CN114957535B - Adhesive gel with adjustable interface binding force and preparation method and application thereof - Google Patents
Adhesive gel with adjustable interface binding force and preparation method and application thereof Download PDFInfo
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- 239000000853 adhesive Substances 0.000 title claims description 64
- 230000001070 adhesive effect Effects 0.000 title claims description 64
- 238000002360 preparation method Methods 0.000 title description 10
- 239000000178 monomer Substances 0.000 claims abstract description 64
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 229920000642 polymer Polymers 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- QBPPRVHXOZRESW-UHFFFAOYSA-N 1,4,7,10-tetraazacyclododecane Chemical compound C1CNCCNCCNCCN1 QBPPRVHXOZRESW-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000005587 bubbling Effects 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- KWXIPEYKZKIAKR-UHFFFAOYSA-N 2-amino-4-hydroxy-6-methylpyrimidine Chemical compound CC1=CC(O)=NC(N)=N1 KWXIPEYKZKIAKR-UHFFFAOYSA-N 0.000 claims description 4
- VJJZJBUCDWKPLC-UHFFFAOYSA-N 3-methoxyapigenin Chemical compound O1C2=CC(O)=CC(O)=C2C(=O)C(OC)=C1C1=CC=C(O)C=C1 VJJZJBUCDWKPLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000001338 self-assembly Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- ZUQIVGCFGVFWNR-UHFFFAOYSA-N isocyanatoethane;2-methylprop-2-enoic acid Chemical compound CCN=C=O.CC(=C)C(O)=O ZUQIVGCFGVFWNR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000037081 physical activity Effects 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 230000003993 interaction Effects 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000001419 dependent effect Effects 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 64
- 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 description 23
- 239000000243 solution Substances 0.000 description 7
- 239000004826 Synthetic adhesive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- XUMIQAOMRDRPMD-UHFFFAOYSA-N (6-oxo-1h-pyrimidin-2-yl)urea Chemical compound NC(=O)NC1=NC(=O)C=CN1 XUMIQAOMRDRPMD-UHFFFAOYSA-N 0.000 description 1
- 208000031737 Tissue Adhesions Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical compound N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000023597 hemostasis Effects 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002677 supramolecular polymer Polymers 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 239000003106 tissue adhesive Substances 0.000 description 1
- 229940075469 tissue adhesives Drugs 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The bonding gel with the adjustable interface bonding force is prepared by reacting methyl methacrylate with UPy monomers and TPY monomers, and the interface bonding force of the bonding gel can be adjusted and controlled by changing the molar ratio of the UPy monomers to the TPY monomers. The driving force for forming the bonding gel with the adjustable interface bonding force is two non-covalent interactions of hydrogen bond and metal coordination, the bonding strength of the interface is enhanced, the bonding gel has excellent mechanical property, the current situation that the bonding strength of the interface is lack of adjustment and control because the traditional bonding gel material is only dependent on single non-covalent interaction is overcome, and a new way is provided for the synthesis of novel bonding gel with the controllable interface bonding force.
Description
Technical Field
The invention relates to the field of supramolecular materials, in particular to an adhesive gel with adjustable and controllable interface binding force, and a preparation method and application thereof.
Background
The adhesion phenomenon is widely present in nature, and inspired by the adhesion phenomenon in nature, a variety of synthetic adhesive materials have been developed in recent years, and show superiority in the fields of tissue engineering, drug delivery, soft actuators, wearable devices, and the like. For example, tissue adhesives are a common adjunct to surgery and are alternatives to suture hemostasis, tissue adhesion, and wound closure. In addition, the adhesive material is widely used in the field of skin sensors for monitoring human body activities due to its flexibility and strong extensibility.
Adhesive gels constructed based on different non-covalent interactions have attracted considerable attention due to their unique physical and chemical properties. To date, a variety of adhesive gels have been synthesized that are based on non-covalent interactions, including hydrogen bonding, pi-pi stacking, electrostatic interactions, host-guest interactions, metal coordination, and van der waals interactions. For example, the Stang group reports a special supramolecular polymer adhesive made from non-tacky, non-polymeric materials by forming hydrogen bonds with water. Liu task group through Fe 3+ The initiated simultaneous polymerization creates a paintable, electrically conductive, adhesive hydrogel patch that exhibits excellent ability to quickly adhere to cardiac surfaces. Scherman et al highly branched polyrotaxane (HBP-CB [ n ] using cucurbituril threads]) Preparation of a compound based on CB [ n ]]A dynamic bonding soft material for mediating molecular recognition. Furthermore, shi et al designed polymeric hydrogel systems by introducing Cyclodextrin (CD)/azobenzene (Azo). Although substantial progress has been made in the study of adhesive materials, the above-described synthetic adhesive materials are generally formed on the basis of a single non-covalent interaction, which possesses limited adhesive strength, i.e., lack of control over the strength of the interfacial bond.
The adhesive gel, once adjusted for the strength of the interface bond, causes the adhesive material to decompose, thus limiting its widespread use. How to regulate the interfacial bonding force of the adhesive material is a problem which needs to be solved, and therefore, it is necessary to develop a novel adhesive material with controllable adhesion.
Disclosure of Invention
The adhesive gel prepared by the method has good interface bonding strength, and the interface bonding force of the adhesive gel can be regulated and controlled by changing the molar ratio of a UPy monomer to a TPY monomer in the preparation process.
In order to achieve the above objects, the present invention provides an adhesive gel having an adjustable interface bonding force, which is prepared by reacting methyl methacrylate with UPy monomers and TPY monomers, and the interface bonding force of which can be adjusted by changing the molar ratio of the UPy monomers to the TPY monomers, wherein: the structural formulas of the TPY monomer and the UPy monomer are respectively shown as a formula (1) and a formula (2):
as a further preferable technical scheme of the invention, the molar ratio of the methyl methacrylate to the UPy monomer to the TPY monomer is 100.
According to another aspect of the present invention, the present invention further provides a method for preparing an adhesive gel with adjustable and controllable interfacial bonding force, comprising the following steps:
1) Dissolving 4-hydroxybenzaldehyde and 4-vinylbenzyl chloride in N, N-dimethylformamide, adding solid KOH, stirring uniformly at room temperature, adding water for precipitation, washing, drying in vacuum, grinding and washing a dried product in hexane, and drying again to obtain a TPY monomer;
2) Under the heating condition, dissolving 6-methylisocytosine in N, N-dimethylformamide, adding methacrylic acid 2-ethyl isocyanate for reaction, then quenching at a rapid cooling speed, washing with cyclohexane, and drying to obtain a UPy monomer;
3) Dissolving methyl methacrylate, UPy monomer and TPY monomer in dimethyl sulfoxide, adding azobisisobutyronitrile as an initiator to form a mixed solution, introducing air into the mixed solution for bubbling, performing polymerization reaction under the conditions of heating and stirring, quenching polymerization by freezing ice water, adding methanol, performing vacuum filtration to obtain white solid precipitate, and drying to obtain a polymer;
4) The polymer is self-assembled to form gel, and the gel is adhered to each other to obtain the adhesive gel.
As a further preferred embodiment of the present invention, in the step 3), the bubbling operation is carried out for 10 to 15min under a nitrogen flow.
As a further preferred embodiment of the present invention, in step 3), the stirring operation is carried out at 70 to 80 ℃ for 5 to 12 hours.
As a further preferable embodiment of the present invention, the operation of adding methanol and then obtaining a white solid precipitate by vacuum filtration in step 3) is repeated several times.
As a further preferable technical scheme of the invention, zn capable of generating Zn is added in the self-assembly process or before the self-assembly process in the step 4) 2+ The compound of (1).
As a further preferred embodiment of the invention, 1,4,7, 10-tetraazacyclododecane or UPy monomer is also added to the adhesive gel obtained in step 4).
According to another aspect of the present invention, the present invention also provides a use of the adhesive gel with adjustable and controllable interfacial bonding force for a skin sensor for monitoring human body activity.
The adhesive gel with adjustable interface bonding force, the preparation method and the application thereof can achieve the following beneficial effects by adopting the technical scheme:
1) According to the adhesive gel with the adjustable interface bonding force, the driving force formed by the gel is two non-covalent interactions of hydrogen bonds and metal coordination, so that the interface bonding strength is enhanced, and the adhesive gel has excellent mechanical properties; the invention overcomes the current situation that the traditional synthetic adhesive gel material only depends on single non-covalent action and the interface bonding strength is lack of regulation and control, and provides a new way for the synthesis of novel adhesive gel with controllable interface bonding force;
2) The adhesive gel with adjustable interface bonding force provided by the invention can realize the adjustment and control of the interface bonding force by destroying the hydrogen bond or metal coordination;
3) The adhesive gel with the adjustable interface bonding force provided by the invention has good interface bonding strength, and the interface bonding force of the adhesive gel can be adjusted and controlled by changing the molar ratio of the UPy monomer to the TPY monomer in the preparation process;
4) The adhesive gel with adjustable interface binding force provided by the invention has great popularization value and wide application prospect in the fields of epidermal sensors for monitoring human activities and the like.
Drawings
The invention is described in further detail below with reference to the drawings and the detailed description.
FIG. 1 is an SEM topography of adhesive gel AG1 of example 1;
FIG. 2 shows the polymers P1, P2, P3 from examples 1 to 3 1 H NMR spectrum (in CDCl) 3 As a solvent, 400MHz and 298K);
FIG. 3 is a rheological profile of the gels AG1, AG2, AG3 of examples 1 to 3;
FIG. 4 is a tensile stress strain plot of adhesive gels AG1, AG2, AG3, AG4, AG5 of examples 1-5;
FIG. 5 is a drawing of a tensile test of the adhesive gels AG1, AG2, AG3 of examples 1 to 3;
FIG. 6 shows the disassembly behavior of the adhesive gels AG4, AG5 of examples 4 and 5;
fig. 7 is a TGA analysis test of the polymers P1, P2, P3 in examples 1 to 3.
The objects, features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments. In the preferred embodiments, the terms "upper", "lower", "left", "right", "middle" and "a" are used for clarity of description only, and are not used to limit the scope of the invention, and the relative relationship between the terms and the terms is not changed or modified substantially without changing the technical content of the invention.
The invention provides an adhesive gel with adjustable interface bonding force, which is a supermolecule adhesive gel and is prepared by the reaction of methyl methacrylate, a UPy monomer and a TPY monomer, and the interface bonding force of the adhesive gel can be adjusted and controlled by changing the molar ratio of the UPy monomer to the TPY monomer, wherein: the structural formulas of the TPY monomer and the UPy monomer are respectively shown as a formula (1) and a formula (2):
in the specific implementation, the molar ratio of the methyl methacrylate to the UPy monomer to the TPY monomer is 100.
The invention also provides a preparation method of the adhesive gel with adjustable interface bonding force, wherein the prepared polymer takes polymethyl methacrylate as a main chain, and also contains 2-ureido-4-pyrimidone (UPy) groups and Terpyridine (TPY) groups, wherein, hydrogen bonds can be formed between the UPy groups, and Zn is added 2+ (e.g., znCl) 2 、Zn(NO 3 ) 2 Etc.) and then, due to the TPY group and Zn contained in the polymer 2+ Complexation, under the drive of metal coordination between gels, the polymer can form gel through self-assembly, and the mutual adhesion between gels can further form adhesive gel.
The adhesive gel is based on hydrogen bond and metal coordination orthogonal non-covalent interaction, namely, based on interface adhesion of double supermolecule force, and in the preparation process, the interface bonding force of the adhesive gel can be regulated and controlled by changing the molar ratio of the UPy monomer to the TPY monomer.
In order to make those skilled in the art further understand the technical solution of the present invention, the technical solution of the present invention is further described in detail by the following specific embodiments.
Example 1
A preparation method of an adhesive gel with adjustable and controllable interface bonding force comprises the following steps:
step 1), dissolving 4-hydroxybenzaldehyde and 4-vinylbenzyl chloride in N, N-Dimethylformamide (DMF), adding solid KOH, stirring at room temperature for 12 hours, adding water for precipitation, washing, drying at 60 ℃ in vacuum, grinding and washing a dried product in hexane, and drying twice by air flow to obtain a TPY monomer, wherein the chemical reaction formula of the TPY monomer is shown as a reaction formula (3);
in the above step 1), the use ratio of 4-hydroxybenzaldehyde, 4-vinylbenzyl chloride, DMF, solid KOH, water, hexane was 20mmol.
Step 2), dissolving 6-methylisocytosine in N, N-Dimethylformamide (DMF) under the heating condition of 170 ℃, adding methacrylic acid 2-ethyl isocyanate for reaction, rapidly quenching by water cooling, washing with cyclohexane, and drying in vacuum to obtain a UPy monomer, wherein the chemical reaction formula of the UPy monomer is shown as a reaction formula (4);
in the step 2), the use amount ratio of the 6-methylisocytosine to the 2-isocyanatoethyl methacrylate is 23.5mmol.
Step 3), dissolving TPY monomer (393978 mg, 0.8mmol), UPy monomer (252mg, 0.8mmol) and methyl methacrylate (9g, 90mmol) in dimethyl sulfoxide, adding azobisisobutyronitrile (22mg, 0.13mmol) as an initiator to form a mixed solution, and introducing nitrogen (N) into the mixed solution 2 ) Bubbling the flow for 15min, heating to 80 ℃, stirring for 10h, carrying out polymerization reaction, then quenching the polymerization by freezing with ice water, finally adding methanol (500 mL), obtaining a white solid through vacuum filtration (repeating for three times), and drying to obtain a polymer (marked as P1), wherein the chemical reaction formula of the polymer is shown as a reaction formula (5);
and 4) self-assembling the polymer to generate gel (marked as G1), and adhering the gel to each other to obtain adhesive gel (marked as AG 1).
Of polymers P1 1 H NMR, mn, mw, PDI data are as follows:
1 H NMR(400MHz,CDCl 3 )δ12.92(s,1H),11.88(s,1H),10.42(s,2H),8.67(d,J＝15.0Hz,66H),7.84(s,44H),7.03(s,35H),5.87–5.71(m,11H),5.03(s,22H),4.66(d,J＝7.6Hz,26H),4.03(d,J＝7.9Hz,20H),3.56(s,3580H),2.88–0.02(m,13470H)。
Mn：4.85×10 4
Mw：9.41×10 4
PDI：1.94
example 2
Example 2 the same production method as in example 1 was used except that the molar ratio of TPY monomer, UPy monomer and methyl methacrylate was changed to 0.6. The polymer in this example is designated P2, the gel is designated G2 and the adhesive gel is designated AG2.
The 1H NMR, mn, mw, PDI data for polymer P2 are as follows:
1H NMR(400MHz,CDCl3)δ12.92(s,1H),11.93(s,1H),10.41(s,1H),8.66(s,3H),7.85(s,2H),7.03(s,2H),5.79(s,1H),5.05(s,2H),4.04(s,3H),3.56(s,214H),2.92–0.51(m,591H).
Mn：3.73×104
Mw：6.53×104
PDI：1.75
example 3
Example 3 the same production method as in example 1 was employed except that the molar ratio of the TPY monomer, UPy monomer and methyl methacrylate was changed to 0.3. The polymer in this example is designated P3, the gel is designated G3 and the adhesive gel is designated AG3.
Example 4
Example 4 the same procedure as in example 1 was followed, except that 1,4,7, 10-tetraazacyclododecane solution was added to the resulting adhesive gel, and the metal coordinate bonds between the gels were broken and the interfacial bonding force was weakened by the addition of 1,4,7, 10-tetraazacyclododecane, thereby forming a new adhesive gel (referred to as AG 4).
Example 5
Example 5 the same procedure as in example 1 was followed, except that UPy monomer solution was added to the resulting adhesive gel, and hydrogen bonding between gels was broken due to the addition of UPy monomer, so that the interfacial bonding force was weakened, and a new adhesive gel (referred to as AG 5) was formed.
To investigate the properties of the adhesive gels with controllable interfacial bonding force according to the present invention, the following tests were performed on the samples of examples 1 to 5, respectively.
FIG. 1 is an SEM topography of the adhesive gel AG1 of example 1, showing the porous network structure of the gel, confirming the formation of crosslinks between polymer chains;
FIG. 2 shows the polymers P1, P2, P3 of examples 1 to 3 1 H NMR spectrum (in CDCl) 3 As a solvent, 400MHz and 298K);
FIG. 3 is a graph of the rheological experiments for the gels AG1, AG2, AG3 of examples 1 to 3, showing that the storage modulus (G ') and the loss modulus (G') increase with increasing frequency and that G 'is always greater than G' in the frequency range of 0.1 to 100rad/s, indicating that all three viscous gels are chemically cross-linked;
FIG. 4 is a graph of the tensile stress strain curves for adhesive gels AG1, AG2, AG3, AG4, AG5 of examples 1 through 5, showing that the ultimate strain at break for AG2 and AG3 is reduced compared to AG1, and that the strain at break for AG4 and AG5 is greatly reduced compared to AG 1;
FIG. 5 is a drawing of a tensile test of the adhesive gels AG1, AG2, AG3 of examples 1 to 3;
FIG. 6 shows the disassembly behavior of the adhesive gels AG4, AG5 of examples 4 and 5, wherein the UPy monomer solution and 1,4,7, 10-tetraazacyclododecane solution are added to AG4 and AG5, respectively, to break the relevant supramolecular forces, after a few minutes the interfacial bonds become loose and the adhesive gel can be easily peeled off, i.e. the adhered adhesive gel can be peeled off in this way in the application;
fig. 7 is a TGA analysis of the polymers P1, P2, P3 of examples 1 to 3, which are relatively stable until the temperature reaches 250 c, above 250 c the polymer starts to decompose, suddenly at around 300 c and loses weight completely at about 420 c.
The mole ratio of methyl methacrylate, UPy monomer and TPY monomer in AG1 prepared in example 1 is 100; the molar ratios of methyl methacrylate, UPy monomer and TPY monomer in AG2 and AG3 prepared in examples 2 and 3 were 100, 0.6 and 100, respectively, and the fracture strain values were reduced to 118% and 79% respectively compared to AG1 due to the reduction in metal coordination. Furthermore, the interfacial bonding force can be controlled by breaking hydrogen bonds or metal coordination, and examples 4 and 5 form new viscous gels AG4 and AG5 respectively by adding 1,4,7, 10-tetraazacyclododecane or UPy monomer solution into AG1, and the breaking strain value is significantly reduced to 38.86 percent and 16.71 percent.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely examples and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims.
Claims (7)
1. An adhesive gel with adjustable interface bonding force, which is prepared by reacting methyl methacrylate with UPy monomer and TPY monomer, and the interface bonding force of which can be adjusted by changing the molar ratio of UPy monomer to TPY monomer, wherein: the structural formulas of the TPY monomer and the UPy monomer are respectively shown as a formula (1) and a formula (2):
the method for preparing the adhesive gel by reacting methyl methacrylate with UPy monomer and TPY monomer is as follows:
dissolving methyl methacrylate, UPy monomer and TPY monomer with the molar ratio of 100; the polymer is self-assembled to generate gel, and the gel is mutually adhered to obtain adhesive gel;
the temperature for polymerization reaction under stirring is 70-80 ℃ and the time is 5-12h.
2. The method for preparing the adhesive gel with controllable interfacial bonding force according to claim 1, comprising the following steps:
1) Dissolving 4-hydroxybenzaldehyde and 4-vinylbenzyl chloride in N, N-dimethylformamide, adding solid KOH, stirring uniformly at room temperature, adding water for precipitation, washing, drying in vacuum, grinding and washing a dried product in hexane, and drying again to obtain a TPY monomer;
2) Under the heating condition, dissolving 6-methylisocytosine in N, N-dimethylformamide, adding methacrylic acid 2-ethyl isocyanate for reaction, then quenching at a rapid cooling speed, washing with cyclohexane, and drying to obtain a UPy monomer;
3) Dissolving methyl methacrylate, UPy monomer and TPY monomer in dimethyl sulfoxide, adding azobisisobutyronitrile as an initiator to form a mixed solution, introducing air into the mixed solution for bubbling, performing polymerization reaction under the conditions of heating and stirring, quenching polymerization by freezing ice water, adding methanol, performing vacuum filtration to obtain white solid precipitate, and drying to obtain a polymer;
4) The polymer is self-assembled to form gel, and the gel is adhered to each other to obtain the adhesive gel.
3. The method for preparing an adhesive gel with controllable interfacial bonding force according to claim 2, wherein the bubbling operation is performed under a nitrogen flow for 10-15min in the step 3).
4. The method for preparing an adhesive gel having a controllable interfacial bonding force according to claim 2, wherein the step 3) of adding methanol and then obtaining a white solid precipitate by vacuum filtration is repeated several times.
5. The method of claim 2, wherein Zn is further added during or before the self-assembly process of the step 4) to generate Zn 2+ The compound of (1).
6. The method of claim 2, wherein 1,4,7, 10-tetraazacyclododecane or UPy monomer is further added to the adhesive gel obtained in step 4).
7. Use of the adhesive gel having controllable interfacial bonding force according to claim 1, in a skin sensor for monitoring human body activity.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012168392A1 (en) * | 2011-06-07 | 2012-12-13 | Technische Universiteit Eindhoven | Hydrogelator with shape-memory properties |
| CN103374132A (en) * | 2013-07-12 | 2013-10-30 | 中科院广州化学有限公司 | Preparation and application of metal ion directly induced fluorescent supramolecular gel |
| CN108059693A (en) * | 2017-12-01 | 2018-05-22 | 浙江大学 | A kind of preparation method of the temperature sensitive type physical hydrogel of multiple hydrogen bonding enhancing |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012168392A1 (en) * | 2011-06-07 | 2012-12-13 | Technische Universiteit Eindhoven | Hydrogelator with shape-memory properties |
| CN103374132A (en) * | 2013-07-12 | 2013-10-30 | 中科院广州化学有限公司 | Preparation and application of metal ion directly induced fluorescent supramolecular gel |
| CN108059693A (en) * | 2017-12-01 | 2018-05-22 | 浙江大学 | A kind of preparation method of the temperature sensitive type physical hydrogel of multiple hydrogen bonding enhancing |
Non-Patent Citations (2)
| Title |
|---|
| Hu Wang, et al..Preparation of a white-light-emitting fluorescent supramolecular polymer gel with a single chromophore and use of the gel to fabricate a protected quick response code.Materials Chemistry Frontiers.2016,167-171. * |
| Xiaofan Ji, et al..Supramolecular Construction of Multifl uorescent Gels: Interfacial Assembly of Discrete Fluorescent Gels through Multiple Hydrogen Bonding.Advanced Materials.2015,第27卷8062-8066. * |
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