photo-thermal/optical dynamic therapy of tumour, sensor and new polymers
It is multi-field to show good application prospect { Journal of Inorganic Materials 2017,32 (06), 561-570 }.
Ti3C2It is that the MXene materials of current most study yet there are no with Ti in the prior art3C2It is poly- for crosslinking agent synthesis
Close the research report of object hydrogel.
Invention content
The technical issues of to solve chemical cross-linking agent poor biocompatibility existing for existing polyalcohol hydrogel preparation process,
The present invention provides a kind of preparation methods of the polyalcohol hydrogel based on two-dimentional titanium carbide layer shape compound crosslink, it is desirable to provide
The good new crosslinking agent of polyalcohol hydrogel biocompatibility.
Second purpose of the invention is, it is obtained based on two-dimentional titanium carbide layer shape chemical combination to provide a kind of preparation method
The crosslinked polyalcohol hydrogel of object (present invention is also referred to as hydrogel).
Third purpose of the present invention is, provides a kind of application of obtained polyalcohol hydrogel as temperature sensing material.
A kind of preparation method of the polyalcohol hydrogel based on two-dimentional titanium carbide layer shape compound crosslink, with Ti3C2Nanometer sheet
Be monomer for crosslinking agent, acrylic compounds and/or acrylamides, carry out polymerisation to get.
Preparation method of the present invention, originally with Ti3C2Nanometer sheet is crosslinking agent, is acrylamide using its design feature
The polymerization of class compound provides crosslink sites, and then the polyalcohol hydrogel is made.Preparation method of the present invention, it is described
Ti3C2Nanometer sheet participates in polymerisation, by way of physics and chemical crosslinking, the polymerization adulterating and be bonded in situ
In object network structure, compared to common physical mixed, it is special that the method for the present invention can not only assign the new photoelectricity of polyalcohol hydrogel
Property, moreover it is possible to assign excellent mechanical property, such as self-healing performance, high tenacity etc..
Temperature sensing polymer hydrogel preparation method of the present invention is simple, and building-up process contains multiple double bond without using other
Chemical cross-linking agent, Ti3C2Nanometer sheet can play crosslinked action under a variety of polymerizing conditions.
Preferably, the Ti3C2Nanometer sheet has both surface hydrophilicity hydroxyl while being with two-dimensional slice layer structure
Base.Using the structure, the Ti of group properties3C2Nanometer sheet is more conducive to monomer being cross-linked with each other on its surface, helps further to carry
Rise the performance of obtained polyalcohol hydrogel.
In the present invention, Ti3C2Nanometer sheet can be used existing method and be made.
Preferably, the Ti3C2Nanometer sheet can be by Ti3YC2It removes to obtain through acid etching, alkali；The Y is Si or Al.
By research, using the preferred preparation method, its performance as crosslinking agent is more conducively promoted, contributes to obtained have excellent performance
Polyalcohol hydrogel.
Preferably, the acid that acid corrosion process uses is HF.
Preferably, the alkali that alkali stripping process uses is alkali metal hydroxide or organic alkali, alkali metal hydroxide
Preferably sodium hydroxide and/or potassium hydroxide；Organic alkali is preferably tetramethyl oxyammonia.
Still more preferably, Ti3C2The preparation process of nanometer sheet is, strong acid HF excessive first is by Ti3AlC2Nanoscale twins
Between Al etchings remove, then with highly basic by Ti3C2Big lamella is removed into, the supernatant that last ultrasound obtains is Ti3C2Nanometer
Piece.
Preparation method of the present invention, the acrylamides are in structural compounds described in formula 1
At least one；The acrylic compounds are at least one of structural compounds described in formula 2：
R1~R3It is H, C alone1~C6Alkyl.
The study found that R1~R3The main performance for influencing material application aspect obtained of group selection.By not isoplastic
It introduces, the different application performance of the polyalcohol hydrogel assigned.
Preferably, the R1、R3For H, the R2For C1~C6Alkyl.The C1~C6Alkyl be carbon number
For 1~6 groups such as straight chain or branched group, such as methyl, ethyl, isopropyl.The study found that 1 chemical combination of preferred formula
Object monomer uses Ti of the present invention3C2The polymer that nanometer sheet is crosslinked has good temperature sensitive effect.
Further preferably, the R1、R3For H, the R2For isopropyl.
In the present invention, using Ti3C2Nanometer sheet is as crosslinking agent, and the acrylamides are as monomer, poly-
It closes and is polymerize under medium.Preferably, the polymerisation medium is the solution of water or predominantly water.
In the present invention, the aqueous solution comprising crosslinking agent, monomer is polymerize, obtains the polyalcohol hydrogel.
Preferably, according to the material classification characteristic in the starting soln of polymerisation, polymerisation can have following three
Kind mode：
Mode 1：Polymerisation is carried out under ultraviolet lighting.Under ultraviolet irradiation, the monomer is in the crosslinking agent
Conduct under cross-linked polymeric, obtain the polyalcohol hydrogel.
In mode 1：Ultraviolet lighting light source is provided by mercury lamp, power be 100~1000W, ultraviolet lighting time 10min~
5h.5~30wt% of monomer concentration of polymerisation starting soln.Crosslinking agent and monomer weight ratio 0.01~0.50；Preferably
0.08~0.2.
Mode 2 (visible light+radical initiator)：Radical initiator is added, and carries out polymerisation under visible light.
That is to say, using comprising crosslinking agent, radical initiator, monomer aqueous solution as polymerization starting soln, it is poly- through visible light exposure
It closes.
In mode 2：Visible light source is provided by xenon lamp, and power is 100~1000W, light application time 10min~5h.It is poly-
Close 5~30wt% of monomer concentration of reaction starting soln.Crosslinking agent and monomer weight ratio 0.01~0.50；Preferably 0.08~
0.2.Initiator and monomer mole ratio 0.005~0.5；Preferably 0.01~0.03.
Mode 3 (radical initiator+catalyst)：Radical initiator is added, and is polymerize under catalyst
Reaction.It that is to say, the aqueous solution comprising crosslinking agent, radical initiator, monomer, catalyst is carried out as polymerization starting soln
Polymerization.
In mode 3：5~30wt% of monomer concentration of polymerisation starting soln.Crosslinking agent and monomer weight ratio 0.01~
0.50.Initiator and monomer mole ratio 0.005~0.5；Preferably 0.01~0.03.Initiator and catalyst molar ratio 0.05~
2.5；Preferably 0.2~0.3.
Preferably, in mode 2 and 3, the radical initiator is persulfate, hydrogen peroxide, riboflavin alone
At least one of；Preferably ammonium persulfate.
Preferably, in mode 3, the catalyst is n,N,N',N'-tetramethylethylenediamine (TEMED), 3- dimethylamine
Propionitrile, 3- dimethylamine propionitrile sulphite, at least one of ferric sulfate-ascorbic acid.
Preferably, polymeric reaction temperature is 0~95 DEG C；Further preferably room temperature, the room temperature is, for example, 15~
35℃；
The invention also includes poly- based on two-dimentional titanium carbide layer shape compound crosslink made from a kind of preparation method
Close object hydrogel.
Preferably, the polyalcohol hydrogel, and pass through the Ti3C2The polypropylene that nanometer sheet is cross-linked with each other
Amides and/or polyacrylic polymer (being obtained by monomer polymerization).
Preferably, the design feature of temperature sensing polymer hydrogel of the present invention is by Ti3C2Crosslinking obtains poly- (N-
N-isopropylacrylamide) hydrogel.
Preferably, the design feature of temperature sensing polymer hydrogel of the present invention is Ti3C2In poly- (N- isopropyls third
Acrylamide) it is predominantly chemically crosslinked in hydrogel.
The present invention also provides made from a kind of preparation method based on two-dimentional titanium carbide layer shape compound crosslink
The application of polyalcohol hydrogel, the polyalcohol hydrogel is by R1、R3For H, R2For C1~C6Alkyl (preferably isopropyl)
1 monomer of formula in the case where the crosslinking agent is used as cross-linked polymeric obtain (being directed to such polyalcohol hydrogel, the present invention is also referred to as temperature
Sensitive polymer hydrogel)；The inventors discovered that can the monomer crosslinked obtained polyalcohol hydrogel be used as temperature sensitive phase transformation
And/or near-infrared optical-thermal conversion material.
The design feature of temperature sensing polymer hydrogel of the present invention be not only have temperature sensitive transformation behavior, and
And there is near infrared light hot-cast socket property, it can quick response property near infrared light and temperature.
Polyalcohol hydrogel produced by the present invention has good self-healing property, under 400% effects of strain, storage
Modulus G ' significantly declines shows that gel is destroyed (from about 1930Pa to 30Pa), and when strain is 1%, system immediately occurs again
Gelation, modulus is restored to original level (about 1910Pa), and this process can be recycled repeatedly, illustrates that the hydrogel has
Extraordinary self-healing property.
Further preferably, in the application, temperature sensitive phase that the polyalcohol hydrogel is responded as near infrared light
Become material.
Before near infrared light, sample bottle inner gel is transparent and is in light yellow (room temperature is 15 DEG C), and closely red in 808nm
Outer light is with 2W/cm2After power illumination 90s, sample solution is brought rapidly up to 25 DEG C, and gel becomes opaque, light transmittance variation ten
Clearly demarcated aobvious, after irradiating 5min, sample temperature increases 32 DEG C, illustrates the quick near infrared light thermo-responsive of polymer gel
Matter.
According to the light transmittance variation of hydrogel under different temperatures, temperature sensing polymer hydrogel of the present invention can be used for intelligence
The fields such as energy window, temperature sensing intelligent device or infrared anti-false.
The Thermo-sensitive water near infrared light response based on two-dimentional titanium carbide layer shape compound crosslink that the present invention develops
Gel has widened the range of choice of temperature-sensitive hydrogel crosslinking agent and the preparation method universality rule of such hydrogel.This
In the implementation of the invention application field new by temperature-sensitive hydrogel is expanded, such as application in temperature sensing intelligent device, water
The near infrared light response property of gel can assign the sensitive regulation and control in its time and space.
Compared with prior art, the beneficial effects of the present invention are：
(1) Ti of the present invention3C2Crosslinking agent is nontoxic, good biocompatibility；
(2) hydrogel preparation method simple possible of the present invention is suitable for a variety of reaction conditions, is suitable for industrializing
Production；
(3) temperature-sensitive hydrogel that the present invention designs not only has temperature sensitive transformation behavior, but also has near-infrared
Photothermal conversion property, near infrared light and temperature can quick response property, therefore the use demand of bigger can be met.
Description of the drawings
Temperature-sensitive hydrogel prepared by Fig. 1 embodiments 2-4
The thixotropy of 2 temperature sensing polymer hydrogel of Fig. 2 embodiments
The self-healing of 2 temperature sensing polymer hydrogel of Fig. 3 embodiments
2 temperature sensing polymer hydrogel near infrared light hot-cast socket property figure of Fig. 4 embodiments
Specific implementation mode
Following embodiment is intended to illustrate invention rather than limitation of the invention further.
Embodiment 1：Ti3C2The preparation of nanometer sheet
By 1-2g Ti3AlC2It is dispersed in 40% hydrofluoric acid solution, stirs stripping reaction at room temperature 3 days,
10min is centrifuged under 10000rpm and takes precipitation, and it is about 5~6 then to be washed repeatedly with deionized water to pH；Then put the precipitate in
After reacting 48h again in 25% tetramethyl oxyammonia (TMAOH) aqueous solution, detached by centrifuging 15min at 3500rpm,
After taking precipitation and deaerated water to mix ultrasound for 24 hours in 1: 300 ratio, 5000rpm centrifugations 30min takes supernatant to obtain Ti3C2Nanometer
Piece.
Embodiment 2：It is ultraviolet it is light-initiated under the temperature sensitive polymer hydrogel based on two-dimentional titanium carbide layer shape compound crosslink
N-isopropyl acrylamide monomer is taken to be dissolved in 1mL Ti3C2In (1.6wt%) nanometer sheet (embodiment 1 is made), obtain
It polymerize starting soln, wherein the concentration of monomer is respectively 8wt%, 15wt%, 20wt%；It will obtain starting soln drum nitrogen
30min deoxygenations；At room temperature, the solution after deoxygenation polymerize under mercury lamp (λ ＞ 260nm) illumination of 500W, polymerization time 60min
The temperature sensing polymer hydrogel of two-dimentional titanium carbide layer shape compound crosslink can be arrived.Obtained product photo is shown in that Fig. 1 (is labeled as mercury
The part of lamp).
When strain is in 0~10% range, storage modulus G ' is basically unchanged and is far longer than loss modulus polymer gel
G " shows as solid gel property (Fig. 2).
Polyalcohol hydrogel produced by the present invention has good self-healing property, under 400% effects of strain, storage
Modulus G ' significantly declines shows that gel is destroyed (from about 1930Pa to 30Pa), and when strain is 1%, system immediately occurs again
Gelation, modulus is restored to original level (about 1910Pa), and this process can be recycled repeatedly, illustrates that the hydrogel has
Extraordinary self-healing property (Fig. 3).
Before near infrared light, sample bottle inner gel is transparent and is in light yellow (room temperature is 15 DEG C), and closely red in 808nm
Outer light is with 2W/cm2After power illumination 90s, sample solution is brought rapidly up to 25 DEG C, and gel becomes opaque, light transmittance variation ten
Clearly demarcated aobvious, after irradiating 5min, sample temperature increases 32 DEG C, illustrates the quick near infrared light thermal response property of polymer gel
(Fig. 4 illustrations).
Embodiment 3：It can be seen that the temperature sensitive polymer hydrogel based on two-dimentional titanium carbide layer shape compound crosslink under light-initiated
N-isopropyl acrylamide monomer is taken to be dissolved in 1mL Ti3C2In (1.6wt%) nanometer sheet (embodiment 1 is made), obtain
It polymerize starting soln, wherein the concentration of monomer is respectively 8wt%, 15wt%, 20wt%；Initiator ammonium sulfate (APS is added；Draw
Hair agent and monomer mole ratio be respectively 0.030,0.015,0.010), solution drum nitrogen 30min deoxygenations will be obtained；Room temperature, deoxygenation
Solution afterwards polymerize under xenon lamp (λ ＞ 420nm) illumination of certain power, and polymerization time, which is 60min, can arrive two-dimentional titanium carbide layer
The temperature sensing polymer hydrogel of shape compound crosslink.Obtained product photo is shown in Fig. 1 (part for being labeled as xenon lamp).
Temperature sensitive polymer hydrogel based on two-dimentional titanium carbide layer shape compound crosslink under 4. non-illumination of embodiment
N-isopropyl acrylamide monomer is taken to be dissolved in 1mL Ti3C2In (1.6wt%) nanometer sheet (embodiment 1 is made), obtain
It polymerize starting soln, wherein the concentration of monomer is respectively 8wt%, 15wt%, 20wt%；Initiator ammonium sulfate (APS is added；Draw
Hair agent and monomer mole ratio be respectively 0.030,0.015,0.010) and tetramethylethylenediamine (TEMED；Catalyst and monomer molar
Than being respectively 0.10,0.05,0.035；5min is reacted at room temperature, and the Thermo-sensitive that can arrive two-dimentional titanium carbide layer shape compound crosslink is poly-
Close object hydrogel.Obtained product photo is shown in Fig. 1 (being labeled as unglazed part)
Comparative example 1：Without Ti3C2The polymerization of the monomer solution of nanometer sheet
It is compared with embodiment 1, difference lies in be dissolved in water n-isopropyl acrylamide monomer, obtaining monomer concentration is
The starting soln of 15wt%.Obtained product photo is shown in described in Fig. 1, is free of Ti3C2The monomer solution of nanometer sheet, in other reactions
When condition is identical, the solution viscosity in sample bottle is basically unchanged, be inverted sample bottle, monomer solution can flow backwards (Fig. 1 be labeled as mercury
The 1st lamp, xenon lamp, the left number in unglazed part sample).And contain Ti3C2The monomer solution of nanometer sheet, in other reaction condition phases
Meanwhile the solution viscosity in sample bottle becomes very big, sample do not occur to flow backwards (Fig. 1 shows as gel state, Fig. 1 labeled as mercury lamp,
The 3rd xenon lamp, the left number in unglazed part sample).Illustrate a bit, under illumination condition, when required monomer concentration is relatively low
(8wt%), sample also show as gel state (Fig. 1 is labeled as mercury lamp, the 2nd sample of the left number in part of xenon lamp).
Embodiment 5
It compares, differs only in embodiment 2, polypropylene can be equally prepared for acrylamide in the monomer used
Amide hydrogel.
Embodiment 6
It compares, differs only in embodiment 2, polyacrylic acid can be equally prepared for acrylic acid in the monomer used
Hydrogel.
Present invention research it has also been found that, the Ti that will be obtained3C2The polymer that nanometer sheet is synthesized with by 1 method of comparative example carries out object
Reason mixing, that is to say, Ti3C2Nanometer sheet is not involved in being cross-linked in situ for polymer, and the polymer form of acquisition is similar with comparative example,
And properties are significantly worse than hydrogel produced by the present invention.
Claims (10)
1. a kind of preparation method of the polyalcohol hydrogel based on two-dimentional titanium carbide layer shape compound crosslink, which is characterized in that with
Ti3C2Nanometer sheet is that crosslinking agent, acrylic compounds and/or acrylamides are monomer, carries out polymerisation, i.e.,
.
2. the preparation method of the polyalcohol hydrogel as described in claim 1 based on two-dimentional titanium carbide layer shape compound crosslink,
It is characterized in that, the Ti3C2The surface of nanometer sheet has hydroxyl.
3. the preparation method of the polyalcohol hydrogel as described in claim 1 based on two-dimentional titanium carbide layer shape compound crosslink,
It is characterized in that, the Ti3C2Nanometer sheet is by Ti3YC2It removes to obtain through acid etching, alkali；The Y is Si or Al.
4. the preparation method of the polyalcohol hydrogel as claimed in claim 3 based on two-dimentional titanium carbide layer shape compound crosslink,
It is characterized in that, the acid that acid corrosion process uses is HF.
5. such as polyalcohol hydrogel of the Claims 1 to 4 any one of them based on two-dimentional titanium carbide layer shape compound crosslink
Preparation method, which is characterized in that the acrylamides are at least one in structural compounds described in formula 1
Kind；The acrylic compounds are at least one of structural compounds described in formula 2：
R1~R3It is H, C alone1~C6Alkyl.
6. the preparation method of the polyalcohol hydrogel as claimed in claim 5 based on two-dimentional titanium carbide layer shape compound crosslink,
It is characterized in that, the R1、R3For H, the R2For C1~C6Alkyl；
Further preferably, the R1、R3For H, the R2For isopropyl.
7. such as the preparation side of the polyalcohol hydrogel described in claim 5 or 6 based on two-dimentional titanium carbide layer shape compound crosslink
Method, which is characterized in that polymerisation uses any one in following three kinds of modes：
Mode 1：Polymerisation is carried out under ultraviolet lighting：
Mode 2：Radical initiator is added, and carries out polymerisation under visible light：
Mode 3：Radical initiator is added, and carries out polymerisation under catalyst：
The radical initiator is at least one of persulfate, hydrogen peroxide, riboflavin；Preferably ammonium persulfate；
The catalyst is n,N,N',N'-tetramethylethylenediamine, 3- dimethylamine propionitrile, 3- dimethylamine propionitrile sulphite, sulphur
At least one of sour iron-ascorbic acid；
Polymeric reaction temperature is 0~95 DEG C.
8. the preparation method of the polyalcohol hydrogel as claimed in claim 7 based on two-dimentional titanium carbide layer shape compound crosslink,
It is characterized in that,
In mode 1：Ultraviolet lighting light source is provided by mercury lamp, power be 100~1000W, ultraviolet lighting time 10min~5h,
5~30wt% of monomer concentration of polymerisation starting soln, crosslinking agent and monomer weight ratio 0.01~0.50；
In mode 2：Visible light source is provided by xenon lamp, and power is 100~1000W, light application time 10min~5h, and polymerization is anti-
Answer 5~30wt% of monomer concentration of starting soln, crosslinking agent and monomer weight ratio 0.01~0.50, initiator and monomer mole ratio
0.005~0.5；
In mode 3：5~30wt% of monomer concentration of polymerisation starting soln, crosslinking agent and monomer weight ratio 0.01~0.50,
Initiator and monomer mole ratio 0.005~0.5, initiator and catalyst molar ratio 0.05~2.5.
9. a kind of claim 1~8 any one of them preparation method is obtained based on two-dimentional titanium carbide layer shape compound crosslink
Polyalcohol hydrogel；Including Ti3C2Nanometer sheet, and pass through the Ti3C2The polyacrylamide that nanometer sheet is cross-linked with each other
And/or polyacrylic polymer.
10. a kind of claim 6~8 any one of them preparation method is obtained based on two-dimentional titanium carbide layer shape compound crosslink
Polyalcohol hydrogel application, which is characterized in that be used as temperature sensitive phase transformation and/or near-infrared optical-thermal conversion material；
Preferably as the temperature sensitive phase-change material of near infrared light response；
Further preferably, it is used for the preparation field of intelligent window, temperature sensing intelligent device or infrared anti-false.
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