CN117683183A - Photo-curing flexible conductive polyurethane and preparation method and application thereof - Google Patents
Photo-curing flexible conductive polyurethane and preparation method and application thereof Download PDFInfo
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- CN117683183A CN117683183A CN202311740223.7A CN202311740223A CN117683183A CN 117683183 A CN117683183 A CN 117683183A CN 202311740223 A CN202311740223 A CN 202311740223A CN 117683183 A CN117683183 A CN 117683183A
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- polyurethane
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 100
- 239000004814 polyurethane Substances 0.000 title claims abstract description 100
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 40
- 229920000570 polyether Polymers 0.000 claims abstract description 40
- -1 acrylic ester Chemical class 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 33
- 150000001412 amines Chemical group 0.000 claims abstract description 29
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims abstract description 15
- 150000003077 polyols Chemical class 0.000 claims abstract description 15
- 238000001723 curing Methods 0.000 claims abstract description 14
- 239000000017 hydrogel Substances 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 38
- 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 35
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 24
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 13
- 238000012644 addition polymerization Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 10
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 9
- 238000006011 modification reaction Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001302 tertiary amino group Chemical group 0.000 claims description 4
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 3
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 claims description 3
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 claims description 3
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- BBAGPRAUWBSYDH-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)=O Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)=O BBAGPRAUWBSYDH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims description 3
- KCWDJXPPZHMEIK-UHFFFAOYSA-N isocyanic acid;toluene Chemical class N=C=O.N=C=O.CC1=CC=CC=C1 KCWDJXPPZHMEIK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 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 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 abstract description 10
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 20
- 239000012975 dibutyltin dilaurate Substances 0.000 description 20
- 238000010146 3D printing Methods 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 15
- 229920005749 polyurethane resin Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 7
- 238000007639 printing Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 230000035945 sensitivity Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of intelligent high polymer materials, and particularly provides a photo-curing flexible conductive polyurethane and a preparation method and application thereof, wherein the photo-curing flexible conductive polyurethane comprises 30g of modified polyurethane acrylic ester, 30-110 g of photo-curing monomer and 0.1-5 g of photoinitiator; the preparation method comprises the steps of preparing modified polyurethane acrylic ester, mixing the modified polyurethane acrylic ester, a photo-curing monomer and a photoinitiator, and stirring; the application of the photo-cured flexible conductive polyurethane in preparing the flexible sensor comprises the steps of preparing conductive hydrogel and infiltrating, curing and drying a photo-cured flexible polyurethane sample; the polyurethane prepolymer is prepared by taking diisocyanate, polyol and trimethylolpropane as raw materials; the polyether amine modified isophorone diisocyanate and hydroxyl-containing acrylic ester are added to jointly end-capped, so that a polyether amine side chain is grafted on polyurethane, and meanwhile, the tensile strength and elongation at break of the resin are improved.
Description
Technical Field
The invention relates to the technical field of intelligent high polymer materials, in particular to photo-curing flexible conductive polyurethane and a preparation method and application thereof.
Background
With flexible ion conductive materials, such as ionic hydrogels, conductive polyurethanes, there is a great deal of interest in the field of flexible wearable electronics. The conductive material has the advantages of continuity, high transparency, high stretchability and the like of a conductive medium, and has been widely applied to sensors, supercapacitors, lithium ion batteries and nano friction generators. The photo-curing polyurethane has no VOC emission in the production process, has high curing speed and simple process, and can be used for preparing flexible sensors used in extreme environments or for long-term monitoring. Meanwhile, the polyurethane material with multiple and precise structures can be obtained through 3D printing.
In the prior art, in order to obtain the conductivity meeting the actual requirement, the polyurethane needs to be subjected to conductive modification, but the polyurethane is also subjected to the modification, so that the mechanical property of the polyurethane is greatly reduced.
Thus, how to prepare a photo-cured flexible conductive polyurethane with good mechanical properties remains a great challenge.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a photo-cured flexible conductive polyurethane, and a preparation method and application thereof, which are used for solving the problem of the prior art that the mechanical properties of the modified polyurethane are greatly reduced.
According to the invention, the tensile strength and the elongation at break of polyurethane can be improved simultaneously by grafting a polyether amine branched chain on the polyurethane. The polyurethane in the invention is prepared by photo-curing 3D printing. The conductive properties of the polyurethane of the present invention are obtained by curing a layer of conductive hydrogel on the surface of the polyurethane. The photo-cured flexible conductive polyurethane prepared by the invention can be applied to flexible sensors to monitor various movements of human bodies.
To achieve the above and other related objects, the present invention provides a photo-curable flexible conductive polyurethane, comprising 30g of modified polyurethane acrylate, 30 to 110g of photo-curable monomer, and 0.1 to 5g of photo-initiator;
the modified polyurethane acrylate consists of diisocyanate, hydroxyl-terminated polyol, hydroxymethyl propane, isophorone diisocyanate modified by polyether amine and hydroxyl-containing (methyl) acrylate.
In an embodiment of the invention, the photo-curing monomer is at least one selected from acrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, isobornyl acrylate, N-acryloylmorpholine and decayl acrylate.
In one embodiment of the present invention, the initiator is at least one selected from the group consisting of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, ethyl (2, 4, 6-trimethylbenzoyl) phosphonate, benzophenone, isopropylthioxanthone, and 2, 4-dimethylthioxanthone.
In an embodiment of the present invention, the diisocyanate is at least one selected from toluene diisocyanate, hydrogenated phenyl methane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, phenyl methane diisocyanate;
the hydroxyl-terminated polyol is at least one selected from polytetrahydrofuran ether glycol, polyethylene glycol, polycarbonate glycol, polycaprolactone glycol and poly (neopentyl glycol adipate) glycol;
the isophorone diisocyanate modified by polyetheramine is prepared by semi-end capping modification of isophorone diisocyanate by polyetheramine;
the polyether amine is mono-amino end capped polyether amine with the molecular weight of 1000;
the hydroxyl-containing (methyl) acrylic ester is at least one selected from hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
A preparation method of photo-curing flexible conductive polyurethane is used for preparing the photo-curing flexible conductive polyurethane, and comprises the following steps:
s1, mixing diisocyanate and hydroxyl-terminated polyol in the presence of a catalyst, and performing gradual addition polymerization reaction to obtain isocyanate-terminated prepolymer 1;
s2, carrying out chain extension reaction on the prepolymer 1 and trimethylolpropane to obtain a prepolymer 2;
s3, polyether amine and isophorone diisocyanate are mixed according to the proportion of 1:1, mixing in proportion, and carrying out gradual addition polymerization reaction to obtain polyether amine modified isophorone diisocyanate;
s4, carrying out modification reaction on the prepolymer 2, isophorone diisocyanate modified by polyether amine and hydroxyl-containing acrylic ester, and adding a polymerization inhibitor during the modification reaction to obtain modified polyurethane acrylic ester;
s5, weighing the modified polyurethane acrylic ester, the photo-curing monomer and the photo-initiator, pouring the mixture into a stirrer, and uniformly stirring the mixture at a low speed under the condition of avoiding light.
In one embodiment of the invention, the catalyst is a tertiary amine or organometallic catalyst;
the polymerization inhibitor is selected from any one of hydroquinone and p-methoxyphenol;
in one embodiment of the present invention, in the step S1, the catalyst is used in an amount of 200 to 600ppm; the gradual addition polymerization reaction temperature is 40-80 ℃ and the reaction time is 1-3 h;
in the step S2, the temperature of the chain extension reaction is 60-90 ℃ and the reaction time is 1-3 h;
in the step S3, the dosage of the catalyst is 100-300 ppm; the gradual addition polymerization reaction temperature is 40-70 ℃ and the reaction time is 0.5-2 h;
in the step S4, the dosage of the polymerization inhibitor is 50-1000 ppm; the modification reaction temperature is 70-100 ℃ and the reaction time is 2-4 h.
In one embodiment of the invention, the molar ratio of diisocyanate, hydroxyl terminated polyol and trimethylolpropane is 1: (0.65-0.85): (0.25-0.5);
the molar ratio of the prepolymer 2 to the polyetheramine modified isophorone diisocyanate to the hydroxyl-containing acrylic ester is 3: (0-2): (1-3).
In one embodiment of the present invention, in step S5, the stirring speed of the stirrer is 300r/min.
Use of a photocurable flexible conductive polyurethane according to the above in the preparation of a flexible sensor, comprising the steps of:
1. preparing conductive hydrogel, which comprises mixing 1-20g of acrylamide, 8-160g of deionized water, 10-20% of PEG700DA, 1-5% of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone and 5-10% of lithium chloride, pouring into a stirrer, and uniformly stirring at a low speed under the condition of light shielding;
2. and (3) curing and drying the photo-cured flexible polyurethane sample after the photo-cured flexible polyurethane sample is treated in the conductive hydrogel in an infiltration mode.
As described above, the photo-curing flexible conductive polyurethane and the preparation method and application thereof have the following beneficial effects:
the polyurethane prepolymer is prepared by taking diisocyanate, polyol and trimethylolpropane as raw materials; the polyether amine modified isophorone diisocyanate and hydroxyl-containing acrylic ester are added to jointly end-capped, so that a polyether amine side chain is grafted on polyurethane, the tensile strength and elongation at break of the resin are improved, and good mechanical properties of the polyurethane are ensured while the polyurethane is modified.
Drawings
FIG. 1 is a graph showing the mechanical properties of the photocurable polyurethane resin prepared in example 4 of the present invention and comparative examples 1-2.
Fig. 2 is a schematic view of the mechanical properties of the 3D printing flexible polyurethane resin prepared in examples 4-8 of the present invention.
Fig. 3 is a sample graph of the photo-curable polyurethane resin prepared in example 6 of the present invention prepared by 3D printing.
Fig. 4 is a schematic diagram showing compression properties of a model prepared by 3D printing of the photo-curable polyurethane resin prepared in example 6 of the present invention.
FIG. 5 is a graph showing the various stresses detected by the piezoresistive sensor fabricated by the 3D printed photo-cured flexible conductive polyurethane model according to example 6 of the present invention.
Detailed Description
Further advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure of the present invention, which is described by the following specific examples.
Please refer to fig. 1 to 5. It should be understood that the structures, proportions, sizes, etc. shown in the drawings are for illustration purposes only and should not be construed as limiting the invention to the extent that it can be practiced, since modifications, changes in the proportions, or otherwise, used in the practice of the invention, are not intended to be critical to the essential characteristics of the invention, but are intended to fall within the spirit and scope of the invention.
The invention provides light-cured flexible conductive polyurethane, which comprises 30g of modified polyurethane acrylic ester, 30-110 g of light-cured monomer and 0.1-5 g of photoinitiator.
The modified polyurethane acrylic ester is composed of diisocyanate, hydroxyl-terminated polyol, hydroxymethyl propane, isophorone diisocyanate modified by polyether amine and hydroxyl-containing (methyl) acrylic ester; specifically, the diisocyanate is at least one selected from toluene diisocyanate, hydrogenated phenyl methane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and phenyl methane diisocyanate; the hydroxyl-terminated polyol is at least one selected from polytetrahydrofuran ether glycol, polyethylene glycol, polycarbonate glycol, polycaprolactone glycol and poly (neopentyl glycol adipate) glycol; the isophorone diisocyanate modified by polyetheramine is prepared by semi-end capping modification of isophorone diisocyanate by polyetheramine; the polyether amine is mono-amino end capped polyether amine with the molecular weight of 1000; the hydroxyl-containing (methyl) acrylic ester is at least one selected from hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The light-cured monomer is at least one selected from acrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, isobornyl acrylate, N-acryloylmorpholine and ten acrylate.
The initiator is at least one selected from (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, ethyl (2, 4, 6-trimethylbenzoyl) phosphonate, diphenyl ketone, isopropyl thioxanthone and 2, 4-dimethylthioxanthone.
The polyurethane prepolymer is prepared by taking diisocyanate, polyol and trimethylolpropane as raw materials; the polyether amine modified isophorone diisocyanate and hydroxyl-containing acrylic ester are added to jointly end-capped, so that a polyether amine side chain is grafted on polyurethane, the tensile strength and elongation at break of the resin are improved, and good mechanical properties of the polyurethane are ensured while the polyurethane is modified.
Embodiment 2, based on embodiment 1, this embodiment provides a method for preparing a photo-cured flexible conductive polyurethane, which is used for preparing the photo-cured flexible conductive polyurethane, and includes the following steps:
s1, mixing diisocyanate and hydroxyl-terminated polyol in the presence of a catalyst, and performing gradual addition polymerization reaction to obtain isocyanate-terminated prepolymer 1; the catalyst is tertiary amine or organic metal catalyst, and the dosage of the catalyst is 200-600 ppm; the gradual addition polymerization reaction temperature is 40-80 ℃ and the reaction time is 1-3 h;
s2, carrying out chain extension reaction on the prepolymer 1 and trimethylolpropane to obtain a prepolymer 2; the temperature of the chain extension reaction is 60-90 ℃ and the reaction time is 1-3 h;
s3, polyether amine and isophorone diisocyanate are mixed according to the proportion of 1:1, mixing in proportion, and carrying out gradual addition polymerization reaction to obtain polyether amine modified isophorone diisocyanate; the catalyst is tertiary amine or organic metal catalyst, and the dosage of the catalyst is 100-300 ppm; the gradual addition polymerization reaction temperature is 40-70 ℃ and the reaction time is 0.5-2 h;
s4, carrying out modification reaction on the prepolymer 2, isophorone diisocyanate modified by polyether amine and hydroxyl-containing acrylic ester, and adding a polymerization inhibitor during the modification reaction to obtain modified polyurethane acrylic ester; the polymerization inhibitor is selected from any one of hydroquinone and p-methoxyphenol, and the dosage of the polymerization inhibitor is 50-1000 ppm; the modification reaction temperature is 70-100 ℃ and the reaction time is 2-4 h;
s5, weighing the modified polyurethane acrylic ester, the photo-curing monomer and the photo-initiator, pouring the mixture into a stirrer, and uniformly stirring the mixture at a low speed under the condition of avoiding light; specifically, the stirring rotation speed of the stirrer is 300r/min.
In this example, the molar ratio of diisocyanate, hydroxyl terminated polyol and trimethylolpropane is 1: (0.65-0.85): (0.25-0.5); the molar ratio of the prepolymer 2 to the polyetheramine modified isophorone diisocyanate to the hydroxyl-containing acrylic ester is 3: (0-2): (1-3).
Example 3 based on examples 1 and 2, the application of the photo-cured flexible conductive polyurethane in preparing a flexible sensor according to the present embodiment includes the following steps:
1. preparing conductive hydrogel, which comprises mixing 1-20g of acrylamide, 8-160g of deionized water, 10-20% of PEG700DA, 1-5% of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone and 5-10% of lithium chloride, pouring into a stirrer, and uniformly stirring at a low speed under the condition of light shielding, wherein the stirring speed is 300r/min.
2. And (3) curing and drying the photo-cured flexible polyurethane sample after the photo-cured flexible polyurethane sample is treated in the conductive hydrogel in an infiltration mode.
Embodiment 4, based on embodiments 1 and 2, the present embodiment provides a method for preparing a photo-curable flexible conductive polyurethane, which includes the following steps:
s1, adding 39.96g (0.18 mol) of isophorone diisocyanate (IPDI) and 90g (0.09 mol) of polytetrahydrofuran ether glycol (PTMG) into a dry three-neck flask connected with a stirrer, a condenser and a thermometer; adding 0.073g of catalyst dibutyl tin dilaurate (DBTDL), heating to 45 ℃ at a speed of 3 ℃/min, and continuing to react for 2 hours after the temperature is reached to obtain a prepolymer 1;
s2, adding 6.03g (0.015 mol) of Trimethylolpropane (TMP), heating to 60 ℃, and continuously stirring for reaction for 3 hours to obtain a polyurethane prepolymer, namely prepolymer 2;
s3, adding 22.2g (0.1 mol) of IPDI and 100g (0.1 mol) of Polyetheramine (PEA) into a dry three-neck flask connected with a stirrer, a condenser and a thermometer; adding 0.015g of DBTDL, heating to 60 ℃ at 3 ℃/min, and reacting for 2 hours after the temperature is reached to obtain polyether amine modified isophorone diisocyanate (IPDI-PEA);
s4, adding 61.1g (0.05 mol) of IPDI-PEA obtained in the step (2) and 11.6g (0.1 mol) of hydroxyethyl acrylate (HEA) into the prepolymer in the step (1), and reacting at 80 ℃ for 3 hours to obtain polyether amine branched modified polyurethane acrylate (PUA-g-PEA-1);
s5, sequentially pouring 30g of PUA-g-PEA-1, 70g N-acryloylmorpholine, 0g of acrylic acid decaester and 1g of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide into a three-neck flask, and uniformly stirring at a low speed under a light-shielding condition to obtain the photocuring flexible polyurethane resin, wherein the stirring speed is 300r/min, and the stirring time is 2h.
Embodiment 5, this embodiment provides a method for preparing photo-curing flexible conductive polyurethane, which comprises the following steps:
s1, adding 39.96g (0.18 mol) of isophorone diisocyanate (IPDI) and 90g (0.09 mol) of polytetrahydrofuran ether glycol (PTMG) into a dry three-neck flask connected with a stirrer, a condenser and a thermometer; adding 0.073g of catalyst dibutyl tin dilaurate (DBTDL), heating to 45 ℃ at a speed of 3 ℃/min, and continuing to react for 2 hours after the temperature is reached to obtain a prepolymer 1;
s2, adding 6.03g (0.015 mol) of Trimethylolpropane (TMP), heating to 60 ℃, and continuously stirring for reaction for 3 hours to obtain a polyurethane prepolymer, namely prepolymer 2;
s3, adding 22.2g (0.1 mol) of IPDI and 100g (0.1 mol) of Polyetheramine (PEA) into a dry three-neck flask connected with a stirrer, a condenser and a thermometer; adding 0.015g of DBTDL, heating to 60 ℃ at 3 ℃/min, and reacting for 2 hours after the temperature is reached to obtain polyether amine modified isophorone diisocyanate (IPDI-PEA);
s4, adding 61.1g (0.05 mol) of IPDI-PEA obtained in the step (2) and 11.6g (0.1 mol) of hydroxyethyl acrylate (HEA) into the prepolymer in the step (1), and reacting at 80 ℃ for 3 hours to obtain polyether amine branched modified polyurethane acrylate (PUA-g-PEA-1);
s5, sequentially pouring 30g of PUA-g-PEA-1, 60g N-acryloylmorpholine, 10g of acrylic acid decaester and 1g of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide into a three-neck flask, and uniformly stirring at a low speed under a light-shielding condition to obtain the photocuring flexible polyurethane resin, wherein the stirring speed is 300r/min, and the stirring time is 2h.
Embodiment 6, this embodiment provides a method for preparing photo-curing flexible conductive polyurethane, which includes the following steps:
s1, adding 39.96g (0.18 mol) of isophorone diisocyanate (IPDI) and 90g (0.09 mol) of polytetrahydrofuran ether glycol (PTMG) into a dry three-neck flask connected with a stirrer, a condenser and a thermometer; adding 0.073g of catalyst dibutyl tin dilaurate (DBTDL), heating to 45 ℃ at a speed of 3 ℃/min, and continuing to react for 2 hours after the temperature is reached to obtain a prepolymer 1;
s2, adding 6.03g (0.015 mol) of Trimethylolpropane (TMP), heating to 60 ℃, and continuously stirring for reaction for 3 hours to obtain a polyurethane prepolymer, namely prepolymer 2;
s3, adding 22.2g (0.1 mol) of IPDI and 100g (0.1 mol) of Polyetheramine (PEA) into a dry three-neck flask connected with a stirrer, a condenser and a thermometer; adding 0.015g of DBTDL, heating to 60 ℃ at 3 ℃/min, and reacting for 2 hours after the temperature is reached to obtain polyether amine modified isophorone diisocyanate (IPDI-PEA);
s4, adding 61.1g (0.05 mol) of IPDI-PEA obtained in the step (2) and 11.6g (0.1 mol) of hydroxyethyl acrylate (HEA) into the prepolymer in the step (1), and reacting at 80 ℃ for 3 hours to obtain polyether amine branched modified polyurethane acrylate (PUA-g-PEA-1);
s5, sequentially pouring 30g of PUA-g-PEA-1, 50g N-acryloylmorpholine, 20g of acrylic acid decaester and 1g of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide into a three-neck flask, and uniformly stirring at a low speed under a light-shielding condition to obtain the photocuring flexible polyurethane resin, wherein the stirring speed is 300r/min, and the stirring time is 2h.
Embodiment 7, this embodiment provides a method for preparing photo-curing flexible conductive polyurethane, which includes the following steps:
s1, adding 39.96g (0.18 mol) of isophorone diisocyanate (IPDI) and 90g (0.09 mol) of polytetrahydrofuran ether glycol (PTMG) into a dry three-neck flask connected with a stirrer, a condenser and a thermometer; adding 0.073g of catalyst dibutyl tin dilaurate (DBTDL), heating to 45 ℃ at a speed of 3 ℃/min, and continuing to react for 2 hours after the temperature is reached to obtain a prepolymer 1;
s2, adding 6.03g (0.015 mol) of Trimethylolpropane (TMP), heating to 60 ℃, and continuously stirring for reaction for 3 hours to obtain a polyurethane prepolymer, namely prepolymer 2;
s3, adding 22.2g (0.1 mol) of IPDI and 100g (0.1 mol) of Polyetheramine (PEA) into a dry three-neck flask connected with a stirrer, a condenser and a thermometer; adding 0.015g of DBTDL, heating to 60 ℃ at 3 ℃/min, and reacting for 2 hours after the temperature is reached to obtain polyether amine modified isophorone diisocyanate (IPDI-PEA);
s4, adding 61.1g (0.05 mol) of IPDI-PEA obtained in the step (2) and 11.6g (0.1 mol) of hydroxyethyl acrylate (HEA) into the prepolymer in the step (1), and reacting at 80 ℃ for 3 hours to obtain polyether amine branched modified polyurethane acrylate (PUA-g-PEA-1);
s5, sequentially pouring 30g of PUA-g-PEA-1, 40g N-acryloylmorpholine, 30g of acrylic acid decaester and 1g of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide into a three-neck flask, and uniformly stirring at a low speed under a light-shielding condition to obtain the photocuring flexible polyurethane resin, wherein the stirring speed is 300r/min, and the stirring time is 2h.
Embodiment 8, this embodiment provides a method for preparing photo-curing flexible conductive polyurethane, which includes the following steps:
s1, adding 39.96g (0.18 mol) of isophorone diisocyanate (IPDI) and 90g (0.09 mol) of polytetrahydrofuran ether glycol (PTMG) into a dry three-neck flask connected with a stirrer, a condenser and a thermometer; adding 0.073g of catalyst dibutyl tin dilaurate (DBTDL), heating to 45 ℃ at a speed of 3 ℃/min, and continuing to react for 2 hours after the temperature is reached to obtain a prepolymer 1;
s2, adding 6.03g (0.015 mol) of Trimethylolpropane (TMP), heating to 60 ℃, and continuously stirring for reaction for 3 hours to obtain a polyurethane prepolymer, namely prepolymer 2;
s3, adding 22.2g (0.1 mol) of IPDI and 100g (0.1 mol) of Polyetheramine (PEA) into a dry three-neck flask connected with a stirrer, a condenser and a thermometer; adding 0.015g of DBTDL, heating to 60 ℃ at 3 ℃/min, and reacting for 2 hours after the temperature is reached to obtain polyether amine modified isophorone diisocyanate (IPDI-PEA);
s4, adding 61.1g (0.05 mol) of IPDI-PEA obtained in the step (2) and 11.6g (0.1 mol) of hydroxyethyl acrylate (HEA) into the prepolymer in the step (1), and reacting at 80 ℃ for 3 hours to obtain polyether amine branched modified polyurethane acrylate (PUA-g-PEA-1);
s5, sequentially pouring 30g of PUA-g-PEA-1, 30g N-acryloylmorpholine, 40g of acrylic acid decaester and 1g of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide into a three-neck flask, and uniformly stirring at a low speed under a light-shielding condition to obtain the photocuring flexible conductive polyurethane, wherein the stirring speed is 300r/min, and the stirring time is 2h.
Embodiment 9, based on embodiment 3, this embodiment provides a method for preparing a polyurethane sample by photo-curing 3D printing, comprising the steps of:
pouring the prepared photo-curing polyurethane resin into a resin groove of a DLP 3D printer for model printing, and setting printing parameters of 3D printing according to requirements;
after printing, placing the model into ethanol for ultrasonic cleaning for 10min, and then placing the model into an ultraviolet curing box for curing for 15min to finally obtain a 3D printing polyurethane product;
and thirdly, dip-coating the prepared 3D printing polyurethane part in the prepared conductive hydrogel solution for 30min, and then placing the prepared 3D printing polyurethane part in an ultraviolet curing box for curing for 1h to finally obtain the 3D printing photocuring flexible conductive polyurethane model.
Comparative example 1, this comparative example provides a process for the preparation of urethane acrylate comprising the steps of:
(1) 26.64g (0.12 mol) of isophorone diisocyanate (IPDI) and 60g (0.06 mol) of polytetrahydrofuran ether glycol (PTMG) were charged into a dry three-neck flask equipped with a stirrer, condenser, thermometer; 0.073g of catalyst dibutyl tin dilaurate (DBTDL) is added, the temperature is increased to 45 ℃ at 3 ℃/min, and after the temperature is reached, the reaction is continued for 2 hours; 6.96g (0.06 mol) of hydroxyethyl acrylate (HEA) is added, the temperature is raised to 65 ℃, and the polyurethane prepolymer is obtained after continuous stirring reaction for 3 hours;
(2) 2.68g (0.02 mol) of trimethylolpropane is added to the prepolymer of step (1) and reacted at 80℃for 3 hours to give a polyurethane acrylate (PUA-g-PEA-0) having no polyether amine segment. A step of
Comparative example 2, this comparative example provides a polyetheramine modified urethane acrylate comprising the steps of:
(1) 39.96g (0.18 mol) of isophorone diisocyanate (IPDI) and 90g (0.09 mol) of polytetrahydrofuran ether glycol (PTMG) were charged into a dry three-necked flask equipped with a stirrer, condenser, thermometer; 0.073g of catalyst dibutyl tin dilaurate (DBTDL) is added, the temperature is increased to 45 ℃ at 3 ℃/min, and after the temperature is reached, the reaction is continued for 2 hours; 6.03g (0.015 mol) of Trimethylolpropane (TMP) is added, the temperature is raised to 60 ℃, and the polyurethane prepolymer is obtained after continuous stirring reaction for 3 hours;
(2) 22.2g (0.1 mol) of IPDI and 100g (0.1 mol) of Polyetheramine (PEA) were charged into a dry three-necked flask equipped with a stirrer, a condenser and a thermometer; 0.015g of DBTDL was added and the temperature was raised to 60℃at 3℃per minute, after which the reaction was carried out for 2 hours to give polyetheramine-modified isophorone diisocyanate (IPDI-PEA).
(3) 122.2g (0.1 mol) of IPDI-PEA obtained in the step (2) and 5.8g (0.05 mol) of hydroxyethyl acrylate (HEA) are added into the prepolymer in the step (1), and the mixture is reacted for 3 hours at 80 ℃ to obtain polyether amine branched modified polyurethane acrylate (PUA-g-PEA-2).
Example 10 the mechanical properties of the polyurethane products prepared in comparative examples 1-2 and examples 4-8 were tested by mechanical stretching in this example as follows:
referring to fig. 1, fig. 1 shows the mechanical properties of the photo-cured flexible conductive polyurethane prepared in example 4 of the present invention compared with urethane acrylate prepared in comparative examples 1-2 with different polyether amine segment contents; as shown in fig. 1, as the content of polyetheramine in the polyurethane chain segment increases, the mechanical properties increase and decrease, which may be due to the fact that a proper amount of polyetheramine side chains provide more hydrogen bonds, thereby enhancing the toughening effect; and when the content of the polyether amine side chain is continuously increased, the content of double bonds is reduced, and the crosslinking density after curing is reduced, so that the mechanical property is reduced.
Referring to fig. 2, fig. 2 shows a comparative graph of curing depth and mechanical properties of the photo-curable 3D printing polyurethane resin prepared in examples 4 to 8 of the present invention; as can be seen from fig. 2, when the content of acryloylmorpholine is continuously reduced and the content of acrylic acid decaester is continuously increased, the flexibility of polyurethane can be gradually improved, but the higher reactivity of acryloylmorpholine can lead to the continuous reduction of the curing depth of resin, which is unfavorable for the subsequent model printing in a 3D printer.
Referring to fig. 3, fig. 3 shows a polyurethane sample of the photocurable resin system prepared in example 6 of the present invention by DLP type 3D printing. As can be seen from fig. 3, the photocurable resin system has good printing performance, and can be used for manufacturing a complex structural model with high precision, high resolution and smooth surface.
Referring to fig. 4, fig. 4 shows a cyclic loading-unloading curve of the 3D printed flexible polyurethane prepared in example 6 of the present invention; as can be seen from fig. 4, the 3D printing flexible polyurethane still has higher compression stress after 100 times of cyclic compression, and has better durability and rebound resilience.
Referring to fig. 5, fig. 5 shows a sensor manufactured by dip-coating a conductive hydrogel on the surface of the 3D printing flexible polyurethane prepared in example 6 of the present invention; as can be seen from FIG. 5, the sensor can detect various stress changes, and has high sensitivity.
Therefore, the photo-curing flexible conductive polyurethane prepared by the invention has better mechanical property (the tensile strength is 18.46MPa, and the elongation at break is 298%).
In conclusion, the photocuring flexible conductive polyurethane provided by the invention has the advantages of low viscosity, high curing speed, high activity and the like, is suitable for photocuring 3D printing equipment common in the market, and has high printing precision; the polyether amine modified polyurethane acrylic ester and the conductive hydrogel provided by the invention have the advantages of rich raw materials, simple and controllable synthesis process, low cost and the like, and are favorable for industrial production and application of resins and 3D printing models. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. A light-cured flexible conductive polyurethane, characterized in that: comprises 30g of modified polyurethane acrylic ester, 30-110 g of photo-curing monomer and 0.1-5 g of photoinitiator;
the modified polyurethane acrylate consists of diisocyanate, hydroxyl-terminated polyol, hydroxymethyl propane, isophorone diisocyanate modified by polyether amine and hydroxyl-containing (methyl) acrylate.
2. The light-curable flexible conductive polyurethane of claim 1, wherein: the light-cured monomer is at least one selected from acrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, isobornyl acrylate, N-acryloylmorpholine and ten acrylate.
3. The light-curable flexible conductive polyurethane of claim 1, wherein: the initiator is at least one selected from (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, ethyl (2, 4, 6-trimethylbenzoyl) phosphonate, diphenyl ketone, isopropyl thioxanthone and 2, 4-dimethylthioxanthone.
4. The light-curable flexible conductive polyurethane of claim 1, wherein: the diisocyanate is at least one selected from toluene diisocyanate, hydrogenated phenyl methane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and phenyl methane diisocyanate;
the hydroxyl-terminated polyol is at least one selected from polytetrahydrofuran ether glycol, polyethylene glycol, polycarbonate glycol, polycaprolactone glycol and poly (neopentyl glycol adipate) glycol;
the isophorone diisocyanate modified by polyetheramine is prepared by semi-end capping modification of isophorone diisocyanate by polyetheramine;
the polyether amine is mono-amino end capped polyether amine with the molecular weight of 1000;
the hydroxyl-containing (methyl) acrylic ester is at least one selected from hydroxyethyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
5. A method for preparing the photo-cured flexible conductive polyurethane, which is used for preparing the photo-cured flexible conductive polyurethane according to any one of claims 1 to 4, and is characterized by comprising the following steps:
s1, mixing diisocyanate and hydroxyl-terminated polyol in the presence of a catalyst, and performing gradual addition polymerization reaction to obtain isocyanate-terminated prepolymer 1;
s2, carrying out chain extension reaction on the prepolymer 1 and trimethylolpropane to obtain a prepolymer 2;
s3, polyether amine and isophorone diisocyanate are mixed according to the proportion of 1:1, mixing in proportion, and carrying out gradual addition polymerization reaction to obtain polyether amine modified isophorone diisocyanate;
s4, carrying out modification reaction on the prepolymer 2, isophorone diisocyanate modified by polyether amine and hydroxyl-containing acrylic ester, and adding a polymerization inhibitor during the modification reaction to obtain modified polyurethane acrylic ester;
s5, weighing the modified polyurethane acrylic ester, the photo-curing monomer and the photo-initiator, pouring the mixture into a stirrer, and uniformly stirring the mixture at a low speed under the condition of avoiding light.
6. The method for preparing the photo-curing flexible conductive polyurethane according to claim 5, wherein: the catalyst is tertiary amine or organic metal catalyst;
the polymerization inhibitor is selected from any one of hydroquinone and p-methoxyphenol.
7. The method for preparing the photo-curing flexible conductive polyurethane according to claim 6, wherein: in the step S1, the dosage of the catalyst is 200-600 ppm; the gradual addition polymerization reaction temperature is 40-80 ℃ and the reaction time is 1-3 h;
in the step S2, the temperature of the chain extension reaction is 60-90 ℃ and the reaction time is 1-3 h;
in the step S3, the dosage of the catalyst is 100-300 ppm; the gradual addition polymerization reaction temperature is 40-70 ℃ and the reaction time is 0.5-2 h;
in the step S4, the dosage of the polymerization inhibitor is 50-1000 ppm; the modification reaction temperature is 70-100 ℃ and the reaction time is 2-4 h.
8. The method for preparing the photo-curing flexible conductive polyurethane according to claim 5, wherein: the molar ratio of diisocyanate, hydroxyl terminated polyol and trimethylolpropane is 1: (0.65-0.85): (0.25-0.5);
the molar ratio of the prepolymer 2 to the polyetheramine modified isophorone diisocyanate to the hydroxyl-containing acrylic ester is 3: (0-2): (1-3).
9. The method for preparing the photo-curing flexible conductive polyurethane according to claim 5, wherein: in the step S5, the stirring rotating speed of the stirrer is 300r/min.
10. Use of a photocurable flexible conductive polyurethane according to any one of claims 1-4 for the preparation of a flexible sensor, characterized in that: the method comprises the following steps:
1. preparing conductive hydrogel, which comprises mixing 1-20g of acrylamide, 8-160g of deionized water, 10-20% of PEG700DA, 1-5% of photoinitiator 2-hydroxy-4- (2-hydroxyethoxy) -2-methyl propiophenone and 5-10% of lithium chloride, pouring into a stirrer, and uniformly stirring at a low speed under the condition of light shielding;
2. and (3) curing and drying the photo-cured flexible polyurethane sample after the photo-cured flexible polyurethane sample is treated in the conductive hydrogel in an infiltration mode.
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| CN115677969A (en) * | 2022-11-10 | 2023-02-03 | 江南大学 | UV (ultraviolet) curing self-repairing self-adhesive polyurethane resin and preparation method and application thereof |
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| CN109054623A (en) * | 2018-08-22 | 2018-12-21 | 广东昊辉新材料有限公司 | A kind of curable urethane acrylate aqueous dispersion and preparation method thereof |
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