CN112079960B - Flexible hydrogel based on orthogonal photochemical reaction and preparation method thereof - Google Patents
Flexible hydrogel based on orthogonal photochemical reaction and preparation method thereof Download PDFInfo
- Publication number
- CN112079960B CN112079960B CN202010794329.5A CN202010794329A CN112079960B CN 112079960 B CN112079960 B CN 112079960B CN 202010794329 A CN202010794329 A CN 202010794329A CN 112079960 B CN112079960 B CN 112079960B
- Authority
- CN
- China
- Prior art keywords
- parts
- hydrogel
- polymerizable monomer
- initiator
- material containing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000017 hydrogel Substances 0.000 title claims abstract description 58
- 238000006552 photochemical reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000499 gel Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 25
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000013522 chelant Substances 0.000 claims abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 239000011941 photocatalyst Substances 0.000 claims abstract description 8
- VSANUNLQSRKIQA-UHFFFAOYSA-K trichlororuthenium hexahydrate Chemical compound O.O.O.O.O.O.Cl[Ru](Cl)Cl VSANUNLQSRKIQA-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001002 functional polymer Polymers 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims 1
- 239000003814 drug Substances 0.000 abstract description 3
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- MHMNJMPURVTYEJ-UHFFFAOYSA-N fluorescein-5-isothiocyanate Chemical compound O1C(=O)C2=CC(N=C=S)=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 MHMNJMPURVTYEJ-UHFFFAOYSA-N 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229920005615 natural polymer Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000000518 rheometry Methods 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- 108010022355 Fibroins Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a tough hydrogel based on orthogonal photochemical reaction and a preparation method thereof, wherein the hydrogel comprises the following components in parts by weight: 2-30 parts of macromolecular material containing phenol group, 2-30 parts of polymerizable monomer, 1-10 parts of metal ion chelate and a crosslinking agent: the addition amount of the cross-linking agent is 0.02-0.15% of the polymerizable monomer, and the initiator: the addition amount of the initiator is 0.5-5% of the total mass of the hydrogel, and the addition amount of the terpyridine ruthenium chloride hexahydrate photocatalyst is as follows: the addition amount of the terpyridyl ruthenium chloride hexahydrate photocatalyst is 0.01-0.1% of the total mass of the gel, and 60-95 parts of solvent. The invention has very important significance for promoting the application of the tough gel material in the fields of minimally invasive medicine, flexible electronics, bioelectronics, soft robots and the like.
Description
Technical Field
The invention belongs to the technical field of hydrogel, and particularly relates to a tough hydrogel based on orthogonal photochemical reaction and a preparation method thereof.
Background
A hydrogel is a functional polymeric material with a three-dimensional network structure that can absorb large amounts of water while being insoluble in water. The unique properties of excellent water absorption and retention performance, excellent biocompatibility, high permeability to small molecules and the like make the material one of soft materials with the most application value. At present, hydrogel materials have shown application prospects in a plurality of fields such as agricultural water retention, sanitary products, biological cartilages, medical treatment, drug loading, sensing, multifunctional materials and the like. However, the internal molecular structure of the traditional hydrogel is mainly a single chemical crosslinking structure, so that the hydrogel has the key problems of poor mechanical properties, fragility and the like, and the practical process of the hydrogel is greatly hindered. Therefore, the preparation of hydrogel materials with excellent mechanical properties is an important direction for the development of current hydrogel materials.
A tough hydrogel is an important branch of hydrogel materials. A plurality of physical and chemical crosslinking network structures exist in the molecular structure of the material. When external force is applied, under the synergistic effect of the multiple network structures, mechanical energy is rapidly dissipated, and then rapid propagation of cracks in the gel is effectively prevented, so that the gel is not easy to damage. It follows that tough hydrogels, while having the unique properties of traditional hydrogels, can also exhibit excellent and tunable mechanical properties. Based on the above advantages, the tough hydrogel has attracted attention in recent years in high and new technology fields such as wearable electronic devices, bioelectronic devices, implantable electronic devices, tissue engineering, protein/cell release, and the like.
The preparation method commonly used for the flexible hydrogel mainly comprises the following steps: (1) diffusing a second monomer into the first heavy rigid network, polymerizing by a heating or ultraviolet irradiation method to form a double-network gel (2), preparing an aqueous solution of a double-toughness network polymer in advance, and then forming a rigid network (3) by freezing crystallization or soaking in an ionic solution to introduce an energy dissipation structure such as a microgel or fiber gel structure into the second heavy gel network. Although these methods have shown some effectiveness in improving the mechanical properties of the gel material, they usually involve two-step or even multi-step chemical reaction processes, and the preparation process is complicated and is not favorable for the practical application of the tough gel. In recent years, a simple and efficient method of one-pot synthesis and in-situ polymerization has been used to prepare tough hydrogel materials. However, such methods, while achieving simple preparation of tough gels, still have the following problems to consider: (1) the reaction time is longer, and usually more than 1 hour is needed to complete the preparation of the whole gel; (2) the formation of gel networks is mostly dependent on long-term uv irradiation, gamma irradiation or high temperature heating; (3) the preparation process usually adopts nonselective thermal initiation and spontaneous polymerization methods, and the controllability is poor. The problems lead the tough gel material to be difficult to be used for preparing complex two-dimensional and three-dimensional microstructures with high resolution, and the biocompatibility is poor, thereby greatly limiting the application of the tough gel in the fields of biomedicine, electronic information and the like.
Therefore, the development of a novel biocompatible tough hydrogel material and the development of a simple, efficient, rapid and controllable synthesis preparation method thereof have important theoretical and practical significance for realizing patterning of tough hydrogel and expanding the application range of the tough hydrogel.
Disclosure of Invention
In order to solve the problems, the invention provides a flexible hydrogel based on orthogonal photochemical reaction and a preparation method thereof, wherein the hydrogel comprises the following components in parts by weight: 2-30 parts of macromolecular material containing phenol group, 2-30 parts of polymerizable monomer, 1-10 parts of metal ion chelate and a crosslinking agent: the addition amount of the cross-linking agent is 0.02-0.15% of the polymerizable monomer, and the initiator: the addition amount of the initiator is 0.5-5% of the total mass of the hydrogel, and the addition amount of the terpyridine ruthenium chloride hexahydrate photocatalyst is as follows: the addition amount of the terpyridyl ruthenium chloride hexahydrate photocatalyst is 0.01-0.1% of the total mass of the gel, and 60-95 parts of solvent.
A preparation method of a tough hydrogel based on orthogonal photochemical reaction is characterized by comprising the following steps:
step 1: adding 2-30 parts of phenolic group-containing monomer into 60-95 parts of solvent and continuously stirring;
step 2: after complete dissolution, respectively adding 2-30 parts of polymerizable monomer, 1-10 parts of metal ion chelate and crosslinking agent accounting for 0.02-0.15% of the mass of the polymerizable monomer, and uniformly stirring until complete dissolution;
and step 3: adding a catalyst accounting for 0.5-5% of the total mass of the hydrogel and an initiator accounting for 0.02-0.15% of the total mass of the hydrogel, and uniformly stirring until the mixture is completely dissolved to prepare a reaction solution;
and 4, step 4: the reaction solution was poured into a suitable mold, and after removing air bubbles from the solution, the blue light was passed through 15mM cm-2Irradiating for 2min to obtain the toughness hydrogel based on orthogonal photochemical reaction.
The further proposal is that the macromolecular material containing the phenolic group is a natural macromolecular material containing the phenolic group or a synthetic macromolecular material containing the phenolic group which is grafted and modified by itself.
In a further embodiment, the polymerizable monomer is a single component or a mixture of multiple polymerizable monomers or a functional polymer monomer.
In a further scheme, the initiator is a water-soluble initiator or an oil-soluble initiator.
In a further scheme, the solvent is water.
It should be noted that: the orthogonal photochemical reaction can be a plurality of chemical reactions such as phenol-based crosslinking, free radical polymerization, oxidative polymerization and the like, and different chemical reactions can be introduced through reasonable design to form different polymer network structures, so that the intelligent/functional tough hydrogel material with shape memory, self-repairing and the like can be prepared.
The invention has the beneficial effects that:
(1) the invention provides a preparation method of a tough hydrogel based on orthogonal photochemical reactions, which can simultaneously excite a plurality of chemical reaction processes without influencing each other, thereby realizing one-step construction of a multiple network structure in the gel without any post-treatment process. The preparation of the tough gel can be completed within dozens of seconds, the whole reaction process can be carried out only under the mild illumination at room temperature, the reaction condition is very mild, and the method is suitable for biological application.
(2) The preparation method of the tough hydrogel based on the orthogonal photochemical reaction has universality and universality. The dissipation mechanism and raw materials in the tough hydrogel can be freely designed according to the use requirements, so that the gel is endowed with excellent mechanical properties, mechanical toughness and other electric, magnetic and other functionalities. More importantly, even the gel material constructed by the method can still maintain a relatively high strength and toughness even in extremely harsh environments (such as acidic, alkaline or other ionic solutions).
(3) The preparation method of the controllable orthogonal photochemical reaction flexible hydrogel can be carried out at room temperature and has rapid reaction. And compared with thermal initiation, photo-initiation has good controllability. Therefore, the tough gel constructed by the method can be well suitable for various advanced manufacturing technologies (such as photoetching or 3D printing), further realizes the preparation of fine patterns and complex three-dimensional structures based on the tough gel, and has very important significance for promoting the application of tough gel materials in the fields of minimally invasive medicine, flexible electronics, bioelectronics, soft robots and the like.
Drawings
FIG. 1: synthetic mechanism (Ru (II)/S) of tough hydrogel material with multiple network structure based on orthogonal photochemical reaction2O8 2-Catalysis of (2) as an example);
FIG. 2: preparing a tough hydrogel subjected to orthogonal photochemical reaction (a), performing in-situ rheology (b), performing in-situ rheology under intermittent illumination, and preparing a large-size tough gel;
FIG. 3: a tough gel mechanical curve (a) prepared from different monomers and ions based on orthogonal photochemical reaction is a stress-strain curve; (b) stretching to a two-fold cycle curve;
FIG. 4: tough gels prepared using classical printing techniquesFine patterns and complex structures. (a) Mask method, line, ball, square, knot; (b) laser guided direct writing a grid structure. Irradiation intensity of 200mwcm-2Scanning rate of 90mms-1(ii) a (c)3D printing, namely, pyramid-shaped structures, porous frameworks, grids (5 layers) and flexible hydrogel tubes. (a) The thickness of the sample in (a) and (b) is 2 mm. (c) The scale in (1) is 1 mm.
Detailed Description
The invention will be further explained with reference to the drawings and the embodiments.
Example 1
This example provides a method for preparing a tough hydrogel based on orthogonal photochemical reaction, which includes adding sodium alginate (2.25 wt%) and gelatin (5 wt%) of a natural polymer containing a phenol group into deionized water, stirring for 2 hours, adding a polymerizable monomer acrylamide monomer (30 wt%) and a metal ion chelate EDTA-Ca (2 wt%) after completely dissolving, and stirring for 10 minutes; then bipyridine ruthenium (31.2 mu M), ammonium persulfate (131mM) and N, N-methylene bisacrylamide (0.7mM) are added and stirred uniformly in dark; then poured into a mold and vacuumed to remove air bubbles from the solution, passing through a blue light (15 mcm)-2) Irradiating for 2min to obtain the tough hydrogel with a multiple network structure.
Example 2
In addition to example 1, the natural polymer containing phenol groups used in this example was fibroin (7 wt%).
Example 3
In addition to example 1, bovine serum albumin (5 wt%) was used as the natural polymer containing a phenol group in this example.
Example 4
This example provides a method for preparing a tough hydrogel based on orthogonal photochemical reaction, in which modified sodium alginate (2.25 wt%) containing phenol groups and a metal ion chelate EDTA-Ca (2 wt%) are dissolved in deionized water and stirred for 2 hours, and after complete dissolution, a polymerizable monomer acrylamide (30 wt%) is added and stirred for 10 min; then bipyridine ruthenium (31.2 mu M), ammonium persulfate (131mM) and N, N-methylene bisacrylamide (0.7mM) are added and stirred uniformly in dark; then theThe prepolymer solution was poured into a mold, degassed of air bubbles, and passed through a blue light (15 mcm)-2) Irradiating for 2min to obtain the tough hydrogel with a multiple network structure.
Example 5
Based on example 4, the polymerizable monomer used in this example was isopropylacrylamide (30 wt%).
Example 6
Based on example 4, the polymerizable monomer used in this example was polyethylene glycol diacrylate (30 wt%).
Example 7
Based on example 4, the metal ion chelate compound used in this example was EDTA-Tb (2 wt%).
Example 8
Based on example 4, the metal ion chelate compound used in this example is EDTA-Eu (2 wt%).
The mechanism, in-situ rheology and mechanical property curves of the prepared tough gel based on orthogonal photochemical reactions of examples 4-8 are shown in the attached figures 1-3.
Example 9
On the basis of the embodiment 4, the prepared flexible hydrogel can be applied to a mask method to prepare the hydrogel with delicate patterns. The specific method comprises the following steps: the pre-polymerization solution prepared in example 4 was first applied and dropped onto a slide; placing a mask with a circle, a square and a line on the upper part of the glass slide, turning on a blue light source right above the mask, irradiating for 30 seconds, carefully washing the glass slide by deionized water, removing unreacted prepolymerization solution, and observing the appearance of the glass slide under an optical microscope.
Example 10
On the basis of the embodiment 8, the prepared flexible hydrogel can be applied to a mask method to prepare the hydrogel with delicate patterns. The specific method comprises the following steps: using the pre-polymerization solution prepared in example 8, it was poured into a plastic watch glass, a Chinese knot pattern photomask was placed on the upper side, a light source was turned on right above, irradiation was performed for 30 seconds, and then the unreacted solution was poured out and rinsed with DI water to remove the intermediate pre-polymerization solution. So as to obtain the tough gel pattern with Chinese knot shape.
Example 11
On the basis of the embodiment 4, the prepared flexible hydrogel can be applied to a mask method to prepare the hydrogel with delicate patterns. The specific method comprises the following steps: pouring the prepared pre-polymerization solution in the embodiment 4 into a watch glass, placing the watch glass in a dark room, drawing a grid pattern through SolidWorks software, designing a path of a laser light source, then placing the watch glass containing the pre-polymerization solution on a movable platform, starting the movable platform and simultaneously turning on the laser light source, wherein the scanning speed is 90mms-1. To make the grid more visible we stained with 1mg/ml Fluorescein Isothiocyanate (FITC) in DMSO, soaked for 1h at 40 ℃ and then rinsed with DI water to remove excess FITC.
Example 12
The tough hydrogels described above can also be combined with 3D printing techniques to make hydrogels with complex structures to increase the mechanical properties of the hydrogels. The specific method comprises the following steps: firstly, adding tackifier montmorillonite (10 wt%) into deionized water and stirring for one night, and simultaneously dissolving modified sodium alginate (5 wt%), acrylamide (5M) and EDTA-Ca (100mM) into DI water and stirring for one night; the two solutions were then mixed, equilibrated for one day with stirring, and then APS, Ru (II) and MBA were added and stirred away from light. The prepared printing ink is filled into a black lightproof container for printing, and the needle head is wrapped by tinfoil to avoid light leakage. Drawing software such as solidworks and the like is adopted to draw three-dimensional complex geometric shapes such as pyramids, grids and the like, and the three-dimensional complex geometric shapes are converted into a mode which can be recognized by 3D printer software and then are introduced into the software. The movement direction and the movement speed of the 3D printer are controlled through software, pressure is applied to the needle cylinder through the air pump, and extrusion of the solution is controlled. In the whole process, the extruded solution is irradiated by blue light to initiate orthogonal chemical reaction in the solution, and finally the toughness gel with the pyramid shape and the grid shape can be obtained according to the preset.
The tough gels with fine patterns and complex structures prepared in examples 9-12 are shown in FIG. 4.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (5)
1. The flexible hydrogel based on orthogonal photochemical reaction is characterized by comprising the following components in parts by weight: 2-30 parts of a phenol-containing macromolecule, 2-30 parts of a polymerizable monomer, 1-10 parts of a metal ion chelate and a crosslinking agent: the addition amount of the cross-linking agent is 0.02-0.15% of the polymerizable monomer, and the initiator: the addition amount of the initiator is 0.5-5% of the total mass of the hydrogel, and the addition amount of the terpyridine ruthenium chloride hexahydrate photocatalyst is as follows: the addition amount of the terpyridine ruthenium chloride hexahydrate photocatalyst is 0.01-0.1% of the total mass of the gel, and 60-95 parts of solvent, wherein the macromolecular material containing the phenol group comprises one of a natural macromolecular material containing the phenol group and a self-grafting modified synthetic macromolecular material containing the phenol group; the polymerizable monomer comprises one of acrylamide, isopropyl acrylamide and polyethylene glycol diacrylate; the metal ion chelate comprises one of EDTA-Ca, EDTA-Tb and EDTA-Eu.
2. A preparation method of a tough hydrogel based on orthogonal photochemical reaction is characterized by comprising the following steps:
step 1: adding 2-30 parts of macromolecular material containing phenolic group into 60-95 parts of solvent and continuously stirring;
step 2: after complete dissolution, respectively adding 2-30 parts of polymerizable monomer, 1-10 parts of metal ion chelate and crosslinking agent accounting for 0.02-0.15% of the mass of the polymerizable monomer, and uniformly stirring until complete dissolution;
and step 3: adding terpyridyl ruthenium chloride hexahydrate photocatalyst accounting for 0.5-5% of the total mass of the hydrogel and initiator accounting for 0.02-0.15% of the total mass of the hydrogel, and uniformly stirring until the terpyridyl ruthenium chloride hexahydrate photocatalyst and the initiator are completely dissolved to prepare a reaction solution;
and 4, step 4: will be describedThe reaction solution was poured into a suitable mold, air bubbles were removed from the solution, and the solution was passed through a blue light 15mM cm-2Irradiating for 2min to obtain the toughness hydrogel based on orthogonal photochemical reaction;
wherein the macromolecular material containing the phenolic group comprises one of a natural macromolecular material containing the phenolic group and a synthetic macromolecular material containing the phenolic group, which is self-grafted and modified; the polymerizable monomer comprises one of acrylamide, isopropyl acrylamide and polyethylene glycol diacrylate; the metal ion chelate comprises one of EDTA-Ca, EDTA-Tb and EDTA-Eu.
3. The method of claim 2, wherein the polymerizable monomer is a single component or a mixture of multiple polymerizable monomers or a functional polymer monomer.
4. The method of claim 2, wherein the initiator is a water-soluble initiator or an oil-soluble initiator.
5. The method of claim 2, wherein the solvent is water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010794329.5A CN112079960B (en) | 2020-08-10 | 2020-08-10 | Flexible hydrogel based on orthogonal photochemical reaction and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010794329.5A CN112079960B (en) | 2020-08-10 | 2020-08-10 | Flexible hydrogel based on orthogonal photochemical reaction and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112079960A CN112079960A (en) | 2020-12-15 |
| CN112079960B true CN112079960B (en) | 2021-10-29 |
Family
ID=73735695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010794329.5A Expired - Fee Related CN112079960B (en) | 2020-08-10 | 2020-08-10 | Flexible hydrogel based on orthogonal photochemical reaction and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112079960B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115260544B (en) * | 2022-07-26 | 2024-04-26 | 武汉纺织大学 | Rapid forming method of multi-crosslinked 3D gel material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012035507A2 (en) * | 2010-09-16 | 2012-03-22 | Ulusal Bor Arastirma Enstitusu | Production method of hydrogel-metal composite |
| US8765894B2 (en) * | 2009-12-11 | 2014-07-01 | Promerus, Llc | Norbornene-type polymers having quaternary ammonium functionality |
| CN104136500A (en) * | 2012-01-04 | 2014-11-05 | 莫门蒂夫性能材料股份有限公司 | Polymer composites of silicone ionomers |
| CN104194460A (en) * | 2014-08-12 | 2014-12-10 | 西南交通大学 | Preparation method of chelate coating with copper ions capable of controllably catalyzing release of nitrogen monoxide and polyphenol complex |
| CN108342013A (en) * | 2017-01-25 | 2018-07-31 | 翁秋梅 | A kind of hybrid cross-linked dynamic aggregation object and its application |
| CN108864632A (en) * | 2018-06-29 | 2018-11-23 | 成都华点知享知识产权运营有限公司 | A kind of preparation method of the double-network hydrogel with thermochromic function |
| WO2019164548A2 (en) * | 2017-09-01 | 2019-08-29 | The Johns Hopkins University | A programmable soft robot |
| CN111378137A (en) * | 2019-01-01 | 2020-07-07 | 翁秋梅 | Force-induced responsive polymer with multi-network structure |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102556540B1 (en) * | 2016-10-12 | 2023-07-18 | 어드밴스드 바이오매트릭스, 인코포레이티드 | Three-dimensional (3-D) printing inks made from natural extracellular matrix molecules |
-
2020
- 2020-08-10 CN CN202010794329.5A patent/CN112079960B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8765894B2 (en) * | 2009-12-11 | 2014-07-01 | Promerus, Llc | Norbornene-type polymers having quaternary ammonium functionality |
| WO2012035507A2 (en) * | 2010-09-16 | 2012-03-22 | Ulusal Bor Arastirma Enstitusu | Production method of hydrogel-metal composite |
| CN104136500A (en) * | 2012-01-04 | 2014-11-05 | 莫门蒂夫性能材料股份有限公司 | Polymer composites of silicone ionomers |
| CN104194460A (en) * | 2014-08-12 | 2014-12-10 | 西南交通大学 | Preparation method of chelate coating with copper ions capable of controllably catalyzing release of nitrogen monoxide and polyphenol complex |
| CN108342013A (en) * | 2017-01-25 | 2018-07-31 | 翁秋梅 | A kind of hybrid cross-linked dynamic aggregation object and its application |
| WO2019164548A2 (en) * | 2017-09-01 | 2019-08-29 | The Johns Hopkins University | A programmable soft robot |
| CN108864632A (en) * | 2018-06-29 | 2018-11-23 | 成都华点知享知识产权运营有限公司 | A kind of preparation method of the double-network hydrogel with thermochromic function |
| CN111378137A (en) * | 2019-01-01 | 2020-07-07 | 翁秋梅 | Force-induced responsive polymer with multi-network structure |
Non-Patent Citations (4)
| Title |
|---|
| High strength and self-healable gelatin/polyacrylamide double network hydrogels;Xiaoqiang Yan，等;《JOURNAL OF MATERIALS CHEMISTRY B》;20171007;第5卷(第37期);第7683-7691页 * |
| Hydrogels for the Delivery of Plant-Derived (Poly)Phenols;Nicola Micale，等;《Molecules》;20200716;第25卷(第14期);3254 * |
| Multipotency expression of human adipose stem cells in filament-like alginate and gelatin derivative hydrogel fabricated through visible light- lightinitiated;Mehdi Khanmohammadia;《Materials Science and Engineering C》;20190529;第103卷;109808 * |
| Pb(II), Cu(II) and Cd(II) removal using a humic substance-based double network hydrogel in individual and multicomponent systems;Jianhong Ma,等;《JOURNAL OF MATERIALS CHEMISTRY A 》;20180918;第6卷(第41期);第20110-20120页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112079960A (en) | 2020-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107236135A (en) | Gelatin hydrogel and preparation method and application thereof | |
| CN103205006B (en) | Surface patterning high-strength and high-toughness hybrid hydrogel membrane and preparation method thereof | |
| CN104140630B (en) | A kind of chitosan-based double-network hydrogel and preparation method thereof | |
| Peng et al. | Light manipulation for fabrication of hydrogels and their biological applications | |
| CN106633111A (en) | Method for preparing high-strength polyvinyl alcohol-based dual-network hydrogel | |
| CN113713179A (en) | High-comprehensive-performance photocuring biological 3D printing composite hydrogel and preparation method and application thereof | |
| CN107050510A (en) | A kind of sodium alginate/glutin injectable double-network hydrogel and its preparation and application | |
| CN107118359B (en) | Photo-curing hydrogel and preparation method thereof | |
| CN104448161B (en) | Organic composite hydrogel cross-linked by modified gelatin nano-microsphere and preparation method of organic composite hydrogel | |
| CN106986967B (en) | A kind of method that visible light-initiated one-step method preparation has double cross-linked network structure sodium alginate composite hydrogels | |
| CN105504364A (en) | High-strength fluorescent hydrogel and preparation method thereof | |
| CN111072848A (en) | Hydrogel with controllable viscosity and preparation method and application thereof | |
| WO2020156291A1 (en) | Physical and chemical double cross-linked network high-strength gelatin hydrogel and preparation method therefor | |
| CN105936674B (en) | A kind of preparation method of ultraviolet light 3D printing alginic acid hydrogel matrix | |
| CN103224633A (en) | Self-reinforced hybrid hydrogel used for artificial muscles and preparation method thereof | |
| CN112079960B (en) | Flexible hydrogel based on orthogonal photochemical reaction and preparation method thereof | |
| CN106267366B (en) | A method of high-strength and high ductility polyion hydrogel scaffold is prepared using 3D printing | |
| CN114133486A (en) | Bionic anisotropic hybrid cross-linked hydrogel and preparation method and application thereof | |
| JP2008280406A (en) | Interpenetrating polymer network gel and production method thereof | |
| CN115386259A (en) | Anti-dry and anti-freezing photosensitive hydrogel ink, preparation method thereof, high-precision photocured hydrogel and application thereof | |
| KR102025864B1 (en) | Hydrogel actuator haning acrylic acid and method for fabricating hydrogel actuator | |
| CN110628046B (en) | Method for preparing high-strength hydrogel based on tanning principle | |
| CN106243296A (en) | A kind of secondary cross-linking improves the method for aquagel fibre mechanical property | |
| CN107892732B (en) | Temperature-sensitive hydrogel and preparation method thereof | |
| CN109111555A (en) | A kind of preparation method of high-performance bio compatibility radical photopolymerization visible light initiation system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20211029 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |