CN114920904B - Preparation method and application of colorless transparent high-strength polyurethane anti-counterfeiting material - Google Patents
Preparation method and application of colorless transparent high-strength polyurethane anti-counterfeiting material Download PDFInfo
- Publication number
- CN114920904B CN114920904B CN202210607665.3A CN202210607665A CN114920904B CN 114920904 B CN114920904 B CN 114920904B CN 202210607665 A CN202210607665 A CN 202210607665A CN 114920904 B CN114920904 B CN 114920904B
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- Prior art keywords
- polyurethane
- diisocyanate
- tpe
- preparation
- colorless transparent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 149
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 148
- 239000000463 material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000004970 Chain extender Substances 0.000 claims abstract description 30
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 48
- 150000002009 diols Chemical class 0.000 claims description 41
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 25
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 25
- -1 polyhexamethylene carbonate Polymers 0.000 claims description 16
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 229920001610 polycaprolactone Polymers 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 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
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- 229920006264 polyurethane film Polymers 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 22
- 238000012360 testing method Methods 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 17
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 12
- 238000004220 aggregation Methods 0.000 description 9
- 230000002776 aggregation Effects 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- OOTFVKOQINZBBF-UHFFFAOYSA-N cystamine Chemical compound CCSSCCN OOTFVKOQINZBBF-UHFFFAOYSA-N 0.000 description 5
- 229940099500 cystamine Drugs 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229920003225 polyurethane elastomer Polymers 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- KYNFOMQIXZUKRK-UHFFFAOYSA-N 2,2'-dithiodiethanol Chemical compound OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000011527 polyurethane coating Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- DOXFBSZBACYHFY-UHFFFAOYSA-N phenol;stilbene Chemical group OC1=CC=CC=C1.C=1C=CC=CC=1C=CC1=CC=CC=C1 DOXFBSZBACYHFY-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
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- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Pathology (AREA)
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Abstract
The invention belongs to the technical field of synthesis of functional polymer materials, and discloses a preparation method of a colorless transparent high-strength polyurethane anti-counterfeiting material, which comprises the following steps: (1) Adding TPE-2OH and diisocyanate into a reaction container according to a proportion, reacting for 0.5-2h at 70-90 ℃, then adding macromolecular dihydric alcohol into a reaction system, and continuing to react for 1.5-3h at 70-90 ℃; (2) Cooling the reaction liquid obtained in the step (1) to 0-60 ℃, adding a catalyst and a solvent into the reaction liquid, uniformly mixing, then adding a chain extender into the reaction liquid, and continuously reacting for 1-4h at 40-60 ℃ to obtain the colorless transparent high-strength polyurethane anti-counterfeiting material. The polyurethane material prepared by the invention has high toughness and elasticity, high transparency and good fluorescence stability, and can be used for preparing optical anti-counterfeiting materials.
Description
Technical Field
The invention relates to the technical field of synthesis of functional polymer materials, in particular to a preparation method and application of a colorless transparent high-strength polyurethane anti-counterfeiting material.
Background
Polyurethane (PU) is a short form of Polyurethane, and has been invented by german scientist bayer et al in 1937, and is a synthetic polymer material with multiple uses. Polyurethane is a typical block polymer, can be prepared by reacting different isocyanates and polyols, and has wide application because of the variability of the monomers used, so that polyurethane materials with specific physical properties can be easily prepared. The material has excellent flexibility and toughness, wide hardness range, good tearing strength, good wear resistance, good chemical resistance, heat sealability and the like, and is widely applied to various fields of spinning, transportation, aerospace, chemical industry, electronics, medical treatment and the like at present.
In this information age, anti-counterfeiting is an important issue. Various anti-counterfeiting techniques have been studied, including radio frequency identification, bar codes, holograms, color shifting inks, scratch-off films, and the like. However, these methods have the disadvantages of complex synthesis, expensive materials, high equipment requirements, easy replication and the like. Therefore, optical anti-counterfeit materials, such as fluorescent materials, quantum dots, up-conversion materials, and the like, are receiving more and more attention, and they can easily overcome the above-mentioned drawbacks, and can be used for optical anti-counterfeit labels that can be observed by naked eyes. Among these materials and techniques, fluorescent polyurethanes are of great interest due to their excellent properties. However, most of the conventional fluorescent polyurethane materials currently have an aggregation-induced quenching (ACQ) effect, which greatly limits the application of the materials in an aggregated state. Although inorganic nanoparticles, such as quantum dots or up-conversion nanoparticles, can exhibit bright fluorescence and good light stability in combination with polyurethane, their heavy metal components are liable to cause toxicity problems, and also limit their further applications. Fortunately, the combination of a fluorescent agent with aggregation-induced emission characteristics with polyurethane overcomes the above problems well.
However, the existing anti-counterfeiting material prepared from aggregation-induced emission polyurethane is prone to defects of poor mechanical property, poor transparency, color, poor fluorescence stability and the like.
Disclosure of Invention
Aiming at the problems and the defects existing in the prior art, the invention aims to provide a preparation method and application of a colorless transparent high-strength polyurethane anti-counterfeiting material.
Based on the above purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a colorless transparent high-strength polyurethane anti-counterfeiting material, which comprises the following steps:
(1) Adding TPE-2OH and diisocyanate into a reaction container according to a proportion, reacting for 0.5-2h at 70-90 ℃, then adding macromolecular dihydric alcohol into the reaction container, and continuing to react for 1.5-3h at 70-90 ℃;
(2) Cooling the reaction liquid obtained in the step (1) to 0-60 ℃, adding a catalyst and a solvent into the reaction liquid, uniformly mixing, adding a chain extender, and reacting at 0-60 ℃ for 1-4 hours to obtain the colorless transparent high-strength polyurethane anti-counterfeiting material.
According to the above preparation method, preferably, the molar ratio of diisocyanate, macrodiol and chain extender is 2.1: (0.4-1): (1-1.6).
According to the preparation method, preferably, the mass ratio of the diisocyanate to the TPE-2OH is 1: (0.007 to 0.07).
According to the above-mentioned production method, preferably, the macrodiol is at least one of polyhexamethylene carbonate diol, polycaprolactone diol, and polytetramethylene ether diol. More preferably, the number average molecular weight of the macrodiol is 2000.
According to the above preparation method, preferably, the chain extender is at least one of 1, 4-butanediol, 1, 6-hexanediol, ethylene glycol, 3 '-dichloro-4, 4' -diphenylmethane diamine, ethylenediamine, 2-hydroxyethyl disulfide, and cystamine.
According to the preparation method, preferably, the preparation method of the TPE-2OH comprises the following steps: adding 4-hydroxybenzophenone and zinc powder into anhydrous tetrahydrofuran, and uniformly mixing to obtain a mixed solution; adding titanium tetrachloride into the mixed solution at the temperature of between 5 ℃ below zero and 5 ℃ under the atmosphere of protective gas, condensing and refluxing for 24 to 36 hours, and then adopting K 2 CO 3 Quenching the solution to react, and removing solid impurities by solid-liquid separation to obtain a reaction solution; and removing the solvent in the reaction liquid, and separating and purifying the reaction liquid to obtain TPE-2OH. More preferably, the reaction solution is separated and purified by column chromatography.
According to the above preparation method, preferably, the molar ratio of 4-hydroxybenzophenone, zinc powder and titanium tetrachloride is 1:4.4:2.2.
according to the above-mentioned production method, preferably, the diisocyanate in the step (1) is at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and diphenylmethane diisocyanate.
According to the above preparation method, preferably, in the step (2), the catalyst is an organotin catalyst, and the amount of the organotin catalyst is 0.1% of the total weight of the diisocyanate, the macrodiol and the chain extender. More preferably, the organotin catalyst is dibutyltin dilaurate.
According to the above preparation method, preferably, the solvent in the step (2) is N, N-dimethylacetamide.
The second aspect of the invention provides a colorless transparent high-strength polyurethane anti-counterfeiting material prepared by the preparation method of the first aspect.
The colorless transparent high-strength polyurethane anti-counterfeiting material prepared by the invention can be further prepared into a polyurethane film or a polyurethane coating. The preparation method of the polyurethane film comprises the following steps: pouring the colorless transparent high-strength polyurethane anti-counterfeiting material prepared by the preparation method in the first aspect into a mould (the mould is preferably a polytetrafluoroethylene mould), drying the mould in a vacuum drying oven at 60 ℃ for 3-5 days to remove the solvent, and then stripping the material from the mould to obtain the polyurethane elastomer; in order to obtain a bubble-free polyurethane film with uniform thickness, the obtained polyurethane elastomer is sheared and dissolved in N, N-dimethylacetamide (DMAc), and then added into a single-neck flask, and dissolved for 1-2 hours at 60 ℃ by using magnetic stirring to obtain a uniform and transparent polyurethane solution; and pouring the polyurethane solution into a mould (the mould is preferably a polytetrafluoroethylene mould), and putting the mould into a vacuum oven at 60 ℃ for drying until the weight is constant, thus obtaining the polyurethane film with uniform thickness and no bubbles. The preparation method of the polyurethane coating comprises the following steps: the colorless transparent high-strength polyurethane anti-counterfeiting material prepared by the preparation method of the first aspect is coated on a glass slide, and is placed in a vacuum drying oven at 60 ℃ for drying for 1-2 days, and the solvent is removed, so that the polyurethane coating is obtained.
The third aspect of the invention provides application of the colorless transparent high-strength polyurethane anti-counterfeiting material in anti-counterfeiting products.
Compared with the prior art, the invention has the positive beneficial effects that:
(1) The polyurethane prepared by the preparation method is colorless transparent high-strength AIE polyurethane, has a high linear structure, has better toughness and elasticity, has the tensile strength of up to 69.5MPa and the elongation at break of up to 1249 percent, and is far higher than the existing aggregation-induced emission polyurethane; in addition, the polyurethane prepared by the invention has high transparency, and the transmittance in the wavelength range of 400-600 nm reaches more than 85%, so that the technical problems of poor mechanical property, poor transparency and color of the existing aggregation-induced emission polyurethane are solved.
(2) The polyurethane prepared by the invention has very good fluorescence stability, and the fluorescence intensity does not occur in the environments of salt solutions with different concentrations and acid-base solutions with different pH valuesAnd (3) a change. Meanwhile, the polyurethane material can selectively detect Fe 3+ Fe at a concentration of 50. Mu.M 3+ The fluorescence of the polyurethane solution can be completely quenched, and the material is expected to be used as a chemical sensor. In addition, the material can meet the requirements of relief printing on different base materials such as paper, plastic, glass and the like, has very good fluorescence performance, and can be used as an anti-counterfeiting material with excellent performance.
(3) The polyurethane material prepared by the invention has high toughness and elasticity, high transparency and good fluorescence stability, and can be used for preparing optical anti-counterfeiting materials.
Drawings
FIG. 1 shows nuclear magnetic resonance hydrogen spectrum of 1, 2-bis (4-hydroxyphenyl) -1, 2-stilbene (TPE-2 OH) prepared in example 1 1 HNMR)；
FIG. 2 is a graph showing the DMF/H ratio of the polyurethane samples prepared in example 1 at different water contents 2 Fluorescence spectrum in O mixed solution;
FIG. 3 is a graph showing the effect of moisture content on fluorescence emission peak intensity in the polyurethane DMF solution prepared in example 1;
FIG. 4 is a graph showing fluorescence spectra of polyurethane samples prepared in example 1 under different pH environments;
FIG. 5 is a graph showing fluorescence spectra of polyurethane samples prepared in example 1 under different NaCl concentration environments;
FIG. 6 is a graph showing the fluorescence response of polyurethane samples prepared in example 1 to various metal ions;
FIG. 7 is a graph showing the concentration of Fe in polyurethane samples prepared in example 1 3+ Fluorescence spectrum under environment;
fig. 8 is a graph showing the printing effect of the polyurethane samples prepared in example 1 on different substrates.
Detailed Description
The present invention will be described in further detail by way of the following specific examples, which are not intended to limit the scope of the present invention.
One macromolecular dihydric alcohol type investigation experiment and TPE-2OH influence investigation
In order to investigate the influence of different macromolecular diols on the performance of the prepared colorless transparent high-strength polyurethane anti-counterfeiting material, the inventors performed examples 1 to 3 and comparative examples 1 to 3. The specific contents of examples 1 to 3 and comparative examples 1 to 3 are as follows:
example 1:
a preparation method of a colorless transparent high-strength polyurethane anti-counterfeiting material comprises the following steps:
(1) TPE-2OH and 1.76g (10.5 mmol) of Hexamethylene Diisocyanate (HDI) are added into a reaction vessel under the nitrogen atmosphere, stirred and reacted for 0.5h at 80 ℃, then macromolecular dihydric alcohol (macromolecular dihydric alcohol is dehydrated) is added into the reaction vessel, and the reaction is continued for 3h at 80 ℃; wherein the mass ratio of the diisocyanate to TPE-2OH is 1:0.007, wherein the macromolecular diol is polyhexamethylene carbonate diol (PC 2000).
(2) Cooling the reaction liquid obtained in the step (1) to 60 ℃, adding 0.01g of dibutyl tin dilaurate (DBTDL) and 20mL of N, N-dimethylacetamide (DMAc) into the reaction liquid, uniformly mixing, then dropwise adding a chain extender 1, 4-Butanediol (BDO) into the reaction liquid, and continuously reacting for 3 hours at 60 ℃ to obtain a colorless transparent high-strength polyurethane anti-counterfeiting material; wherein, the mole ratio of hexamethylene diisocyanate, macromolecular dihydric alcohol and chain extender is 2.1:1:1.
the preparation method of the TPE-2OH comprises the following steps: 2.0g (10 mmol) of 4-hydroxybenzophenone and zinc powder were dissolved in 100mL of anhydrous tetrahydrofuran to prepare a mixed solution, and titanium tetrachloride (TiCl) was introduced into the mixed solution under an ice bath and nitrogen atmosphere 4 ) The reaction flask was instilled in portions. After the injection is completed, the temperature of the system is raised to 78 ℃, and the system is condensed and refluxed for 24 hours. After the reaction was completed, 100mL of 10% (mass fraction: 10%) K was rapidly poured 2 CO 3 The solution is quenched and centrifuged to remove solid impurities. Extracting with dichloromethane, and spin-drying the solvent to obtain crude product. Finally, separating the crude product by a column chromatography method, and drying in vacuum to obtain 1, 2-di (4-hydroxy benzene) -1, 2-diphenyl ethylene (TPE-2 OH). Wherein, the mol ratio of the 4-hydroxybenzophenone to the zinc powder to the titanium tetrachloride is 1:4.4:2.2. the TPE-2OH 5mg prepared was dissolved in 0.5mL deuterated chloroform (CDCl) 3 ) In the method, after the ultrasonic treatment is carried out for 10min until the sample is completely dissolved, nuclear magnetism is usedA resonance spectrometer (NMR) was used for the test, and the test results are shown in fig. 1. As can be seen from FIG. 1, TPE-2OH was successfully prepared.
Example 2:
the content of example 2 is basically the same as that of example 1, except that:
the macromolecular diol in the step (2) is polycaprolactone diol (PCL 2000).
Example 3:
the content of example 3 is basically the same as that of example 1, except that:
the macromolecular diol in the step (2) is polytetramethylene ether glycol (PTMG 2000).
Comparative example 1:
the content of comparative example 1 is substantially the same as that of example 1 except that: TPE-2OH is not added in step (1).
The specific operation of the step (1) is as follows: under nitrogen atmosphere, 1.76g (10.5 mmol) of Hexamethylene Diisocyanate (HDI) was added into the reaction vessel, stirred at 80 ℃ for 0.5h, then the macromolecular diol (the macromolecular diol was dehydrated) was added into the reaction vessel, and reacted at 80 ℃ for 3h; wherein the macromolecular diol is polyhexamethylene carbonate diol (PC 2000).
Comparative example 2:
the content of comparative example 2 is substantially the same as that of example 2 except that: TPE-2OH is not added in step (1).
The specific operation of the step (1) is as follows: under nitrogen atmosphere, 1.76g (10.5 mmol) of Hexamethylene Diisocyanate (HDI) was added into the reaction vessel, stirred at 80 ℃ for 0.5h, then the macromolecular diol (the macromolecular diol was dehydrated) was added into the reaction vessel, and reacted at 80 ℃ for 3h; wherein the macromolecular diol is polycaprolactone diol (PCL 2000).
Comparative example 3:
the content of comparative example 3 is substantially the same as that of example 3 except that: TPE-2OH is not added in step (1).
The specific operation of the step (1) is as follows: under nitrogen atmosphere, 1.76g (10.5 mmol) of Hexamethylene Diisocyanate (HDI) was added into the reaction vessel, stirred at 80 ℃ for 0.5h, then the macromolecular diol (the macromolecular diol was dehydrated) was added into the reaction vessel, and reacted at 80 ℃ for 3h; wherein the macromolecular dihydric alcohol is polytetramethylene ether glycol (PTMG 2000).
In order to study the influence of different macromolecular diols and TPE-2OH on the performances of polyurethane materials prepared in examples 1-3 and comparative examples 1-3, the polyurethane materials prepared in the invention are prepared into polyurethane films, and the mechanical properties, transparency and fluorescence properties of the films are tested. The test results are shown in Table 1.
The method for preparing the polyurethane film from the polyurethane material comprises the following steps: pouring the polyurethane material into a mould (the mould is preferably a polytetrafluoroethylene mould), drying the mould in a vacuum drying oven at 60 ℃ for 3-5 days to remove the solvent, and then stripping the material from the mould to obtain a polyurethane elastomer; in order to obtain a bubble-free polyurethane film with uniform thickness, the obtained polyurethane elastomer is sheared and dissolved in N, N-dimethylacetamide (DMAc), and then added into a single-neck flask, and dissolved for 1-2 hours at 60 ℃ by using magnetic stirring to obtain a uniform and transparent polyurethane solution; and pouring the polyurethane solution into a mould (the mould is preferably a polytetrafluoroethylene mould), and putting the mould into a vacuum oven at 60 ℃ for drying until the weight is constant, thus obtaining the polyurethane film with uniform thickness and no bubbles.
The mechanical property test conditions are as follows: the polyurethane film was cut into standard dumbbell-shaped tensile bars (gauge length 13mm, width 2 mm), and its tensile properties were tested using an electronic universal tester at a tensile rate of 100mm/min, each sample was repeated 5 times, and the results averaged over 5 measurements.
The transparency test conditions were: cutting a polyurethane film into a size of 2cm multiplied by 4cm, placing the size on a film sample frame, and testing at room temperature by using an ultraviolet spectrophotometer to obtain an ultraviolet-visible light transmission spectrum of the polyurethane film, wherein the wavelength range is 400-600 nm, and the blank reference is air.
The fluorescent performance test conditions were: the polyurethane film is cut into 1cm multiplied by 2cm and fixed on a film sample frame, a fluorescence spectrometer is used for testing, the data acquisition wavelength is 1nm, and the spectrum scanning is carried out within the wavelength range of 400-600 nm.
TABLE 1 influence of macrodiols and TPE-2OH on polyurethane Properties
From table 1, from the viewpoint of mechanical properties, different macromolecular diols are selected in the experiment, and the mechanical properties of the prepared polyurethane film have obvious differences, wherein when PTMG2000 is used as the macromolecular diol, the tensile strength of the prepared polyurethane film is the minimum (27.1 MPa); when PC2000 is used as macromolecular dihydric alcohol, the tensile strength of the prepared polyurethane is maximum and reaches 69.5MPa, the elongation at break reaches 1249%, and the toughness reaches 373.6MJ/m 3 Therefore, the mechanical properties of the polyurethane film prepared by taking PC2000 as macromolecular dihydric alcohol are optimal by combining the tensile strength, the elongation at break and the toughness; from the perspective of light transmittance in a visible light region, when PC2000, PCL2000 and PTMG2000 are respectively selected as macromolecular dihydric alcohol, the prepared three different polyurethane films have high transparency, and the light transmittance in the visible light region of 400-600 nm can reach more than 80%, wherein when PC2000 and PTMG2000 are selected as macromolecular dihydric alcohol, the prepared polyurethane (example 1 and example 2) has higher transparency; from the aspect of fluorescence performance, when PC2000 is taken as macromolecular diol, the prepared polyurethane (PC type polyurethane) has the highest fluorescence intensity, and secondly, PCL type polyurethane prepared by taking PCL2000 as macromolecular diol, PTMG2000 is the weakest in fluorescence intensity; the reason is that ester groups exist in the PC type polyurethane soft segment, carbonyl groups exist in the PCL type polyurethane soft segment, ether groups exist in the PTMG type polyurethane soft segment, the formed intermolecular hydrogen bonds are respectively ester groups, carbonyl groups and ether groups from strong to weak, the stronger the hydrogen bond action is, the more difficult the introduced tetraphenyl ethylene dissipates energy through intermolecular movement, more energy dissipates through the form of light energy, and therefore the PC type polyurethane has the highest fluorescence intensity. Therefore, the mechanical property and the transmission in the visible light region are comprehensively consideredThe macromolecular dihydric alcohol is preferably PC2000, and the prepared polyurethane has high tensile property, high transparency and excellent fluorescence property.
In addition, as can be seen from Table 1, the introduction of TPE-2OH has little effect on the transparency of polyurethane, and mainly affects the fluorescence intensity and mechanical properties of polyurethane. From the aspect of fluorescence performance, when TPE-2OH is not added, the prepared polyurethane has lower fluorescence intensity at 500nm and does not have fluorescence performance.
From the mechanical property, the tensile strength and the elongation at break of PC type polyurethane (example 1 and comparative example 1) can be improved by the introduction of TPE-2OH, and compared with comparative example 1, the tensile strength of the polyurethane prepared in example 1 is improved by 13.6%, and the elongation at break is improved by 17.8%; the reason is that the tetraphenyl ethylene molecule is a rigid molecule with larger steric hindrance, the introduction of polyurethane can increase the rigidity of polyurethane molecular chains to a certain extent, and meanwhile, the access of molecules with large steric hindrance can also increase the distance between polyurethane molecular chains to a certain extent, so that the flexibility of the molecular chains is improved, and the mechanical property of PC type polyurethane is improved; the introduction of TPE-2OH increases the tensile strength and toughness of PCL-type polyurethanes (example 2 and comparative example 2), but decreases the elongation at break. The reason is that the introduction of the tetraphenyl ethylene molecules increases the rigidity of the PCL type polyurethane molecular chain to a certain extent, so that the tensile strength and the toughness are improved, but the introduction of the tetraphenyl ethylene molecules also damages the PCL type polyurethane crystal structure to a certain extent, and the elongation at break is reduced; the introduction of TPE-2OH reduced the tensile strength and toughness of PTMG type polyurethanes (example 3 and comparative example 3) and increased the elongation at break. The reason is that the main functional groups in PTMG polyurethane molecular chain are only carbamate groups and ether groups, and the PTMG polyurethane molecular chain is a highly linear molecular structure, and the regularity of the molecular chain has a great relation with the mechanical strength. The introduction of the tetraphenyl ethylene molecules damages the regularity of PTMG type polyurethane molecular chains to a certain extent, and the mechanical properties of the PTMG type polyurethane molecular chains are reduced.
(II) discussion of chain extender type experiments and discussion of TPE-2OH influence
To investigate the effect of different chain extenders on the properties of the prepared colorless transparent high-strength polyurethane anti-counterfeiting material, the inventors conducted experiments of examples 4 to 6 and comparative examples 4 to 6. The specific contents of examples 4 to 6 and comparative examples 4 to 6 are as follows:
example 4:
the content of example 4 is substantially the same as that of example 1, except that:
the chain extender added in step (2) is 1, 6-Hexanediol (HDO).
Example 5:
the content of example 5 is substantially the same as that of example 1, except that:
the chain extender added in step (2) is 2-hydroxyethyl disulfide (HEDS).
Example 6:
the content of example 6 is substantially the same as that of example 1, except that:
in the step (2), no catalyst is added in the reaction process, and the added chain extender is Cystamine (CY).
The step (2) comprises the following steps: cooling the reaction liquid obtained in the step (1) to 0 ℃, adding 20mL of N, N-dimethylacetamide (DMAc) into the reaction liquid, uniformly mixing, adding chain extender Cystamine (CY) into the reaction liquid, and reacting for 2 hours at 0 ℃ to obtain a colorless transparent high-strength polyurethane anti-counterfeiting material; wherein, the mole ratio of hexamethylene diisocyanate, macromolecular dihydric alcohol and chain extender is 2.1:1:1.
comparative example 4:
the content of comparative example 4 is substantially the same as that of example 4, except that: TPE-2OH is not added in step (1).
The specific operation of the step (1) is as follows: under nitrogen atmosphere, 1.76g (10.5 mmol) of Hexamethylene Diisocyanate (HDI) was added into the reaction vessel, stirred at 80 ℃ for 0.5h, then the macromolecular diol (the macromolecular diol was dehydrated) was added into the reaction vessel, and reacted at 80 ℃ for 3h; wherein the macromolecular diol is polyhexamethylene carbonate diol (PC 2000).
Comparative example 5:
the content of comparative example 5 is substantially the same as that of example 5 except that: TPE-2OH is not added in step (1).
The specific operation of the step (1) is as follows: under nitrogen atmosphere, 1.76g (10.5 mmol) of Hexamethylene Diisocyanate (HDI) was added into the reaction vessel, stirred at 80 ℃ for 0.5h, then the macromolecular diol (the macromolecular diol was dehydrated) was added into the reaction vessel, and reacted at 80 ℃ for 3h; wherein the macromolecular diol is polyhexamethylene carbonate diol (PC 2000).
Comparative example 6:
the content of comparative example 6 is substantially the same as that of example 6, except that: TPE-2OH is not added in step (1).
The specific operation of the step (1) is as follows: under nitrogen atmosphere, 1.76g (10.5 mmol) of Hexamethylene Diisocyanate (HDI) was added into the reaction vessel, stirred at 80 ℃ for 0.5h, then the macromolecular diol (the macromolecular diol was dehydrated) was added into the reaction vessel, and reacted at 80 ℃ for 3h; wherein the macromolecular diol is polyhexamethylene carbonate diol (PC 2000).
In order to study the influence of different chain extenders and TPE-2OH on the properties of polyurethane materials prepared in example 1, example 4 to example 6 and comparative examples 4 to 6, the polyurethane materials prepared in the above were prepared into polyurethane films (the preparation method of the polyurethane films is the same as that of example 1), and the mechanical properties, transparency and fluorescence properties of the films were tested (the test method is the same as that of example 1). The test results are shown in Table 2.
TABLE 2 impact of chain extender and TPE-2OH on polyurethane Properties
As can be seen from Table 2, the transparency of the polyurethane prepared from different chain extenders is not greatly different and can reach more than 95%, but the fluorescence performance and the mechanical property are obviously different; polyurethane materials (example 1 and example 4) prepared by using 1, 4-butanediol (HDO) and 1, 6-Hexanediol (HDO) as chain extenders have better mechanical properties and fluorescence properties. The reason is that the polyurethane samples prepared in the examples 1 and 4 have relatively obvious strong hydrogen bonding action between molecular chains, so that the phenyl groups of TPE-OH are difficult to rotate freely, more energy can be dissipated in the form of light energy, and the polyurethane samples have relatively high mechanical strength and fluorescence strength; whereas example 1 had stronger intermolecular hydrogen bonds than example 4, example 1 had the best mechanical and fluorescent properties. In addition, the polyurethane samples prepared in example 5 and example 6 have lower mechanical strength and fluorescence strength because of the presence of disulfide bond structure in the chain extender, resulting in reduced hydrogen bonding between molecular chains.
Mass ratio of diisocyanate to TPE-2OH
In order to study the influence of the mass ratio of diisocyanate to TPE-2OH on the performance of the prepared colorless transparent high-strength polyurethane anti-counterfeiting material, the inventors conducted experiments of examples 7 to 8.
Example 7:
the content of example 7 is substantially the same as that of example 1, except that: the mass ratio of the diisocyanate to the TPE-2OH in the step (1) is 1:0.021.
Example 8:
the content of example 8 is substantially the same as that of example 1, except that: the mass ratio of diisocyanate to TPE-2OH in the step (1) is 1:0.035.
In order to investigate the influence of the mass ratio of diisocyanate to TPE-2OH on the properties of the polyurethane materials prepared in examples 1, 7 and 8, the polyurethane materials prepared as described above were prepared into polyurethane films (the preparation method of the polyurethane films is the same as that of example 1), and the mechanical properties, transparency and fluorescence properties of the films were tested (the test method is the same as that of example 1). The test results are shown in Table 3.
TABLE 3 influence of the mass ratio of HDI to TPE-2OH on polyurethane Properties
As is clear from Table 3, the tensile strength and elongation at break of the polyurethane gradually decrease with the addition of TPE-2OH, because the introduction of tetraphenyl ethylene molecules breaks the regularity of the polyurethane molecular chain to some extent, resulting in a decrease in mechanical properties. In addition, with the increase of the addition amount of TPE-2OH, the fluorescence intensity of polyurethane is gradually increased, the quenching effect (ACQ) caused by aggregation does not appear, and the polyurethane has excellent fluorescence performance as shown in the case that most organic and inorganic fluorescent materials, such as carbon quantum dots and the like, can only be used under the condition of low concentration. As can be seen from comparison of examples 1, 7 and 8, when the mass ratio of HDI to TPE-2OH is 1:0.007, the mass of TPE-2OH used is the least, the cost of preparing polyurethane is the lowest, and the mechanical properties of polyurethane are the highest, and the polyurethane has excellent transparency and fluorescence intensity. Therefore, considering the mechanical properties and cost in combination, the mass ratio of HDI to TPE-2OH is preferably 1:0.007.
Molar ratio of diisocyanate, macrodiol and chain extender
In order to study the influence of the mass ratio of diisocyanate, macromolecular diol and chain extender on the performance of the prepared colorless transparent high-strength polyurethane anti-counterfeiting material, the inventor performs an experiment of example 9.
Example 9:
a preparation method of a colorless transparent high-strength polyurethane anti-counterfeiting material comprises the following steps:
(1) TPE-2OH and 1.76g (10.5 mmol) of Hexamethylene Diisocyanate (HDI) are added into a reaction vessel under the nitrogen atmosphere, stirred and reacted for 0.5h at 80 ℃, then macromolecular dihydric alcohol (macromolecular dihydric alcohol is dehydrated) is added into the reaction system, and the reaction is continued for 3h at 80 ℃; wherein the mass ratio of the diisocyanate to the TPE-2OH is 1:0.007, and the macromolecular diol is polyhexamethylene carbonate diol (PC 2000).
(2) Cooling the reaction liquid obtained in the step (1) to 60 ℃, adding 0.01g of dibutyl tin dilaurate (DBTDL) and 20mL of N, N-dimethylacetamide (DMAc) into the reaction liquid, uniformly mixing, then dropwise adding a chain extender 1, 4-Butanediol (BDO) into the reaction liquid, and continuously reacting for 3 hours at 60 ℃ to obtain a colorless transparent high-strength polyurethane anti-counterfeiting material; wherein the molar ratio of hexamethylene diisocyanate, polyhexamethylene carbonate diol and 1, 4-butanediol is 2.1:0.4:1.6.
in order to investigate the influence of mass ratio of diisocyanate, macrodiol and chain extender on the performance of the polyurethane materials prepared in example 1 and example 9, the polyurethane materials prepared as described above were prepared into polyurethane films (the preparation method of the polyurethane films is the same as that of example 1), and the mechanical properties, transparency and fluorescence properties of the films were tested (the test method is the same as that of example 1). The test results are shown in Table 4.
TABLE 4 influence of the molar ratios of diisocyanate, macrodiol and chain extender on polyurethane Properties
As is clear from Table 4, the mechanical properties and fluorescence intensity of polyurethane decreased with increasing proportion of chain extender. Thus, the molar ratio of hexamethylene diisocyanate, polyhexamethylene carbonate diol and 1, 4-butanediol is preferably 2.1:1:1.
(V) characterization of the colorless transparent high-strength polyurethane anti-counterfeiting material prepared by the invention:
according to the invention, through the discussion of macromolecular dihydric alcohol types, chain extender types, mass ratio of diisocyanate to TPE-2OH and the like, an optimal experimental scheme of the example 1 is finally determined, and the colorless and transparent high-strength polyurethane anti-counterfeiting material prepared in the example 1 is subjected to performance characterization, and specific characterization and results thereof are shown below.
1. Polyurethane aggregation-induced emission performance analysis
In order to investigate the aggregation-induced emission properties of polyurethane, the present invention conducted a liquid fluorescence test on the polyurethane prepared in example 1. The specific method for testing comprises the following steps: 1g of polyurethane was dissolved in 10mL of a chromatographically pure grade N, N-Dimethylformamide (DMF) solution to prepare primarily 100mg/mL of polyurethane solution. The polyurethane solution was transferred into 10mL sample bottles in ten equal parts, and appropriate amounts of DMF and water were added with vigorous stirring to obtain 10mg/mL polyurethane solutions of different moisture contents (0-90 vol%). The fluorescence performance of the solution is tested by using a fluorescence spectrometer, the data acquisition wavelength is 1nm, the excitation wavelength is 320nm, and the spectrum scanning is carried out within the wavelength range of 400-600 nm. The test results are shown in fig. 2 and 3.
As can be seen from fig. 2 and 3, the fluorescence intensity of the polyurethane solution gradually increases with the increase of the moisture content in the solution, demonstrating that the polyurethane prepared according to the present invention has excellent aggregation-induced emission properties.
2. Analysis of acid-alkali resistance and salt resistance of polyurethane
In order to explore the influence of acid-base salts on the fluorescence performance of polyurethane, the invention tests the liquid fluorescence of the polyurethane prepared in example 1 under the environments of different pH and different concentration salt solutions. The specific method for testing comprises the following steps: 2g of polyurethane was dissolved in 20mL of a chromatographically pure grade N, N-Dimethylformamide (DMF) solution to prepare initially 100mg/mL of polyurethane solution. The polyurethane solution was transferred into a 10mL sample bottle in twenty aliquots, to which were added 8mL of DMF solution and 1mL of deionized water solution to give 10mg/mL polyurethane solutions of varying moisture content (10 vol%). NaCl solutions (C=0.5-3M) with different concentrations and acid-base with different pH values (1-12) are prepared, and then 1mL of the NaCl solutions are respectively dripped into the prepared polyurethane solutions to measure the fluorescence intensity of the NaCl solutions. The data acquisition wavelength is 1nm, the excitation wavelength is 365nm, and the spectrum scanning is carried out within the wavelength range of 400-600 nm. The test results are shown in fig. 4 and 5.
As can be seen from fig. 4 and 5, the prepared polyurethane has very good fluorescence stability, and the fluorescence intensity does not change significantly in the environments of salt solutions with different concentrations and acid-base solutions with different pH.
3. Polyurethane ion detection performance analysis
In order to explore the influence of metal ions on the fluorescence performance of polyurethane, the invention tests the liquid fluorescence of polyurethane prepared in example 1 under different metal ion environments. The specific test process is as follows:2g of polyurethane was dissolved in 20mL of a chromatographically pure grade N, N-Dimethylformamide (DMF) solution to prepare initially 100mg/mL of polyurethane solution. The polyurethane solution was transferred into a 10mL sample bottle in twenty aliquots, to which were added 8mL of DMF solution and 1mL of deionized water solution to give 10mg/mL polyurethane solutions of varying moisture content (10 vol%). Then the hydrochloride is taken as a cation source to prepare K with the concentration of 0.5mol/L + 、Na + 、Al 3+ 、Co 2+ 、Cu 2+ 、Fe 3+ 、Mg 2+ 、Ni 2+ 、Zn 3+ 、Ca 2+ An aqueous solution of metal ions. Then, 100 mu L of metal ion solution is respectively dripped into the prepared polyurethane solution, the fluorescence performance of the polyurethane solution is tested by a fluorescence spectrometer, the excitation wavelength is 365nm, and the spectrum scanning is carried out within the wavelength range of 400-600 nm. The results are shown in fig. 6 and 7.
As can be seen from FIGS. 6 and 7, the polyurethane material can selectively detect Fe 3+ Fe at a concentration of 50. Mu.M 3+ The fluorescence of the polyurethane solution can be completely quenched, which shows that the polyurethane solution has great potential application value in the field of ion detection.
4. Polyurethane anti-counterfeiting performance analysis
In order to explore the application of the polyurethane in anti-counterfeiting paint, the anti-counterfeiting performance test is carried out on the polyurethane prepared in the embodiment 1, and the specific test process is as follows: 1g of the prepared polyurethane film is sheared and dissolved in 10mL of chloroform to prepare polyurethane solution, and the polyurethane solution is transferred onto different base materials such as paper, plastic, glass and the like by using a heart-shaped seal, and the specific effect is shown in figure 8.
As can be seen from FIG. 8, the polyurethane solution can meet the requirements of relief printing on different base materials such as paper, plastic, glass and the like, and has very good fluorescence performance, which shows that the polyurethane solution has good market prospect in the anti-counterfeiting field.
The above-described embodiments are provided to illustrate the gist of the present invention, but are not intended to limit the scope of the present invention. It will be understood by those skilled in the art that various modifications and equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (6)
1. The preparation method of the colorless transparent high-strength polyurethane anti-counterfeiting material is characterized by comprising the following steps of:
(1) Adding TPE-2OH and diisocyanate into a reaction container according to a proportion, reacting for 0.5-2h at 70-90 ℃, then adding macromolecular dihydric alcohol into the reaction container, and continuing to react for 1.5-3h at 70-90 ℃; the macromolecular dihydric alcohol is polyhexamethylene carbonate dihydric alcohol or polycaprolactone diol, and the TPE-2OH is 1, 2-bis (4-hydroxyphenyl) -1, 2-stilbene;
(2) Cooling the reaction liquid obtained in the step (1) to 0-60 ℃, adding a catalyst and a solvent into the reaction liquid, uniformly mixing, adding a chain extender, and reacting at 0-60 ℃ for 1-4 hours to obtain a colorless transparent high-strength polyurethane anti-counterfeiting material; wherein the molar ratio of diisocyanate, macromolecular dihydric alcohol and chain extender is 2.1:1:1; the mass ratio of the diisocyanate to TPE-2OH is 1: (0.007 to 0.07), wherein the chain extender is 1, 4-butanediol or 1, 6-hexanediol.
2. The preparation method of the TPE-2OH according to claim 1, wherein the preparation method comprises the following steps: adding 4-hydroxybenzophenone and zinc powder into anhydrous tetrahydrofuran, and uniformly mixing to obtain a mixed solution; adding titanium tetrachloride into the mixed solution at the temperature of between 5 ℃ below zero and 5 ℃ under the atmosphere of protective gas, condensing and refluxing for 24 to 36 hours, and then adopting K 2 CO 3 Quenching the solution to react, and removing solid impurities by solid-liquid separation to obtain a reaction solution; and removing the solvent in the reaction liquid, and separating and purifying the reaction liquid to obtain TPE-2OH.
3. The preparation method according to claim 2, wherein the molar ratio of 4-hydroxybenzophenone, zinc powder and titanium tetrachloride is 1:4.4:2.2.
4. the method according to claim 3, wherein the diisocyanate in the step (1) is at least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and diphenylmethane diisocyanate; the catalyst in the step (2) is an organotin catalyst, and the dosage of the organotin catalyst accounts for 0.1 percent of the total weight of diisocyanate, macromolecular dihydric alcohol and chain extender; the solvent is N, N-dimethylacetamide.
5. A colorless transparent high-strength polyurethane anti-counterfeiting material prepared by the preparation method of any one of claims 1 to 4.
6. The use of the colorless transparent high-strength polyurethane anti-counterfeiting material as claimed in claim 5 in anti-counterfeiting products.
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