CN116284651B - Method for preparing high-performance quantum dot composite material by using imidazole derivative - Google Patents
Method for preparing high-performance quantum dot composite material by using imidazole derivative Download PDFInfo
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- CN116284651B CN116284651B CN202211093524.0A CN202211093524A CN116284651B CN 116284651 B CN116284651 B CN 116284651B CN 202211093524 A CN202211093524 A CN 202211093524A CN 116284651 B CN116284651 B CN 116284651B
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- quantum dot
- monomer
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- imidazole derivative
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 150000002460 imidazoles Chemical class 0.000 title claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 66
- 238000005286 illumination Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 3
- 229920006295 polythiol Polymers 0.000 claims description 29
- 239000005056 polyisocyanate Substances 0.000 claims description 21
- 229920001228 polyisocyanate Polymers 0.000 claims description 21
- 230000004888 barrier function Effects 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000011159 matrix material Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 13
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 3
- 229920006037 cross link polymer Polymers 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 15
- 238000006862 quantum yield reaction Methods 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000012948 isocyanate Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 abstract description 5
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 150000002513 isocyanates Chemical class 0.000 abstract description 4
- 150000003573 thiols Chemical class 0.000 abstract description 4
- 230000000903 blocking effect Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- -1 1-dimethylethyl Chemical group 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 10
- 239000007983 Tris buffer Substances 0.000 description 6
- 150000004291 polyenes Chemical class 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007429 general method Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- CFKONAWMNQERAG-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis[2-(3-sulfanylpropanoyloxy)ethyl]-1,3,5-triazinan-1-yl]ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCN1C(=O)N(CCOC(=O)CCS)C(=O)N(CCOC(=O)CCS)C1=O CFKONAWMNQERAG-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 description 1
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 description 1
- YAAUVJUJVBJRSQ-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2-[[3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propoxy]methyl]-2-(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS YAAUVJUJVBJRSQ-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- OLFGELRSPCAAOJ-UHFFFAOYSA-N butyl 3-sulfanylbutanoate Chemical compound CCCCOC(=O)CC(C)S OLFGELRSPCAAOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 238000012733 comparative method Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- QEBJRRFIWCWPMA-UHFFFAOYSA-N diethyl-bis(sulfanyl)-$l^{4}-sulfane Chemical compound CCS(S)(S)CC QEBJRRFIWCWPMA-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G18/52—Polythioethers
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
- C09K11/562—Chalcogenides
- C09K11/565—Chalcogenides with zinc cadmium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
- C09K11/701—Chalcogenides
- C09K11/703—Chalcogenides with zinc or cadmium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/883—Chalcogenides with zinc or cadmium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
- C08K2003/3036—Sulfides of zinc
Abstract
The invention relates to a method for preparing a high-performance quantum dot composite material by using imidazole derivatives, which is characterized in that in a system of thiol, isocyanate and alkene, the imidazole derivatives of an illumination and latent base catalyst are sequentially used for polymerization and curing, so that the method is favorable for controlling the curing heat of high-quality quantum dot products, realizing uniform curing process among monomers, and the prepared quantum dot composite material has excellent capability of blocking water and oxygen, can prolong the service life of the quantum dot products and has higher quantum yield.
Description
Technical Field
The invention relates to a method for preparing a high-performance quantum dot composite material by using an imidazole derivative, in particular to a method for preparing a quantum dot composite material with a mercaptan-alkene-isocyanate matrix by using the imidazole derivative as a latent base.
Background
The quantum dot display has the advantages of wide color gamut, vivid display color and the like, but the preparation process of the quantum dot is complex, and restricts the development of industry, specifically, for example, the general structure of a quantum dot film product is that a barrier layer carries out sandwich type encapsulation on a quantum dot luminous layer, and the outermost side is a diffusion layer with a light diffusion function, wherein the quantum dot luminous layer disperses quantum dots in a polymer matrix to avoid the damage of oxygen or water. Polymer matrices generally have a high light transmittance, wherein click reactions involving thiols are widely used in the preparation of such polymer matrices. Among them, a polymerization system using thiol, isocyanate and alkene as functional monomers is reported, but because three polymerization components exist, the polymerization reaction is difficult to control, and the conditions of uneven curing of a quantum dot film and the like easily occur, so that the quantum yield of the quantum dot is low, and the stability is poor (such as poor high temperature resistance, poor humidity resistance and the like). Therefore, the applicant is combined with the current state of the industry on the basis of the previous research, and still needs to continuously optimize the polymerization conditions of thiol, isocyanate and alkene polymerization systems so as to realize good control over the reaction process, and obtain a high-performance quantum dot film product with advantages in the aspects of quantum yield, stability and the like.
Disclosure of Invention
The invention relates to a preparation method of a quantum dot composite material, which has better controllability of the preparation process, even composition distribution of a matrix and provides acceptable color stability for a long time.
In one aspect of the invention, a method is provided for preparing a quantum dot composite comprising quantum dots dispersed in a polymer matrix, wherein the polymer matrix is prepared from at least one polythiol monomer having functionality greater than or equal to 2, at least one polyalkenyl monomer having functionality greater than or equal to 2, and at least one polyisocyanate-based monomer having functionality greater than or equal to 2;
the method for preparing the quantum dot composite material comprises the following steps:
i) Providing a quantum dot material, at least one polythiol monomer having functionality greater than or equal to 2, at least one polyalkenyl monomer having functionality greater than or equal to 2, and at least one polyisocyanate-based monomer having functionality greater than or equal to 2;
ii) mixing at least one polythiol monomer having a functionality of not less than 2, an imidazole derivative of formula (I) and a photoinitiator, then mixing with at least one polyalkenyl monomer having a functionality of not less than 2 and at least one polyisocyanate-based monomer having a functionality of not less than 2, and finally mixing with quantum dots;
iii) Subjecting the mixture of step ii) to light irradiation and heating treatment to obtain a crosslinked polymer;
the imidazole derivative of formula (I) has the structure:
wherein,
r1 is selected from one of C1-C15 alkyl, C3-C15 cycloalkyl, aryl and aralkyl;
r2 is selected from hydrogen, C1 to C15 alkyl, C3 to C15 cycloalkyl;
r3 is selected from C1 to C15 alkyl, -CH 2 CH 2 One of COOR4, C3 to C15 cycloalkyl, aryl, aralkyl;
r4 is selected from one of C1-C15 alkyl, C3-C15 cycloalkyl, aryl and aralkyl.
In another aspect of the invention, a quantum dot article is provided.
According to the preparation method of the quantum dot composite material, the imidazole derivative serving as the latent base catalyst is used, after the polymerization reaction of mercaptan and alkene occurs under the photoinitiation, the imidazole derivative is activated under the heating to have the activity of basic catalysis, so that the polymerization reaction of mercaptan and isocyanate is rapidly completed, the mercaptan-isocyanate and mercaptan-alkene are cured step by step under different curing conditions, the curing heat control of high-quality quantum dot products is facilitated, particularly for the quantum dot products which can generate significant heat during simultaneous curing, the curing process between monomers can be uniformly carried out for thicker products, the composition uniformity can be realized in the whole product, and the prepared quantum dot material has excellent capability of blocking water and oxygen, can prolong the service life of the quantum dot products and has higher quantum yield; furthermore, the use of different imidazole derivatives allows for control of the heat of cure.
As used herein, C1 to C15 alkyl is understood to be a linear or branched alkyl radical having a chain length of up to 15 carbon atoms, which in particular has the general formula C n H 2n+1 Where n=1 to 15, can be methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl or 1-ethylpropyl.
As used herein, C3 to C15 cycloalkyl is understood to be a mono-or bicyclic cycloalkyl having 3 to 15 carbon atoms, having the general formula C n H 2n-1 Wherein n=3 to 15, can represent 1-methyl-1-cyclopropyl, 1-methyl-1-cyclobutyl, 1-methyl-1-cyclopentyl, 1-methyl-1-cyclohexyl, 1-methyl-1-cycloheptyl, 2-methyl-1-cyclopropyl, 2-methyl-1-cyclobutyl, 2-methyl-1-cyclopentyl, 2-methyl-1-cyclohexyl, 2-methyl-1-cycloheptyl, 3-methyl-1-cyclobutyl, 3-methyl-1-cyclopentyl, 3-methyl-1-cyclohexyl, 3-methyl-1-cycloheptyl, 4-methyl-1-cyclohexyl, 4-methyl-1-cycloheptyl.
Aryl as used herein denotes aromatic aryl having 3 to 20 carbon atoms, which may itself be further preferably monosubstituted or polysubstituted with C1-to C5-alkyl having the meaning indicated above, and may be phenyl, naphthyl, anthracenyl or perylenyl.
As used herein, aralkyl means a C1-C15-alkyl group having the above-mentioned meaning substituted with an aryl group having the above-mentioned meaning, and specifically, aralkyl is benzyl.
Detailed Description
The invention provides a method for preparing a quantum dot composite material, which comprises quantum dots dispersed in a polymer matrix, and is characterized in that the polymer matrix is prepared from at least one polythiol monomer with functionality more than or equal to 2, at least one polyalkenyl monomer with functionality more than or equal to 2 and at least one polyisocyanate-based monomer with functionality more than or equal to 2;
the method for preparing the quantum dot composite material comprises the following steps:
i) Providing a quantum dot material, at least one polythiol monomer having functionality greater than or equal to 2, at least one polyalkenyl monomer having functionality greater than or equal to 2, and at least one polyisocyanate-based monomer having functionality greater than or equal to 2;
ii) mixing at least one polythiol monomer having a functionality of not less than 2, an imidazole derivative of formula (I) and a photoinitiator, then mixing with at least one polyalkenyl monomer having a functionality of not less than 2 and at least one polyisocyanate-based monomer having a functionality of not less than 2, and finally mixing with quantum dots;
iii) Sequentially carrying out illumination and heating treatment on the mixture obtained in the step ii) to obtain a crosslinked polymer;
the imidazole derivative of formula (I) has the structure:
wherein,
r1 is selected from one of C1-C15 alkyl, C3-C15 cycloalkyl, aryl and aralkyl;
r2 is selected from hydrogen, C1 to C15 alkyl, C3 to C15 cycloalkyl;
r3 is selected from C1 to C15 alkyl, -CH 2 CH 2 One of COOR4, C3 to C15 cycloalkyl, aryl, aralkyl;
r4 is selected from one of C1-C15 alkyl, C3-C15 cycloalkyl, aryl and aralkyl.
In one embodiment, R3 in the imidazole derivative is selected from the group consisting of-CH 2 CH 2 COOR4。
Further preferred imidazole derivatives are selected from the following compounds:
the imidazole derivatives of the invention are known compounds, can be prepared by a known method in the prior art, and have the following specific synthetic route:
preparing imidazole compound into solution, adding triethylamine, introducing nitrogen, slowly adding solution of acyl chloride compound, continuously reacting for 5-10h after dripping, and post-treating after the reaction is completed to obtain imidazole derivative.
In one embodiment, the polythiol monomer in the reactive monomer of the polymer matrix has the formula: r is R x (SH) y Wherein R is x Is a hydrocarbyl group or heterohydrocarbyl group having a valence of y, and y is greater than or equal to 2.
Preferably the polythiol monomer is selected from one or more of the following compounds:
wherein n is an integer of 2 to 10, R 1 And R is 2 Identical or different and independently selected from-CH 2 -CH(SH)CH 3 and-CH 2 -CH 2 -SH；
Or,
wherein R is 3 、R 4 、R 5 And R is 6 Identical or different and independently selected from-C (O) -CH 2 -CH 2 -SH、-(O)-CH 2 -CH(SH)CH 3 、-CH 2 -C(-CH 2 -O-C(O)-CH 2 -CH 2 -SH) 3 、-C(O)-CH 2 -SH and-C (O) -CH (SH) -CH 3 ；
Wherein R is 7 、R 8 And R is 9 Identical or different and independently selected from-C (O) -CH 2 -CH 2 -SH、-C(O)-CH 2 -CH(SH)CH 3 、-C(O)-CH 2 -SH and-C (O) -CH (SH) -CH 3 。
Preferred polythiol monomers are selected from one or more of the following compounds: ethylene glycol bis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) and 1, 4-bis 3-mercaptobutyryloxybutane, tris [2- (3-mercaptopropionyloxy ] ethyl ] isocyanurate, trimethylolpropane tris (mercaptoacetate), 2, 4-bis (mercaptomethyl) -1,3,5, -triazine-2, 4-dithiol, 2, 3-bis (2-mercaptoethyl) thio) -1-propanethiol, dimercaptodiethylsulfide and ethoxylated trimethylpropyl-tris (3-mercaptopropionate). More preferred are ethylene glycol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylol propane tris (mercaptoacetate), trimethylol propane tris (3-mercaptopropionate), and trimethylol propane tris (mercaptoacetate).
In one embodiment, the reactive monomer of the polymer matrix, the polyisocyanate-based monomer is selected from one or more of the following compounds:
or alternatively, the first and second heat exchangers may be,
wherein m, n and p are integers of 1-10.
Preferred polyisocyanate-based monomers are selected from one or more of the following compounds:
in one embodiment, the polyalkenyl monomer is selected from one or more of the following compounds in the reactive monomers of the polymer matrix:
or alternatively, the first and second heat exchangers may be,
wherein m, n and p are integers of 1-10.
Preferred polyalkenyl monomers are selected from one or more of the following compounds:
in one embodiment, the stoichiometric molar ratio of thiol groups of the polythiol monomer, isocyanate groups of the polyisocyanate monomer, and double bond groups of the polyalkenyl in the reactive monomers of the polymer matrix is (1.4-1.8): 1-1.2): 0.8-1.2.
In one embodiment, the imidazole derivative in step ii) is used in an amount of 0.005 to 0.05wt% based on the total amount of all monomers.
In one embodiment, after the quantum dots of the present invention are illuminated by a blue LED, the blue light of the LED is down-converted to green and red light, and the respective portions of the red, green and blue light can be controlled to achieve white light emitted by a display device containing the quantum dot article.
In the present invention, the quantum dots are selected from CdSe/ZnS, inP/ZnS, and CdS/ZnS.
In an exemplary embodiment, the quantum dot comprises a coating of external ligands bearing amino, carboxyl or mercapto groups, in particular for example mercaptopropionic acid, oleic acid, oleylamine, amino-substituted silicone carrier liquids, long chain sulfides with carboxyl end groups, preferably long chain sulfides with carboxyl end groups, such as H- [ CH (CO) 2 C 12 H 25 -n)CH 2 ] 3 -S-CH(CO 2 H)CH 2 CO 2 H、H-[CH(CO 2 C 12 H 25 -n)CH 2 ] 5 -S-CH(CO 2 H)CH 2 CO 2 H、n-C 12 H 25 -S-CH(CO 2 H)CH 2 CO 2 H。
In one embodiment, the light conditions of step iii) are light under ultraviolet light for 10-20 minutes according to the type of monomers used in the present invention in the preparation of the quantum dot composite material of the present invention, so that the polythiol monomer and the polyene monomer are polymerized. Said step ii) adding a photoinitiator to initiate polymerization of the polythiol monomer and the polyene monomer. Preferably the photoinitiating energy source emits ultraviolet radiation, i.e. radiation having a wavelength between about 180 and 460 nanometers, including photoinitiating energy sources such as mercury arc lamps, carbon arc lamps, low, medium or high pressure mercury vapor lamps, turbulent plasma arc lamps, xenon flash lamps, ultraviolet light emitting diodes and ultraviolet light emitting lasers.
In one embodiment, the initiator is a photoinitiator and is capable of activation by ultraviolet radiation. Useful photoinitiators include, for example, benzoin ethers (such as benzoin methyl ether and benzoin isopropyl ether), substituted benzoin ethers, substituted acetophenones (such as 2, 2-dimethoxy-2-phenylacetophenone), and substituted alpha-ketols. Preferred photoinitiators are 2-hydroxy-2-methyl-1-phenyl-propan-1-one (IRGACURE 1173. TM., BASF), 2-dimethoxy-2-phenylacetophenone (IRGACURE 651. TM., BASF)), phenylbis- (2, 4, 6-trimethylbenzoyl) phosphine oxide (IRGACURE 819, BASF). Other suitable photoinitiators include mercaptobenzothiazole, mercaptobenzoxazole and hexaarylbisimidazole. Generally, the amount of initiator is less than 5wt%, preferably less than 2 wt%.
In one embodiment, the heating temperature of step iii) in the preparation of the quantum dot composite material of the present invention depends on the imidazole derivative and the type of monomer, etc., as long as the polymerization of the first polythiol with the polyene can be substantially separated from the polymerization of the second polythiol with the polyisocyanate. From the viewpoint of quantum dot stability, the heating temperature of step iii) is 70-120 ℃. The imidazole derivative used in the invention has high latency and thus high storage stability when not additionally heated, ensures that the polymerization reaction of polythiol and polyene in the first step and the polymerization reaction of polythiol and polyisocyanate in the second step are basically carried out step by step, and the imidazole derivative is activated after further heating to have activity as alkaline catalysis, and can quickly catalyze the polymerization reaction of polythiol monomer and polyisocyanate-based monomer once activated because the polymerization reaction of polythiol monomer and polyisocyanate-based monomer is fast, thereby completing the curing in a short time, and further completing the crosslinking curing of reactive groups such as alkenyl and the like remained in the first step only by properly prolonging the reaction time at the temperature without further heating treatment. The reaction sequence described herein does not necessarily take place in only one reaction per reaction, but the reaction is mainly one reaction, and does not exclude the reaction accompanied by a small amount of polythiol groups and polyene groups when polythiol groups and polyisocyanate groups react, and the reaction accompanied by a small amount of polythiol groups and polyisocyanate groups when polythiol groups and polyene groups react.
The invention also provides a quantum dot product, comprising:
a first barrier layer;
a second barrier layer; and
a quantum dot layer between the first barrier layer and the second barrier layer;
the quantum dot layer comprises the quantum dot composite material prepared by the method.
The first and second barrier layers may be formed of any useful material that protects the quantum dots from exposure to environmental contaminants (e.g., oxygen, water, and water vapor). Suitable barrier layers include, but are not limited to, polymeric films, glass films, and dielectric material films. In some embodiments, suitable materials for the first barrier layer and the second barrier layer include, for example: glass and polymers such as polyethylene terephthalate (PET), PEN, polyether or PMMA; oxides, such as silicon oxide, titanium oxide or aluminum oxide (e.g. SiO 2 、TiO 2 Or Al 2 O 3 ) The method comprises the steps of carrying out a first treatment on the surface of the And suitable combinations thereof. It is desirable that the barrier layer is at least 90%, preferably at least 95%, transmissive to the selected wavelengths of the incident and emitted radiation.
The present invention also provides a method of making a quantum dot article comprising coating the quantum dot composite of the present invention on a first barrier layer, disposing a second barrier layer on the quantum dot composite layer, laminating the second barrier layer, and curing the quantum dot composite.
Intrusion (including edge intrusion) is defined as the loss of quantum dot performance due to intrusion of moisture and/or oxygen into the matrix. In various embodiments, the quantum dot article has a color shift d (x, y) of less than about 0.01 according to CIE1931 (x, y) rules when placed at 65 ℃ and 95% relative humidity for 80 hours, with a quantum yield variation in the range of 10%.
In various embodiments, the quantum dot layer has a thickness of about 25 microns to 500 microns, preferably 40 microns to about 250 microns.
General method 1 for preparing Quantum dot composite Material and Quantum dot film product
Mixing polythiol monomer, 0.01g imidazole derivative and 0.2g photo initiator phenyl bis- (2, 4, 6-trimethylbenzoyl) phosphine oxide, then mixing with polyalkenyl monomer and polyisocyanate based monomer according to the required equivalent ratio, and finally mixing with 1g quantum dot CdSe/ZnS; the three monomers were mixed thoroughly in a nitrogen box at 2000rpm for 3 minutes in total of 20g to prepare quantum dot composites of each of the following examples.
Then, the composite prepared above was knife coated between two 50 μm primer PET barrier films at a thickness of about 80 μm, then first irradiated under uv light for 12 minutes, and then reacted at 85 ℃ for 30 minutes.
General method 2 for preparing Quantum dot composite Material and Quantum dot film product
The procedure was followed in accordance with method 1, except that the reaction was carried out at 85℃for 30 minutes instead of at 100℃for 30 minutes.
Contrast method 1 for preparing quantum dot composite material and quantum dot film product
The procedure was followed as in general procedure 1 above, except that the imidazole derivative was replaced with catalyst DBU-Ant-BPh4, while the curing reaction conditions were changed from first irradiation with ultraviolet light for 12 minutes, then reaction at 85℃for 30 minutes, then irradiation with the preceding ultraviolet light for 5 minutes, and then reaction at 108℃for 30 minutes.
Method for measuring Quantum Yield (QY)
All quantum yields were measured by using an absolute fluorescence quantum yield spectrometer.
Method for aging study
Aging study the aging stability was evaluated by measuring the quantum yield after leaving the cut film prepared in the following examples at 65 ℃ and 95% relative humidity for 80 hours.
Method for determining edge intrusion
After the dicing film was aged as described above, edge intrusion of the cured substrate having two barrier films was measured from the dicing edge of the substrate film by a ruler under a magnifying glass. If the quantum dots are degraded by oxygen and/or moisture and do not fluoresce during aging, the quantum dots at the edges show a black line under blue light.
Monomer Compounds used in examples or comparative examples：
Compound 1: ethylene glycol bis (mercaptoacetate)
Compound 2: trimethylol propane tris (mercaptoacetate)
Compound 3:
compound 4:
compound 5:
compound 6:
compound 7:
compound 8:
compound 9:
compound 10:1, 8-diazabicyclo (5.4.0) undec-7-ene-anthracene-tetraphenylboronic acid ester (DBU-Ant-BPh 4)
Examples 1 to 9
Examples 1-2, 4-5, 7-8 were prepared according to general method 1 described above for preparing quantum dot composites, quantum dot film articles, examples 3, 6, 9 were prepared according to general method 2 described above, and specific preparation conditions are shown in table 1.
Comparative examples 1 to 2
Comparative examples 1-2 were prepared according to comparative method 1 described above for the preparation of quantum dot composites, quantum dot film products, with specific preparation conditions shown in table 1.
Using the test methods described above, the quantum yield and edge intrusion were measured on the prepared samples before and after aging.
TABLE 1
Table 2 below summarizes the QY data at the time of preparing the samples and the QY data after aging for the same samples of the selected examples.
TABLE 2
The result shows that the matrix for preparing the quantum dots by using the method has excellent capability of blocking water and oxygen, so that the color of the quantum dot product is stable, and the service life of the quantum dot product in display application can be prolonged.
Although the invention has been described in connection with specific features and embodiments thereof, it will be apparent that various modifications and combinations can be made without departing from the spirit and scope of the invention. Accordingly, this description is merely exemplary of the invention as defined in the appended claims and is intended to cover any and all modifications, variations, combinations, or equivalents that fall within the scope of the invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (9)
1. A method of preparing a quantum dot composite comprising quantum dots dispersed in a polymer matrix, wherein the polymer matrix is prepared from at least one polythiol monomer having functionality greater than or equal to 2, at least one polyalkenyl monomer having functionality greater than or equal to 2, and at least one polyisocyanate-based monomer having functionality greater than or equal to 2;
the method for preparing the quantum dot composite material comprises the following steps:
i) Providing a quantum dot material, at least one polythiol monomer having functionality greater than or equal to 2, at least one polyalkenyl monomer having functionality greater than or equal to 2, and at least one polyisocyanate-based monomer having functionality greater than or equal to 2;
ii) mixing at least one polythiol monomer having a functionality of not less than 2, an imidazole derivative of formula (I) and a photoinitiator, then mixing with at least one polyalkenyl monomer having a functionality of not less than 2 and at least one polyisocyanate-based monomer having a functionality of not less than 2, and finally mixing with quantum dots;
iii) Sequentially carrying out illumination and heating treatment on the mixture obtained in the step ii) to obtain a crosslinked polymer;
the imidazole derivative of formula (I) has the structure:
wherein,
r1 is selected from one of C1-C15 alkyl, C3-C15 cycloalkyl, aryl and aralkyl;
r2 is selected from hydrogen, C1 to C15 alkyl, C3 to C15 cycloalkyl;
r3 is selected from C1 to C15 alkyl, -CH 2 CH 2 One of COOR4, C3 to C15 cycloalkyl, aryl, aralkyl;
r4 is selected from one of C1-C15 alkyl, C3-C15 cycloalkyl, aryl and aralkyl;
the stoichiometric molar ratio of thiol groups of the polythiol monomer, isocyanate groups of the polyisocyanate monomer, and double bond groups of the polyalkenyl is (1.4-1.8): 1-1.2): 0.8-1.2;
the imidazole derivative in the step ii) is used in an amount of 0.005 to 0.05wt% based on the total amount of all monomers;
the illumination condition of the step iii) is that the light is under ultraviolet light for 10-20 minutes;
the heating temperature in step iii) is 70-120 ℃.
2. The method of claim 1, wherein the polythiol monomer has the formula:
R x (SH) y wherein R is x Is a hydrocarbyl group or heterohydrocarbyl group having a valence of y, and y is greater than or equal to 2.
3. The process according to any one of claims 1-2, wherein the polythiol monomer is selected from one or more of the following compounds:
wherein n is an integer of 2 to 10, R 1 And R is 2 Identical or different and independently selected from-CH 2 -CH(SH)CH 3 and-CH 2 -CH 2 -SH；
Or,
wherein R is 3 、R 4 、R 5 And R is 6 Identical or different and independently selected from-C (O) -CH 2 -CH 2 -SH、
-CH 2 -C(-CH 2 -O-C(O)-CH 2 -CH 2 -SH) 3 、-C(O)-CH 2 -SH and-C (O) -CH (SH) -CH 3 The method comprises the steps of carrying out a first treatment on the surface of the Or,
wherein R is 7 、R 8 And R is 9 Identical or different and independently selected from-C (O) -CH 2 -CH 2 -SH、-C(O)-CH 2 -CH(SH)CH 3 、-C(O)-CH 2 -SH and-C (O) -CH (SH) -CH 3 。
4. The method of claim 1, wherein the polyisocyanate-based monomer is selected from one or more of the following compounds:
or,
wherein m, n and p are integers of 1-10.
5. The method of claim 1, wherein the polyalkenyl monomer is selected from one or more of the following compounds:
or,
wherein m, n and p are integers of 1-10.
6. The method according to claim 1, wherein R3 in the imidazole derivative is selected from the group consisting of-CH 2 CH 2 COOR4。
7. The method according to claim 1, wherein the imidazole derivative is selected from the group consisting of:
8. the method of claim 1, wherein the quantum dots are selected from CdSe/ZnS, inP/ZnS, and CdS/ZnS.
9. A quantum dot article, the quantum dot article comprising:
a first barrier layer;
a second barrier layer; and
a quantum dot layer between the first barrier layer and the second barrier layer;
the quantum dot layer comprises a quantum dot composite material prepared according to the method of any one of claims 1-8.
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| EP3789416A1 (en) * | 2019-09-04 | 2021-03-10 | Henkel AG & Co. KGaA | Thiol/isocyanate/(poly-)ene formulations for additive manufacturing |
| CN114230767A (en) * | 2021-12-13 | 2022-03-25 | 江苏钛得新材料技术有限公司 | Imidazole derivative microcapsule type latent curing agent for adhesive and preparation method thereof |
| CN114907765A (en) * | 2022-05-09 | 2022-08-16 | 南京贝迪新材料科技股份有限公司 | Quantum dot materials containing thiol-alkene-isocyanate matrix |
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