CN109776817A - A kind of photocuring selfreparing conductive hydrogel and preparation method thereof - Google Patents
A kind of photocuring selfreparing conductive hydrogel and preparation method thereof Download PDFInfo
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- CN109776817A CN109776817A CN201811529466.5A CN201811529466A CN109776817A CN 109776817 A CN109776817 A CN 109776817A CN 201811529466 A CN201811529466 A CN 201811529466A CN 109776817 A CN109776817 A CN 109776817A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000000017 hydrogel Substances 0.000 title claims abstract description 34
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 54
- 238000007385 chemical modification Methods 0.000 claims abstract description 34
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 32
- VTGOHKSTWXHQJK-UHFFFAOYSA-N pyrimidin-2-ol Chemical compound OC1=NC=CC=N1 VTGOHKSTWXHQJK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012948 isocyanate Substances 0.000 claims abstract description 22
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 21
- -1 alkenyl acid anhydrides Chemical class 0.000 claims abstract description 17
- 229920005615 natural polymer Polymers 0.000 claims abstract description 16
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 239000004909 Moisturizer Substances 0.000 claims abstract description 6
- 230000001333 moisturizer Effects 0.000 claims abstract description 6
- 239000003792 electrolyte Substances 0.000 claims abstract description 5
- 150000008318 pyrimidones Chemical class 0.000 claims abstract description 5
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000002576 ketones Chemical class 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 21
- 229920001661 Chitosan Polymers 0.000 claims description 20
- 108010010803 Gelatin Proteins 0.000 claims description 19
- 239000008273 gelatin Substances 0.000 claims description 19
- 229920000159 gelatin Polymers 0.000 claims description 19
- 235000019322 gelatine Nutrition 0.000 claims description 19
- 235000011852 gelatine desserts Nutrition 0.000 claims description 19
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 12
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 12
- 239000012965 benzophenone Substances 0.000 claims description 10
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 4
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- JQSSXIRDGUMPNP-UHFFFAOYSA-N (4-decoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 JQSSXIRDGUMPNP-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 claims description 2
- KPTLPIAOSCGETM-UHFFFAOYSA-N benzene 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O.c1ccccc1 KPTLPIAOSCGETM-UHFFFAOYSA-N 0.000 claims description 2
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical class OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims 2
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical class OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims 1
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 claims 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims 1
- 239000000499 gel Substances 0.000 abstract description 26
- 150000003384 small molecules Chemical class 0.000 abstract description 13
- 230000005611 electricity Effects 0.000 abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 30
- 239000000178 monomer Substances 0.000 description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- KWXIPEYKZKIAKR-UHFFFAOYSA-N 2-amino-4-hydroxy-6-methylpyrimidine Chemical compound CC1=CC(O)=NC(N)=N1 KWXIPEYKZKIAKR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 1
- SIMFZBAGLIDEPJ-UHFFFAOYSA-N C1(=CC=CC=C1)CC(C)=O.C(C)OOOCC Chemical compound C1(=CC=CC=C1)CC(C)=O.C(C)OOOCC SIMFZBAGLIDEPJ-UHFFFAOYSA-N 0.000 description 1
- FMRHJJZUHUTGKE-UHFFFAOYSA-N Ethylhexyl salicylate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1O FMRHJJZUHUTGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of photocuring selfreparing conductive hydrogels and preparation method thereof.This hydrogel be the side chain of chemical modification is contained unsaturated double-bond, urea groups pyrimidone block, light-initiated group natural macromolecular material be made solution, be added moisturizer and electrolyte, what resulting mixed liquor formed after photocuring.The natural macromolecular material of the chemical modification obtains the photoinitiator containing isocyanates the preparation method is as follows: 1) react the photoinitiator that side chain contains hydroxyl with isocyanates；2) pyrimidone derivatives are reacted with isocyanates, obtains urea groups pyrimidone；3) side chain is contained to the natural polymers solution and alkenyl acid anhydrides, the photoinitiator containing isocyanates, urea groups pyrimidine reactive ketone of amino, resulting product is dialysed, dry.The photocuring selfreparing conductive hydrogel that the present invention is prepared have many advantages, such as safety it is good, without small molecule systems, mechanical strength is good, gel conducts electricity very well.
Description
Technical field
The present invention relates to a kind of photocuring selfreparing conductive hydrogels and preparation method thereof.
Background technique
Hydrogel refers to that a kind of main chain or branch contain a large amount of hydrophilic radicals and be water-swellable, and has tridimensional network
Cross-linked polymer, it is swollen in water and does not dissolve.Conductive hydrogel combines the chemical property and water of conducting polymer
The flexible nature of gel is with a wide range of applications in terms of electrode for medical service, flexible sensor and wearable device.
According to formation basic theory, hydrogel is divided into chemically crosslinked aquagel and physical cross-linking hydrogel two major classes.Physics is handed over
Join and be not related to chemically reacting in this kind of hydrogel forming process, the crosslinking of molecule interchain passes through intermolecular interaction (Fan De
Hua Li, hydrophobic interaction, hydrogen bond etc.) it is formed, system can not use small molecule monomer, but the hydrogel one being physical crosslinking
As mechanical property it is weaker.Chemically crosslinked aquagel can be divided into the types such as cross-linking agents hydrogel, photo-initiated crosslinking hydrogel, this
The key of kind of method is the suitable cross-linking reaction of selection and crosslinking agent, because as medical material in use, requirement to reaction
Be it is very harsh, this includes: that requirement monomer and solvent do not have toxicity；Polymerization efficiency is high, and only Micro-monomer remains, and does not damage people
Body health.This kind of reaction system, which is crosslinked, by monomer chemistries often there is the residual of the small molecule monomers such as monomer, initiator, crosslinking agent
Stay, bring irritation and toxicity, as the material with direct body contact especially it is some use the higher occasions of safety requirements,
There are biggish limitations.The crosslinked gel network that monomer radical polymerize simultaneously is more crisp and frangible, and mechanical performance is not
Foot.It is had a safety feature by new method preparation, the meaningful work of the conductive hydrogel of satisfactory mechanical property.The prior art
In, " synthesis of the double bond containing unsaturated acrylic compounds macromolecular photoinitiator of side chain and performance study " disclosed in Liu Yongrui etc.
And " Unsaturated macrophotoinitiators with double bonds in side- disclosed in Liu et al.
Chain:synthesis and photopolymerization behaviors ", which is reported, prepares the double bond containing insatiable hunger of side chain
With acrylic compounds macromolecular photoinitiator, which further can be solidified into gel with monomer reaction, system preparation
There is monomer residue and mechanical strength in gel.Also there is relevant report, such as CN107043465A, CN108484808A, Liu
" the photocuring self-healing coatings based on multiple hydrogen bonding effect " of benevolence etc. indicate the photocuring water gel based on multiple hydrogen bonding
System, the gel of acquisition have self-healing properties, and system has initiator residual and needs to react jointly with monomer.
In the prior art, CN107043465A discloses a kind of urea groups pyrimidone modified gelatin injectable self-healing hydrogel
And preparation method thereof, which also needs to act on forming gel using the amino of small-molecule substance iron chloride and gelatin.
CN108484808A discloses a kind of selfreparing conductive hydrogel and preparation method thereof based on multiple hydrogen bonding, which needs
Small molecule photoinitiator and small molecule monomer is added, there are potential hidden danger for biological safety and bio-toxicity aspect.
Summary of the invention
For overcome the deficiencies in the prior art, one of the objects of the present invention is to provide it is a kind of by chemical modification formed
Side chain contains the natural macromolecular material of unsaturated double-bond, urea groups pyrimidone block, light-initiated group；The second object of the present invention
It is to provide the natural macromolecular material system for containing unsaturated double-bond, urea groups pyrimidone block, light-initiated group by this side chain
At photocuring selfreparing conductive hydrogel.
Invention thinking of the invention is as follows: the present invention is prepared for a kind of side chain, and to contain unsaturated double-bond, urea groups pyrimidone embedding
The natural polymer of section, light-initiated group, prepares conductive polymer gel by photo-crosslinking solidification with this.By alkene containing double bonds
Class monomer is reacted with natural polymer, introduces unsaturated double-bond in side chain；Photoinitiator is introduced in side chain by esterification；Together
When urea groups pyrimidone is introduced into the side chain of polymer.
The technical solution used in the present invention is:
A kind of preparation method of the natural macromolecular material of chemical modification, comprising the following steps:
1) photoinitiator that side chain contains hydroxyl is reacted with isocyanates, is obtained containing the light-initiated of isocyanates
Agent；
2) pyrimidone derivatives are reacted with isocyanates, obtains urea groups pyrimidone；
3) side chain is contained the natural polymers solution of amino with alkenyl acid anhydrides, containing the light-initiated of isocyanates
Agent, urea groups pyrimidine reactive ketone, resulting product are dialysed, dry, and obtaining side chain, to contain unsaturated double-bond, urea groups pyrimidone embedding
The natural macromolecular material of section, light-initiated group.
Preferably, in the preparation method step 1) of the natural macromolecular material of this chemical modification, side chain contains hydroxyl
Photoinitiator is 4- dihydroxy benaophenonel, 2,4 dihydroxyl benzophenone, ESCALOL 567,2- hydroxyl -4-
Oxy-octyl benzophenone, 2- hydroxyl -4- decyloxy benzophenone, 2- hydroxyl -4- dodecyloxy benzophenones, 2,2 '-two
Hydroxyl -4- methoxy benzophenone, 2- hydroxyl -4- methoxyl group -2 '-carboxyl benzophenone, 2,2 '-dihydroxy -4,4 '-dimethoxy
Base benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenones, 2- hydroxyl -4- methoxyl group -5- diphenylsulfone ketone, 2,2 '-dihydroxies
Base -4,4 '-dimethoxy -5- diphenylsulfone ketone, 2- hydroxy-2-methyl -1- in ethoxy ether phenylacetone at least
It is a kind of.
Preferably, in the preparation method step 2) of the natural macromolecular material of this chemical modification, pyrimidone derivatives are(2- amino-4-hydroxy -6- methylpyrimidine).
Preferably, in the preparation method step 1) or step 2) of the natural macromolecular material of this chemical modification, isocyanic acid
Ester be hexamethylene diisocyanate, methyl diphenylene diisocyanate, 1,5- naphthalene diisocyanate, paraphenylene diisocyanate,
Isophorone diisocyanate, benzene dimethylene diisocyanate, toluene di-isocyanate(TDI), methylcyclohexane diisocyanate,
At least one of dicyclohexyl methyl hydride diisocyanate, 1,4- cyclohexane diisocyanate.
Preferably, in the preparation method step 3) of the natural macromolecular material of this chemical modification, side chain contains amino
Natural polymers, alkenyl acid anhydrides, the photoinitiator containing isocyanates, urea groups pyrimidone mass ratio be 100:(1~
10): (1~10): (1~10)；It is further preferred that side chain contains the natural polymers of amino, alkenyl acid anhydrides, contains
The mass ratio of the photoinitiator, urea groups pyrimidone that have isocyanates is 100:(3~7): (3~7): (3~7).
Preferably, in the preparation method step 3) of the natural macromolecular material of this chemical modification, side chain contains amino
Natural polymers are at least one of chitosan, chitosan derivatives, gelatin；In some preferred tools of the invention
In body embodiment, the natural polymers structural formula that side chain contains amino be may be expressed as:
Preferably, in the preparation method step 3) of the natural macromolecular material of this chemical modification, alkenyl acid anhydrides is methyl
Acrylic anhydride.
Preferably, a kind of preparation method of the natural macromolecular material of chemical modification, comprising the following steps:
1) side chain is contained to the photoinitiator of hydroxyl(4- dihydroxy benaophenonel) and hexamethylene diisocyanate
It is reacted, obtains the photoinitiator containing isocyanates
2) willSynthetic reaction is carried out with hexamethylene diisocyanate, is obtained
3) by side chain contain amino natural polymers solution, Reaction obtains side chain and contains unsaturated double-bond, urea groups pyrimidone block, light-initiated
The natural macromolecular material solution of group, then dialysed with after freeze-drying process, it obtains side chain and contains unsaturated double-bond, urea groups
The natural macromolecular material of pyrimidone block, light-initiated group.This side chain contain unsaturated double-bond, urea groups pyrimidone block,
The natural macromolecular material structural formula of light-initiated group can indicate are as follows:
Preferably, in the preparation method step 1) of the natural macromolecular material of this chemical modification, 4- dihydroxy benaophenonel
Molar ratio with hexamethylene diisocyanate is 1:(1~6).
Preferably, in the preparation method step 1) of the natural macromolecular material of this chemical modification, the temperature of reaction is 70
DEG C~90 DEG C, the time of reaction is 5h~10h；The solvent of reaction is aprotic polar solvent, preferably N, N- dimethyl formyl
Amine.
Preferably, in the preparation method step 1) of the natural macromolecular material of this chemical modification, esterification is in alkali
With carry out under the action of catalyst；It is further preferred that alkali is N methyldiethanol amine；Catalyst is tin catalyst, excellent
It is selected as dibutyl tin dilaurate.
Preferably, in the preparation method step 2) of the natural macromolecular material of this chemical modification,With
The molar ratio of hexamethylene diisocyanate is 1:(2~8).
Preferably, in the preparation method step 2) of the natural macromolecular material of this chemical modification, the temperature of synthetic reaction
It is 90 DEG C~110 DEG C, time of synthetic reaction is 10h~for 24 hours.
Preferably, in the preparation method step 3) of the natural macromolecular material of this chemical modification, side chain contains amino
Natural polymers be gelatin or chitosan, specifically by gelatin be configured to mass concentration be 15%~30% it is water-soluble
Liquid, or chitosan is configured to the acetum that mass concentration is 2%~10%, it then participates in reacting again.
Preferably, in the preparation method step 3) of the natural macromolecular material of this chemical modification, when side chain contains amino
Natural polymers be gelatin when, gelatin solution, alkenyl acid anhydrides, the photoinitiator containing isocyanates and urea groups is phonetic
Pyridine ketone hybrid reaction；Specific reaction condition is as follows: the pH of reaction system being first adjusted to 9~11 hybrid reaction 1h~3h, then
PH to 5~7 is adjusted again terminates reaction；The temperature of reaction is 35 DEG C~50 DEG C.
Preferably, in the preparation method step 3) of the natural macromolecular material of this chemical modification, when side chain contains amino
Natural polymers when being chitosan, chitosan is made into chitosan-acetic acid solution, adjusts pH value, then with alkenyl acid anhydrides
Obtained product is dialysed in reaction, dry, then that dry products therefrom and the photoinitiator containing isocyanates and urea groups is phonetic
Pyridine ketone hybrid reaction；Specific reaction condition is as follows: adjusting pH is 5~7, and the time with alkenyl anhydride reaction is 4h~8h.
Preferably, in the preparation method step 3) of the natural macromolecular material of this chemical modification, dialysis treatment is specially
With water 2~3 days removing small molecule objects of dialysis and solvent；Further, water used is preferably distilled water.
Preferably, it in the preparation method step 3) of the natural macromolecular material of this chemical modification, will be produced after dialysis treatment
Object freeze-drying.
A kind of natural macromolecular material of chemical modification is that the side chain as made from above-mentioned preparation method contains unsaturated pair
Key, urea groups pyrimidone block, light-initiated group natural macromolecular material.
A kind of preparation method of photocuring selfreparing conductive hydrogel, the natural macromolecular material system that afore mentioned chemical is modified
At solution, moisturizer and electrolyte is added, resulting mixed liquor carries out photocuring, forms photocuring selfreparing conductive hydrogel.
Preferably, in the preparation method of this photocuring selfreparing conductive hydrogel, each raw material of mixed liquor presses quality percentage
The composition of ratio is as follows: 5%~30% chemical modification natural macromolecular material, 10%~30% moisturizer, 2%~15% electrolysis
Matter, surplus are water.
Preferably, in the preparation method of this photocuring selfreparing conductive hydrogel, moisturizer be sorbierite, ethylene glycol,
At least one of glycerol, polyvinyl alcohol；It is further preferred that moisturizer is glycerol.
Preferably, in the preparation method of this photocuring selfreparing conductive hydrogel, electrolyte be ammonium chloride, sodium chloride,
At least one of potassium chloride, lithium chloride；It is further preferred that electrolyte is lithium chloride.
Preferably, in the preparation method of this photocuring selfreparing conductive hydrogel, photocuring is solid using LED-UV light
Change machine photocuring 5min~20min.
One kind photocuring selfreparing conductive hydrogel as made from aforementioned preparation process.
The beneficial effects of the present invention are:
The photocuring selfreparing conductive hydrogel that the present invention is prepared have safety it is good, without small molecule systems, mechanics
The advantages that intensity is good, gel conducts electricity very well.
It is specific as follows:
Natural polymer prepared by the present invention can not need to introduce other small molecule monomers by light-initiated formation gel
And photoinitiator.Urea groups pyrimidone block can form hydrogen bond structure in gel, enhance the mechanical strength of gel, make simultaneously
Obtaining gel has self-healing properties.By adding conductive materials etc. during gel-forming, forming one kind can be residual with monomer-free
Stay the electric conductivity hydrogel material that mechanical property is good.This gel structure had both had the advantages that physical gel good biocompatibility,
There is the structural stability of chemical crosslinking again.
Specific embodiment
The contents of the present invention are described in further detail below by way of specific embodiment.Original used in embodiment
Material unless otherwise specified, can be obtained from routine business approach.
The natural macromolecular material of chemical modification prepares embodiment 1
Side chain contains the gelatin-based natural macromolecular material system of unsaturated double-bond, urea groups pyrimidone block, light-initiated group
It is standby:
1, photoinitiator introduces isocyanates
The 4- dihydroxy benaophenonel for weighing 9g, is dissolved in n,N-Dimethylformamide, is gradually added dropwise in l5min at room temperature
100mL contains in the dimethyl formamide solution of 10g (60mmol) hexamethylene diisocyanate, adds containing 0.536g
N,N-Dimethylformamide solution 5mL and the 0.1mL dibutyl tin dilaurate of (4.5mmol) N methyldiethanol amine, 80
DEG C reaction 6h.Stop heating, be reduced to room temperature to reacting liquid temperature, reaction solution is poured into the n-hexane of 500mL and is precipitated, takes out
Filter, n-hexane, which rinses, repeatedly obtains product 4- (6- isocyano group hexylamino carboxyl) benzophenone, and weigh 8.5g.
2, the synthesis of 2 (6- isocyano group hexylamino carbonylamino) -6- methyl -4 [1H] pyrimidones
0.70mol 2- amino-4-hydroxy -6- methylpyrimidine is in the solution of 4.75mol hexamethylene diisocyanate at 100 DEG C
Heating 16 hours.Pentane is added to be precipitated, filters and is washed with pentane.Gained white powder is done at 50 DEG C under reduced pressure
It is dry.Superfluous hexamethylene diisocyanate is recycled with the way of distillation.Weighing: 174g.M.P.213℃.
3, gelatin side chain introduces a variety of functional groups
In 40 DEG C of configuration 20% gelatin (20g/mL) n,N-Dimethylformamide solution, pH value is adjusted to 10, under stiring
Be gradually added into 5% (quality relative to gelatin) methacrylic anhydride, 5% (quality relative to gelatin) 4- (6- isocyano group oneself
Base amino carboxyl) benzophenone n,N-Dimethylformamide solution, 5% (quality relative to gelatin) 2 (6- isocyano group hexyl
Amino carbonyl amino) -6- methyl -4 [1H] pyrimidone, reaction terminates after reacting 24 hours under nitrogen protection reacts, and decompression is steamed
It is dialysed 2~3 days removings small molecule objects and solvent after evaporating with distilled water, is freeze-dried and obtains side chain and contain unsaturated double-bond, urea groups
The gelatin-based natural macromolecular material of pyrimidone block, light-initiated group.
The natural macromolecular material of chemical modification prepares embodiment 2
Side chain contains the chitosan-based natural macromolecular material of unsaturated double-bond, urea groups pyrimidone block, light-initiated group
Preparation:
1, photoinitiator introduces isocyanates
The 4- dihydroxy benaophenonel for weighing 9g, is dissolved in n,N-Dimethylformamide, is gradually added dropwise in l5min at room temperature
100mL contains in the dimethyl formamide solution of 10g (60mmol) hexamethylene diisocyanate, adds containing 0.536g
N,N-Dimethylformamide solution 5mL and the 0.1mL dibutyl tin dilaurate of (4.5mmol) N methyldiethanol amine, 80
DEG C reaction 6h.Stop heating, be reduced to room temperature to reacting liquid temperature, reaction solution is poured into the n-hexane of 500mL and is precipitated, takes out
Filter, n-hexane, which rinses, repeatedly obtains product 4- (6- isocyano group hexylamino carboxyl) benzophenone, and weigh 8.5g.
2, the synthesis of 2 (6- isocyano group hexylamino carbonylamino) -6- methyl -4 [1H] pyrimidones
0.70mol 2- amino-4-hydroxy -6- methylpyrimidine is in the solution of 4.75mol hexamethylene diisocyanate at 100 DEG C
Heating 16 hours.Pentane is added to be precipitated, filters and is washed with pentane.Gained white powder is done at 50 DEG C under reduced pressure
It is dry.Superfluous hexamethylene diisocyanate is recycled with the way of distillation.Weighing: 174g.M.P.213℃.
3, chitosan side chain introduces a variety of functional groups
The chitosan dilute acetic acid solution of 3% chitosan is configured under room temperature, is adjusted pH value to 6, is gradually added under stiring
5% (quality relative to chitosan) methacrylic anhydride reacts 5 hours, is dialysed 2~3 days after vacuum distillation with distilled water, cold
Jelly is dried to obtain spongy whiteness, is dissolved in n,N-Dimethylformamide, adds the 5% (matter relative to chitosan
Amount) 4- (6- isocyano group hexylamino carboxyl) benzophenone n,N-Dimethylformamide solution, 5% (relative to chitosan
Quality) 2 (6- isocyano group hexylamino carbonylamino) -6- methyl -4 [1H] pyrimidones, reaction 24 is small under nitrogen protection for reaction
When after terminate reaction, dialysed 2~3 days removings small molecule objects and solvent after vacuum distillation with distilled water, be freeze-dried and obtain side chain
Containing unsaturated double-bond, urea groups pyrimidone block, light-initiated group chitosan-based natural macromolecular material, structural formula and reality
Apply the similar of example 1.
Photocuring selfreparing conductive hydrogel preparation example 1
Side chain made from embodiment 1 is contained to the gelatin-based day of unsaturated double-bond, urea groups pyrimidone block, light-initiated group
Right high molecular materialIt is configured to aqueous solution, and it is sweet
Oil, lithium chloride are uniformly mixed, and obtain mixed solution.Wherein, the mass concentration of natural macromolecular material is 20wt%, the matter of glycerol
Amount concentration is 20wt%, and the mass concentration of lithium chloride is 5wt%.Gained mixed liquor is used into LED-UV photo solidification machine photocuring
Thus 10min obtains photocuring selfreparing conduction gelatin based aquagel.
Through detecting, the photocuring selfreparing conduction gelatin based aquagel that the present embodiment is prepared is detected using rheometer,
Storage modulus is 6750Pa, loss modulus 580Pa.After the gel of the present embodiment is cut into two pieces, it can heal in 1 hour
At a monolith, reflect good self-healing performance.The gel biological safety that embodiment 1 obtains is good, no small molecule systems, power
Intensity is good, and gel conducts electricity very well.
It is the cylindric of 8cm that gelatin based aquagel, which is prepared into diameter, tests gel using Agilent LCR test set
Resistance, test value be 1530 Europe.Infrared test is carried out after gel freeze-drying, in 3340cm-1, 3066cm-1, 1700cm-1,
1650cm-1And 1540cm-1There is characteristic peak in place.
Photocuring selfreparing conductive hydrogel preparation example 2
By side chain made from embodiment 2 contain unsaturated double-bond, urea groups pyrimidone block, light-initiated group it is chitosan-based
Natural macromolecular materialIt is configured to aqueous solution, and it is sweet
Oil, lithium chloride are uniformly mixed, and obtain mixed solution.Wherein, the mass concentration of natural macromolecular material is 20wt%, the matter of glycerol
Amount concentration is 20wt%, and the mass concentration of lithium chloride is 5wt%.Gained mixed liquor is used into LED-UV photo solidification machine photocuring
Thus 10min obtains photocuring selfreparing conduction chitosan based aquagel.
Through detecting, the chitosan-based conductive hydrogel of photocuring selfreparing that the present embodiment is prepared is examined using rheometer
It surveys, storage modulus 6450Pa, loss modulus 530Pa.It can be with after the gel of the present embodiment is cut into two pieces, in 1 hour
A monolith is healed into, reflects good self-healing performance.The gel biological safety that embodiment 2 obtains is good, no small molecule body
System, mechanical strength is good, and gel conducts electricity very well.
It is the cylindric of 8cm that chitosan-based hydrogel, which is prepared into diameter, is tested using Agilent LCR test set solidifying
The resistance of glue, test value are 1420 Europe.Infrared test is carried out after gel freeze-drying, in 3340cm-1, 2918cm-1, 1704cm-1,
1658cm-1And 1573cm-1There is characteristic peak in place.
The present invention is prepared for the natural height that a kind of side chain contains unsaturated double-bond, urea groups pyrimidone block, light-initiated group
Molecule with can integrate photoinitiator, reaction monomers and one, while also having multiple hydrogen bonding group.This kind of conduction
Gel can be used in electrode for medical service etc..
Claims (10)
1. a kind of preparation method of the natural macromolecular material of chemical modification, it is characterised in that: the following steps are included:
1) photoinitiator that side chain contains hydroxyl is reacted with isocyanates, obtains the photoinitiator containing isocyanates；
2) pyrimidone derivatives are reacted with isocyanates, obtains urea groups pyrimidone；
3) by side chain contain amino natural polymers solution and alkenyl acid anhydrides, the photoinitiator containing isocyanates,
Urea groups pyrimidine reactive ketone, resulting product are dialysed, dry, obtain side chain contain unsaturated double-bond, urea groups pyrimidone block,
The natural macromolecular material of light-initiated group.
2. a kind of preparation method of the natural macromolecular material of chemical modification according to claim 1, it is characterised in that: step
It is rapid 1) in, side chain contain hydroxyl photoinitiator be 4- dihydroxy benaophenonel, 2,4-DihydroxyBenzophenone, 2- hydroxyl -4- first
Oxygroup benzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- hydroxyl -4- decyloxy benzophenone, 2- hydroxyl -4- 12
Alkoxy benzophenone, 2,2 '-dihydroxy -4- methoxy benzophenones, 2- hydroxyl -4- methoxyl group -2 '-carboxyl benzophenone,
2,2 '-dihydroxy -4,4 '-dimethoxy-benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenones, 2- hydroxyl -4- methoxyl group -5-
Diphenylsulfone ketone, 2,2 '-dihydroxy -4,4 '-dimethoxy -5- diphenylsulfone ketone, 2- hydroxy-2-methyl -1- are to hydroxyl second
At least one of base ether phenylacetone.
3. a kind of preparation method of the natural macromolecular material of chemical modification according to claim 1, it is characterised in that: step
It is rapid 2) in, pyrimidone derivatives are
4. a kind of preparation method of the natural macromolecular material of chemical modification according to claim 2 or 3, feature exist
In: in step 1) or step 2), isocyanates is hexamethylene diisocyanate, methyl diphenylene diisocyanate, 1,5- naphthalene
Diisocyanate, paraphenylene diisocyanate, isophorone diisocyanate, benzene dimethylene diisocyanate, toluene diisocyanate
Acid esters, methylcyclohexane diisocyanate, dicyclohexyl methyl hydride diisocyanate, in 1,4- cyclohexane diisocyanate at least
It is a kind of.
5. a kind of preparation method of the natural macromolecular material of chemical modification according to claim 1, it is characterised in that: step
It is rapid 3) in, it is phonetic that side chain contains the natural polymers of amino, alkenyl acid anhydrides, the photoinitiator containing isocyanates, urea groups
The mass ratio of pyridine ketone is 100:(1~10): (1~10): (1~10).
6. a kind of preparation method of the natural macromolecular material of chemical modification, feature exist according to claim 1 or 5
In: in step 3), the natural polymers that side chain contains amino be chitosan, chitosan derivatives, in gelatin at least
It is a kind of.
7. a kind of preparation method of the natural macromolecular material of chemical modification, feature exist according to claim 1 or 5
In: in step 3), alkenyl acid anhydrides is methacrylic anhydride.
8. a kind of natural macromolecular material of chemical modification, it is characterised in that: be by the preparation of any one of claim 1~7
Side chain made from method contains the natural macromolecular material of unsaturated double-bond, urea groups pyrimidone block, light-initiated group.
9. a kind of preparation method of photocuring selfreparing conductive hydrogel, it is characterised in that: by chemical modification described in claim 8
Natural macromolecular material be made solution, moisturizer and electrolyte is added, resulting mixed liquor carries out photocuring, forms photocuring
Selfreparing conductive hydrogel.
10. photocuring selfreparing conductive hydrogel made from a kind of preparation method as described in claim 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110258127A (en) * | 2019-05-27 | 2019-09-20 | 武汉纺织大学 | Thermoplastic polymer nanofiber tunica fibrosa or aerogel material of a kind of reversible selfreparing and preparation method thereof |
| CN110483804A (en) * | 2019-05-24 | 2019-11-22 | 深圳先进技术研究院 | Modified biopolymer and its application in 3D printing |
| CN112321760A (en) * | 2019-08-05 | 2021-02-05 | 天津大学 | Electrolyte material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140002123A (en) * | 2012-06-28 | 2014-01-08 | 조광페인트주식회사 | Paint composition for decorative sheet and manufacturing method of decorative sheet |
| CN105153359A (en) * | 2015-08-25 | 2015-12-16 | 东莞市万康医疗器械有限公司 | Conductive hydrogel, conductive hydrogel coil and their preparation methods |
| CN107636049A (en) * | 2015-04-02 | 2018-01-26 | 密歇根大学董事会 | From integration hydrogel and preparation method thereof |
-
2018
- 2018-12-14 CN CN201811529466.5A patent/CN109776817B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140002123A (en) * | 2012-06-28 | 2014-01-08 | 조광페인트주식회사 | Paint composition for decorative sheet and manufacturing method of decorative sheet |
| CN107636049A (en) * | 2015-04-02 | 2018-01-26 | 密歇根大学董事会 | From integration hydrogel and preparation method thereof |
| CN105153359A (en) * | 2015-08-25 | 2015-12-16 | 东莞市万康医疗器械有限公司 | Conductive hydrogel, conductive hydrogel coil and their preparation methods |
Non-Patent Citations (1)
| Title |
|---|
| 吕波: ""自引发纯丙烯酸酯的合成及光聚合性质研究"", 《精细与专用化学品》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483804A (en) * | 2019-05-24 | 2019-11-22 | 深圳先进技术研究院 | Modified biopolymer and its application in 3D printing |
| CN110258127A (en) * | 2019-05-27 | 2019-09-20 | 武汉纺织大学 | Thermoplastic polymer nanofiber tunica fibrosa or aerogel material of a kind of reversible selfreparing and preparation method thereof |
| CN112321760A (en) * | 2019-08-05 | 2021-02-05 | 天津大学 | Electrolyte material and preparation method and application thereof |
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