CN115991662A - Antioxidant compound and preparation method and application thereof - Google Patents
Antioxidant compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN115991662A CN115991662A CN202310095712.5A CN202310095712A CN115991662A CN 115991662 A CN115991662 A CN 115991662A CN 202310095712 A CN202310095712 A CN 202310095712A CN 115991662 A CN115991662 A CN 115991662A
- Authority
- CN
- China
- Prior art keywords
- antioxidant
- diisocyanate
- antioxidant compound
- isocyanate
- compound
- 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.)
- Pending
Links
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 100
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 89
- 150000001875 compounds Chemical class 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000004814 polyurethane Substances 0.000 claims abstract description 29
- 229920002635 polyurethane Polymers 0.000 claims abstract description 29
- 239000012948 isocyanate Substances 0.000 claims abstract description 27
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 26
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 230000007760 free radical scavenging Effects 0.000 claims abstract description 10
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 235000006708 antioxidants Nutrition 0.000 claims description 84
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 18
- -1 rhein Chemical compound 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 235000013824 polyphenols Nutrition 0.000 claims description 14
- YDQWDHRMZQUTBA-UHFFFAOYSA-N Aloe emodin Chemical compound C1=CC=C2C(=O)C3=CC(CO)=CC(O)=C3C(=O)C2=C1O YDQWDHRMZQUTBA-UHFFFAOYSA-N 0.000 claims description 12
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 9
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 claims description 8
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 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 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 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 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- XMOCLSLCDHWDHP-IUODEOHRSA-N epi-Gallocatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-IUODEOHRSA-N 0.000 claims description 6
- PKUBGLYEOAJPEG-UHFFFAOYSA-N physcion Natural products C1=C(C)C=C2C(=O)C3=CC(C)=CC(O)=C3C(=O)C2=C1O PKUBGLYEOAJPEG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- DXDRHHKMWQZJHT-FPYGCLRLSA-N isoliquiritigenin Chemical compound C1=CC(O)=CC=C1\C=C\C(=O)C1=CC=C(O)C=C1O DXDRHHKMWQZJHT-FPYGCLRLSA-N 0.000 claims description 5
- JBQATDIMBVLPRB-UHFFFAOYSA-N isoliquiritigenin Natural products OC1=CC(O)=CC=C1C1OC2=CC(O)=CC=C2C(=O)C1 JBQATDIMBVLPRB-UHFFFAOYSA-N 0.000 claims description 5
- 235000008718 isoliquiritigenin Nutrition 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 claims description 4
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 4
- VWDXGKUTGQJJHJ-UHFFFAOYSA-N Catenarin Natural products C1=C(O)C=C2C(=O)C3=C(O)C(C)=CC(O)=C3C(=O)C2=C1O VWDXGKUTGQJJHJ-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000010282 Emodin Substances 0.000 claims description 4
- RBLJKYCRSCQLRP-UHFFFAOYSA-N Emodin-dianthron Natural products O=C1C2=CC(C)=CC(O)=C2C(=O)C2=C1CC(=O)C=C2O RBLJKYCRSCQLRP-UHFFFAOYSA-N 0.000 claims description 4
- PLAPMLGJVGLZOV-UHFFFAOYSA-N Epi-orientin Natural products OC1C(O)C(O)C(CO)OC1C1=C(O)C=C(O)C2=C1OC(C=1C=C(O)C(O)=CC=1)=CC2=O PLAPMLGJVGLZOV-UHFFFAOYSA-N 0.000 claims description 4
- WMBWREPUVVBILR-UHFFFAOYSA-N GCG Natural products C=1C(O)=C(O)C(O)=CC=1C1OC2=CC(O)=CC(O)=C2CC1OC(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-UHFFFAOYSA-N 0.000 claims description 4
- YOOXNSPYGCZLAX-UHFFFAOYSA-N Helminthosporin Natural products C1=CC(O)=C2C(=O)C3=CC(C)=CC(O)=C3C(=O)C2=C1O YOOXNSPYGCZLAX-UHFFFAOYSA-N 0.000 claims description 4
- XMOCLSLCDHWDHP-UHFFFAOYSA-N L-Epigallocatechin Natural products OC1CC2=C(O)C=C(O)C=C2OC1C1=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-UHFFFAOYSA-N 0.000 claims description 4
- NTGIIKCGBNGQAR-UHFFFAOYSA-N Rheoemodin Natural products C1=C(O)C=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1O NTGIIKCGBNGQAR-UHFFFAOYSA-N 0.000 claims description 4
- LQGUBLBATBMXHT-UHFFFAOYSA-N chrysophanol Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(O)=C3C(=O)C2=C1O LQGUBLBATBMXHT-UHFFFAOYSA-N 0.000 claims description 4
- 235000012754 curcumin Nutrition 0.000 claims description 4
- 229940109262 curcumin Drugs 0.000 claims description 4
- 239000004148 curcumin Substances 0.000 claims description 4
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 claims description 4
- RHMXXJGYXNZAPX-UHFFFAOYSA-N emodin Chemical compound C1=C(O)C=C2C(=O)C3=CC(C)=CC(O)=C3C(=O)C2=C1O RHMXXJGYXNZAPX-UHFFFAOYSA-N 0.000 claims description 4
- VASFLQKDXBAWEL-UHFFFAOYSA-N emodin Natural products OC1=C(OC2=C(C=CC(=C2C1=O)O)O)C1=CC=C(C=C1)O VASFLQKDXBAWEL-UHFFFAOYSA-N 0.000 claims description 4
- DZYNKLUGCOSVKS-UHFFFAOYSA-N epigallocatechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3cc(O)c(O)c(O)c3 DZYNKLUGCOSVKS-UHFFFAOYSA-N 0.000 claims description 4
- FFWOKTFYGVYKIR-UHFFFAOYSA-N physcion Chemical compound C1=C(C)C=C2C(=O)C3=CC(OC)=CC(O)=C3C(=O)C2=C1O FFWOKTFYGVYKIR-UHFFFAOYSA-N 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 230000002000 scavenging effect Effects 0.000 claims description 4
- 239000013638 trimer Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- IPMYMEWFZKHGAX-UHFFFAOYSA-N Isotheaflavin Natural products OC1CC2=C(O)C=C(O)C=C2OC1C(C1=C2)=CC(O)=C(O)C1=C(O)C(=O)C=C2C1C(O)CC2=C(O)C=C(O)C=C2O1 IPMYMEWFZKHGAX-UHFFFAOYSA-N 0.000 claims description 3
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 3
- UXRMWRBWCAGDQB-UHFFFAOYSA-N Theaflavin Natural products C1=CC(C2C(CC3=C(O)C=C(O)C=C3O2)O)=C(O)C(=O)C2=C1C(C1OC3=CC(O)=CC(O)=C3CC1O)=CC(O)=C2O UXRMWRBWCAGDQB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011527 polyurethane coating Substances 0.000 claims description 3
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 3
- SXWZSWLBMCNOPC-UHFFFAOYSA-M potassium;6-methylheptanoate Chemical compound [K+].CC(C)CCCCC([O-])=O SXWZSWLBMCNOPC-UHFFFAOYSA-M 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- IPMYMEWFZKHGAX-ZKSIBHASSA-N theaflavin Chemical compound C1=C2C([C@H]3OC4=CC(O)=CC(O)=C4C[C@H]3O)=CC(O)=C(O)C2=C(O)C(=O)C=C1[C@@H]1[C@H](O)CC2=C(O)C=C(O)C=C2O1 IPMYMEWFZKHGAX-ZKSIBHASSA-N 0.000 claims description 3
- 235000014620 theaflavin Nutrition 0.000 claims description 3
- 229940026509 theaflavin Drugs 0.000 claims description 3
- XMOCLSLCDHWDHP-SWLSCSKDSA-N (+)-Epigallocatechin Natural products C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-SWLSCSKDSA-N 0.000 claims description 2
- LSHVYAFMTMFKBA-PZJWPPBQSA-N (+)-catechin-3-O-gallate Chemical compound O([C@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=CC=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 LSHVYAFMTMFKBA-PZJWPPBQSA-N 0.000 claims description 2
- PFTAWBLQPZVEMU-ZFWWWQNUSA-N (+)-epicatechin Natural products C1([C@@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-ZFWWWQNUSA-N 0.000 claims description 2
- WMBWREPUVVBILR-GHTZIAJQSA-N (+)-gallocatechin gallate Chemical compound O([C@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=C(O)C=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-GHTZIAJQSA-N 0.000 claims description 2
- WMBWREPUVVBILR-WIYYLYMNSA-N (-)-Epigallocatechin-3-o-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=C(O)C=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-WIYYLYMNSA-N 0.000 claims description 2
- PFTAWBLQPZVEMU-UKRRQHHQSA-N (-)-epicatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-UKRRQHHQSA-N 0.000 claims description 2
- LSHVYAFMTMFKBA-TZIWHRDSSA-N (-)-epicatechin-3-O-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=CC=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 LSHVYAFMTMFKBA-TZIWHRDSSA-N 0.000 claims description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
- ODBRNZZJSYPIDI-UHFFFAOYSA-N 3',4',5,7-tetrahydroxy-6-C-glucopyranosylflavone Natural products OC1C(O)C(O)C(CO)OC1C1=C(O)C=C(OC(=CC2=O)C=3C=C(O)C(O)=CC=3)C2=C1O ODBRNZZJSYPIDI-UHFFFAOYSA-N 0.000 claims description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- AFHJQYHRLPMKHU-XXWVOBANSA-N Aloin Natural products O=C1c2c(O)cc(CO)cc2[C@H]([C@H]2[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O2)c2c1c(O)ccc2 AFHJQYHRLPMKHU-XXWVOBANSA-N 0.000 claims description 2
- MQVRGDZCYDEQML-UHFFFAOYSA-N Astragalin Natural products C1=CC(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 MQVRGDZCYDEQML-UHFFFAOYSA-N 0.000 claims description 2
- PVOIIIFPOJQCIF-UHFFFAOYSA-N CC(C=CC=C1N=C=O)=C1N(C(N(C1=C(C)C=CC=C1N=C=O)C(N1C2=C(C)C=CC=C2N=C=O)=O)=O)C1=O Chemical compound CC(C=CC=C1N=C=O)=C1N(C(N(C1=C(C)C=CC=C1N=C=O)C(N1C2=C(C)C=CC=C2N=C=O)=O)=O)C1=O PVOIIIFPOJQCIF-UHFFFAOYSA-N 0.000 claims description 2
- LSHVYAFMTMFKBA-UHFFFAOYSA-N ECG Natural products C=1C=C(O)C(O)=CC=1C1OC2=CC(O)=CC(O)=C2CC1OC(=O)C1=CC(O)=C(O)C(O)=C1 LSHVYAFMTMFKBA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004378 Glycyrrhizin Substances 0.000 claims description 2
- UGNZSMZSJYOGNX-UHFFFAOYSA-N Isoviocristine Natural products O=C1C=C(C)C(=O)C2=CC3=CC(OC)=CC(O)=C3C(O)=C21 UGNZSMZSJYOGNX-UHFFFAOYSA-N 0.000 claims description 2
- PTNJRKBWIYNFSY-UHFFFAOYSA-N Lirinin-O-methyl-ether Natural products COc1ccc-2c(CC3N(C)CCc4cc(OC)c(OC)c-2c34)c1 PTNJRKBWIYNFSY-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- RBVAFYCFAFADAG-UHFFFAOYSA-N Orientin Natural products OCC1OC(C(O)c2c(O)cc(O)c3C(=O)C=C(Oc23)c4ccc(O)c(O)c4)C(O)C1O RBVAFYCFAFADAG-UHFFFAOYSA-N 0.000 claims description 2
- WJJFWGUVMIUWGG-UHFFFAOYSA-N Stereolensin Natural products OC1C(O)C(O)C(CO)OC1OC1=C(O)C=C(OC(=CC2=O)C=3C=C(O)C(O)=CC=3)C2=C1O WJJFWGUVMIUWGG-UHFFFAOYSA-N 0.000 claims description 2
- LQSNPVIQIPKOGP-UHFFFAOYSA-N UNPD159785 Natural products OC1C(O)C(O)C(CO)OC1OC1=C(O)C=C(O)C2=C1OC(C=1C=C(O)C(O)=CC=1)=CC2=O LQSNPVIQIPKOGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- CPUHNROBVJNNPW-UHFFFAOYSA-N aloin A Natural products OC1C(O)C(O)C(CO)OC1OC1C2=CC(CO)=CC(O)=C2C(=O)C2=C(O)C=CC=C21 CPUHNROBVJNNPW-UHFFFAOYSA-N 0.000 claims description 2
- AFHJQYHRLPMKHU-WEZNYRQKSA-N aloin B Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1[C@H]1C2=CC(CO)=CC(O)=C2C(=O)C2=C(O)C=CC=C21 AFHJQYHRLPMKHU-WEZNYRQKSA-N 0.000 claims description 2
- WLXGUTUUWXVZNM-UHFFFAOYSA-N anthraglycoside A Natural products C1=C(C)C=C2C(=O)C3=CC(OC)=CC(O)=C3C(=O)C2=C1OC1OC(CO)C(O)C(O)C1O WLXGUTUUWXVZNM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 2
- NZPQWZZXRKZCDU-UHFFFAOYSA-N chrysophanol Natural products Cc1cc(O)c2C(=O)c3c(O)cccc3Oc2c1 NZPQWZZXRKZCDU-UHFFFAOYSA-N 0.000 claims description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- LPTRNLNOHUVQMS-UHFFFAOYSA-N epicatechin Natural products Cc1cc(O)cc2OC(C(O)Cc12)c1ccc(O)c(O)c1 LPTRNLNOHUVQMS-UHFFFAOYSA-N 0.000 claims description 2
- 235000012734 epicatechin Nutrition 0.000 claims description 2
- 229940030275 epigallocatechin gallate Drugs 0.000 claims description 2
- VNUQOJUAIRBYQO-UHFFFAOYSA-N esculentin Natural products COC1CC(OC2CCC3(C)C4C(O)C(O)C5(C)C(O)(CCC5(O)C4(O)CC=C3C2)C(=O)C)OC(C)C1OC6CC(OC)C(OC7OC(C)C(O)C(OC)C7O)C(C)O6 VNUQOJUAIRBYQO-UHFFFAOYSA-N 0.000 claims description 2
- VNUQOJUAIRBYQO-PPAUOFQQSA-N esculentin Chemical compound O([C@H]1[C@@H](OC)C[C@@H](O[C@@H]1C)O[C@@H]1[C@@H](C)O[C@@H](O[C@@H]2CC3=CC[C@@]4(O)[C@@]5(O)CC[C@](O)([C@@]5(C)[C@H](O)[C@@H](O)C4[C@@]3(C)CC2)C(C)=O)C[C@H]1OC)[C@@H]1O[C@H](C)[C@@H](O)[C@H](OC)[C@H]1O VNUQOJUAIRBYQO-PPAUOFQQSA-N 0.000 claims description 2
- 239000012458 free base Substances 0.000 claims description 2
- LVJJFMLUMNSUFN-UHFFFAOYSA-N gallocatechin gallate Natural products C1=C(O)C=C2OC(C=3C=C(O)C(O)=CC=3)C(O)CC2=C1OC(=O)C1=CC(O)=C(O)C(O)=C1 LVJJFMLUMNSUFN-UHFFFAOYSA-N 0.000 claims description 2
- LPLVUJXQOOQHMX-UHFFFAOYSA-N glycyrrhetinic acid glycoside Natural products C1CC(C2C(C3(CCC4(C)CCC(C)(CC4C3=CC2=O)C(O)=O)C)(C)CC2)(C)C2C(C)(C)C1OC1OC(C(O)=O)C(O)C(O)C1OC1OC(C(O)=O)C(O)C(O)C1O LPLVUJXQOOQHMX-UHFFFAOYSA-N 0.000 claims description 2
- 229960004949 glycyrrhizic acid Drugs 0.000 claims description 2
- UYRUBYNTXSDKQT-UHFFFAOYSA-N glycyrrhizic acid Natural products CC1(C)C(CCC2(C)C1CCC3(C)C2C(=O)C=C4C5CC(C)(CCC5(C)CCC34C)C(=O)O)OC6OC(C(O)C(O)C6OC7OC(O)C(O)C(O)C7C(=O)O)C(=O)O UYRUBYNTXSDKQT-UHFFFAOYSA-N 0.000 claims description 2
- 235000019410 glycyrrhizin Nutrition 0.000 claims description 2
- LPLVUJXQOOQHMX-QWBHMCJMSA-N glycyrrhizinic acid Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@@H]1C([C@H]2[C@]([C@@H]3[C@@]([C@@]4(CC[C@@]5(C)CC[C@@](C)(C[C@H]5C4=CC3=O)C(O)=O)C)(C)CC2)(C)CC1)(C)C)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O LPLVUJXQOOQHMX-QWBHMCJMSA-N 0.000 claims description 2
- AFHJQYHRLPMKHU-UHFFFAOYSA-N isobarbaloin Natural products OC1C(O)C(O)C(CO)OC1C1C2=CC(CO)=CC(O)=C2C(=O)C2=C(O)C=CC=C21 AFHJQYHRLPMKHU-UHFFFAOYSA-N 0.000 claims description 2
- ODBRNZZJSYPIDI-VJXVFPJBSA-N isoorientin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1C1=C(O)C=C(OC(=CC2=O)C=3C=C(O)C(O)=CC=3)C2=C1O ODBRNZZJSYPIDI-VJXVFPJBSA-N 0.000 claims description 2
- UYJGIAWJIRZBNU-UHFFFAOYSA-N isoorientin Natural products OCC1OC(C(O)C(O)C1O)c2cc(O)c(O)c3C(=O)C=C(Oc23)c4ccc(O)c(O)c4 UYJGIAWJIRZBNU-UHFFFAOYSA-N 0.000 claims description 2
- JPUKWEQWGBDDQB-QSOFNFLRSA-N kaempferol 3-O-beta-D-glucoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C(C=2C=CC(O)=CC=2)OC2=CC(O)=CC(O)=C2C1=O JPUKWEQWGBDDQB-QSOFNFLRSA-N 0.000 claims description 2
- PEFNSGRTCBGNAN-UHFFFAOYSA-N nephrocizin Natural products OC1C(O)C(O)C(CO)OC1OC1=CC(O)=C2C(=O)C=C(C=3C=C(O)C(O)=CC=3)OC2=C1 PEFNSGRTCBGNAN-UHFFFAOYSA-N 0.000 claims description 2
- PLAPMLGJVGLZOV-VPRICQMDSA-N orientin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1C1=C(O)C=C(O)C2=C1OC(C=1C=C(O)C(O)=CC=1)=CC2=O PLAPMLGJVGLZOV-VPRICQMDSA-N 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 125000005628 tolylene group Chemical group 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 abstract description 14
- OHDRQQURAXLVGJ-HLVWOLMTSA-N azane;(2e)-3-ethyl-2-[(e)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N/N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-HLVWOLMTSA-N 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 238000003756 stirring Methods 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000000203 mixture Substances 0.000 description 15
- 230000036542 oxidative stress Effects 0.000 description 12
- 206010052428 Wound Diseases 0.000 description 11
- 208000027418 Wounds and injury Diseases 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 230000006870 function Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 206010061218 Inflammation Diseases 0.000 description 4
- 230000002292 Radical scavenging effect Effects 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000004054 inflammatory process Effects 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- 239000004632 polycaprolactone Substances 0.000 description 4
- 230000035755 proliferation Effects 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 230000000451 tissue damage Effects 0.000 description 3
- 231100000827 tissue damage Toxicity 0.000 description 3
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 2
- 235000005487 catechin Nutrition 0.000 description 2
- 238000013043 cell viability test Methods 0.000 description 2
- 230000001684 chronic effect Effects 0.000 description 2
- 229950001002 cianidanol Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 206010012601 diabetes mellitus Diseases 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000013013 elastic material Substances 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- 230000029663 wound healing Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 108010087230 Sincalide Proteins 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- OHDRQQURAXLVGJ-AXMZSLBLSA-N azane;(2z)-3-ethyl-2-[(z)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N\N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-AXMZSLBLSA-N 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010609 cell counting kit-8 assay Methods 0.000 description 1
- 230000003915 cell function Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000008260 defense mechanism Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 230000013632 homeostatic process Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001575 pathological effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000003244 pro-oxidative effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- IZTQOLKUZKXIRV-YRVFCXMDSA-N sincalide Chemical compound C([C@@H](C(=O)N[C@@H](CCSC)C(=O)NCC(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CC(O)=O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)NC(=O)[C@@H](N)CC(O)=O)C1=CC=C(OS(O)(=O)=O)C=C1 IZTQOLKUZKXIRV-YRVFCXMDSA-N 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides an antioxidant compound, a preparation method and application thereof, wherein the preparation raw materials comprise a functional reagent, isocyanate and a catalyst; the functional reagent is alcohol containing a phenolic hydroxyl structure or amine containing a phenolic hydroxyl structure. The phenolic hydroxyl is introduced into the molecular structure of isocyanate, so that the compound has higher antioxidant activity and shows excellent free radical scavenging activity. Antioxidant compounds have wide application in the synthesis of polyurethane materials. The experimental results show that: the free radical clearance of the antioxidant compound is 70.67 +/-1.98% -85.29 +/-0.86%; the ABTS plus free radical clearance of the antioxidant polyurethane material is 82.58 plus or minus 5.62 percent to 100 plus or minus 0.95 percent.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to an antioxidant compound, and a preparation method and application thereof.
Background
Oxidative stress is a state of the body in which pro-oxidant and antioxidant homeostasis is imbalanced, free radical production is increased, or the body's, tissue's antioxidant capacity is reduced, and excessive oxidative stress can lead to tissue damage, thereby causing a number of diseases. Normally, the body's defense mechanisms balance the production and removal of free radicals. However, under certain pathological conditions, in vivo free radicals are rapidly increased, and the overproduced active oxygen free radicals exceed the scavenging capacity of the antioxidant system of cells or tissues, so that oxidative stress occurs due to unbalance of free radical generation and scavenging, thereby causing tissue damage, disease occurrence and the like. Particularly has great influence on wound healing and biological material medical appliances.
In the wound healing process, many cells in the wound microenvironment can generate free radicals such as active oxygen and the like to different degrees. For acute wounds, the wound tissues are exposed to inflammation for a short time and are less damaged by active oxygen. For chronic wound surfaces, the duration of inflammatory reaction is long, active oxygen can be continuously or excessively generated, tissue damage can be continuously generated, and simultaneously excessive active oxygen free radicals can promote the duration of inflammatory reaction, so that the wound surfaces enter a vicious circle, and the wound surfaces are difficult to heal. For chronic wounds, especially diabetic wounds, various approaches can lead to the generation of oxidative stress, so that measures such as antioxidation treatment on the wounds in the treatment process of the wounds difficult to heal due to diabetes are very effective for the healing of the wounds. In the case of the bio-implant material, more active oxygen radicals are generated at the implant site of the material due to the local increase of the degradation products of the bio-degradable material, so that oxidative stress is induced and inflammatory reaction is induced, and normal cell functions are damaged.
Therefore, in view of the above medical problems induced by oxidative stress, it is extremely important to develop an antioxidant material having a radical scavenging function to eliminate the adverse effects of oxidative stress. At present, some documents propose grafting functional agents with antioxidant properties into polyurethane molecular chains. For example, the literature (China Plastics Industry,2021,12,29-33) of "preparation and performance of pH responsive color-changing bio-based polyurethane" proposes that a polyhydric alcohol is reacted with isocyanate, then a dimethylolpropionic acid cross-linking agent is added for chain extension, and simultaneously, isocyanate and aloe-emodin are additionally added, so that aloe-emodin with an antioxidant function is introduced into a polyurethane molecular chain through polymerization reaction, however, the preparation method is complicated, the molecular structure is complex, byproducts are more, the content of functional reagents is low, and the material performance is not ideal. In addition, the literature (Polymer Bulletin,2021,7,51-57) on "research on ageing resistance of grafted hindered phenol polyurethane foam" proposes that hindered phenol with oxidation resistance is reacted with isocyanate to prepare modified isocyanate, which is then polymerized with polyol, chain extender and the like, and finally preparation of a hindered phenol modified polyurethane material is achieved. The hindered phenol structure contains 1 phenolic hydroxyl group and 1 carboxyl group, and when the hindered phenol structure reacts with isocyanate, the phenolic hydroxyl group preferentially reacts with the isocyanate, so that the antioxidant activity of the modified isocyanate is obviously reduced, in other words, the antioxidant activity of the polyurethane material prepared by the method is very low.
Therefore, the compound with simple preparation method, low cost and high antioxidant activity is found, and particularly can be used for preparing polyurethane materials, is a problem to be solved by the person skilled in the art, and has high application value.
Disclosure of Invention
In view of the above, the present invention aims to provide an antioxidant compound, a preparation method and an application thereof, wherein the antioxidant compound has high antioxidant activity and shows excellent free radical scavenging activity.
The invention provides an antioxidant compound, which is prepared from the following raw materials of a functional reagent, isocyanate and a catalyst;
the functional reagent is alcohol containing a phenolic hydroxyl structure or amine containing a phenolic hydroxyl structure.
The antioxidant compound provided by the invention is prepared by introducing phenolic hydroxyl into an isocyanate molecular structure, so that the antioxidant compound has higher antioxidant activity, and shows excellent free radical scavenging activity, thus having great significance in synthesizing antioxidant polyurethane materials.
In the invention, the feeding mole ratio of the functional reagent, isocyanate and catalyst is 1: (3-35): (0 to 0.1).
In the invention, the chemical structure of the functional reagent is one or more of the following structures and isomers thereof:
r in formula 101, formula 102, formula 103 and formula 104 1 Independently selected from-H, aliphatic, araliphatic, aryl, or cycloalkyl; the R is 1 Preferably selected from C1-C30 alkyl, C6-C20 aryl, C6-C12 aryl or C3-C20 cycloalkyl; r in the formulas 102 and 103 is selected from aliphatic, araliphatic, aryl or cycloalkyl; preferably selected from C1-C20 alkyl, C6-C16 aryl, C6-C8 aryl or C3-C16 cycloalkyl.
In the present invention, the functional agent is selected from one or more of chrysophanol, rhein, emodin, aloe-emodin, physcion, aloin, curcumin, theaflavin, isoorientin, esculentin, orientin, glycyrrhizin, isoliquiritigenin, astragalin, catechin, epicatechin, gallocatechin, epigallocatechin, catechin-3-gallate, epicatechin-3-gallate, gallocatechin gallate, epigallocatechin gallate and para-aminophenol.
In the present invention, the isocyanate is a di-isocyanate and/or a polyisocyanate;
the diisocyanate is selected from one or more of isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, 1, 5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 3' -dimethyl-4, 4' -biphenyl diisocyanate, 1, 3-dimethyl isocyanate cyclohexane and dicyclohexylmethane 4,4' -diisocyanate;
the polyisocyanate is selected from one or more of triphenylmethane triisocyanate, 1, 3-bis (3-isocyanato-4-methylphenyl) -1, 3-diazacyclo-2, 4-butanedione, 1,3, 5-tris (3-isocyanatotolyl) -1,3, 5-triazine-2, 4, 6-trione, a tolylene diisocyanate-trimethylolpropane adduct, hexamethylene diisocyanate trimer, hexamethylene diisocyanate dimer, hexamethylene diisocyanate biuret and isophorone diisocyanate trimer.
The catalyst is selected from one or more of bismuth isooctanoate, potassium isooctanoate, stannous octoate, dibutyltin dilaurate, triethylenediamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 4-dimethylpiperazine, triethylenediamine, bis (dimethylaminoethyl) ether, dimethylcyclohexylamine and pentamethyldiethylenetriamine, preferably from one or more of stannous octoate, dibutyltin dilaurate, triethylenediamine and triethylenediamine.
The invention provides a preparation method of the antioxidant compound, which comprises the following steps:
mixing and reacting a functional reagent, isocyanate and a catalyst in the presence or absence of an organic solvent to obtain an antioxidant compound;
the organic solvent is selected from one or more of toluene, acetone, dichloromethane, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, dioxane, cyclohexane, acetonitrile and chloroform.
The invention selectively adds the organic solvent according to the reaction viscosity.
The preparation method disclosed by the invention is simple, convenient and green in process, free of metal ions, mild in reaction condition and environment-friendly; compared with the method for synthesizing the functional compound in the prior art, the method disclosed by the invention is simpler and has the step economy; the preparation method disclosed by the invention has a wide substrate range, can obtain more antioxidant compounds with complex structures, and is an important synthetic intermediate or a drug intermediate.
Specifically, the invention can prepare the antioxidant compound by mixing and reacting the functional reagent, isocyanate and the catalyst;
or dissolving the functional reagent in an organic solvent, and then mixing with isocyanate under the action of a catalyst to react to prepare the antioxidant compound; the mass ratio of the functional reagent to the organic solvent is 1:1-500.
In the present invention, the temperature of the reaction is 40 to 120 ℃.
The application of the antioxidant compound in preparing antioxidant and free radical scavenging material;
the antioxidant compound is the antioxidant compound according to the technical scheme.
The antioxidant compound provided by the invention has wide application in the synthesis of polyurethane materials, can be used as functional isocyanate to introduce phenolic hydroxyl groups with antioxidant function into polyurethane molecular main chains, so that the material has antioxidant function, and can maintain cell survival and proliferation capability in an oxidative stress environment. In the invention, the antioxidant and scavenging free base material is specifically an antioxidant polyurethane sponge, an antioxidant polyurethane adhesive, an antioxidant polyurethane elastomer or an antioxidant polyurethane coating.
The invention provides an antioxidant compound, which is prepared from the following raw materials of a functional reagent, isocyanate and a catalyst; the functional reagent is alcohol containing a phenolic hydroxyl structure or amine containing a phenolic hydroxyl structure. The phenolic hydroxyl is introduced into the molecular structure of isocyanate, so that the compound has higher antioxidant activity and shows excellent free radical scavenging activity. Antioxidant compounds have wide application in the synthesis of polyurethane materials. The experimental results show that: the free radical clearance of the antioxidant compound is 70.67 +/-1.98% -85.29 +/-0.86%; the ABTS plus free radical clearance of the antioxidant polyurethane material is 82.58 plus or minus 5.62 percent to 100 plus or minus 0.95 percent.
Detailed Description
In order to further illustrate the present invention, an antioxidant compound, a preparation method and application thereof, provided by the present invention, are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
100g of toluene diisocyanate (a mixture of 80 mass% of 2, 4-toluene diisocyanate and 20 mass% of 2, 6-toluene diisocyanate) and 0.2g of stannous octoate were added to 8.26g of emodin powder under the protection of nitrogen, and stirred at 70 ℃ to react until the NCO value was stable, thus obtaining an antioxidant compound.
Example 2
186g of toluene diisocyanate (a mixture of 80% by mass of 2, 4-toluene diisocyanate and 20% by mass of 2, 6-toluene diisocyanate) was added to 11.49g of isoliquiritigenin under nitrogen protection, and the mixture was stirred at 70℃until the NCO value was stable, to obtain an antioxidant compound.
Example 3
100g of isophorone diisocyanate and 30mL of tetrahydrofuran are added to 6.17g of curcumin powder under the protection of nitrogen, and stirring reaction is carried out at 70 ℃ until NCO value is stable, thus obtaining the antioxidant compound.
Example 4
110g of diphenylmethane diisocyanate and 0.25g of dibutyltin dilaurate were added to 11.53g of catechin powder under nitrogen protection, and stirred at 70 ℃ to react until NCO value was stable, to obtain an antioxidant compound.
Example 5
8.46g of p-aminophenol was dissolved in 300mL of a dry DMF solution under nitrogen protection, and then 22.25g of toluene diisocyanate and 0.31g of dibutyltin dilaurate were added thereto, and reacted under stirring at 70℃until the NCO value was stable, to obtain an antioxidant compound.
Example 6
Under the protection of nitrogen, 12.36g of aloe-emodin is dissolved in 420mL of cyclohexane and toluene (volume ratio is 1:1), 31.47g of triphenylmethane triisocyanate and 0.26g of stannous octoate are added, and stirring reaction is carried out at 70 ℃ until NCO value is stable, thus obtaining the antioxidant compound.
The antioxidant compounds synthesized in the examples above are synthetic material intermediates, and preferred embodiments of the present invention are described below in connection with the application examples, but it should be understood that these descriptions are merely intended to further illustrate the features and advantages of the present invention, and are not intended to limit the claims of the present invention.
Application example 1
To 100g of anhydrous polyether triol (number average molecular weight: 5000) was added 12.05g of toluene diisocyanate (a mixture of 80% by mass of 2, 4-toluene diisocyanate and 20% by mass of 2, 6-toluene diisocyanate) under nitrogen protection, and the mixture was stirred at 80℃until the NCO value was stable, to obtain a prepolymer. 100g of toluene diisocyanate (a mixture of 80% by mass of 2, 4-toluene diisocyanate and 20% by mass of 2, 6-toluene diisocyanate) was added to 8.26g of emodin powder under nitrogen protection, and the mixture was stirred at 70℃until the NCO value was stable, to obtain an antioxidant compound. 100g of deionized water, 51.23g of glycerol, 29.98g of polycaprolactone triol (molecular weight 540), 1.75g of polyoxyethylene and polyoxypropylene block polymer (L-64), 0.78g of sorbitan fatty acid ester, 2.56g of polyoxyethylene sorbitan fatty acid ester, 3.26g of C8-10 fatty alcohol polyoxyethylene ether and 0.95g of 3-aminopropyl trimethoxysilane are uniformly mixed at 20 ℃ to obtain a mixed chain extender B material. Mixing 100g of prepolymer with 23.29g of antioxidant compound, mechanically stirring uniformly at 550rpm for 5min to obtain material A, mechanically stirring 50g of material A and 41.66g of material B at 15 ℃ for free foaming at 1500rpm for 15s, pouring into a mould with 20cm x 30cm x 0.5cm, and restricting foaming for 30min under 15kg pressure to obtain the antioxidant polyurethane sponge material.
Application example 2
To 100g of anhydrous polyether triol (number average molecular weight: 5000) was added 14.39g of toluene diisocyanate (a mixture of 80% by mass of 2, 4-toluene diisocyanate and 20% by mass of 2, 6-toluene diisocyanate) under nitrogen protection, and the mixture was stirred at 80℃to react until the NCO value was stable, to obtain a prepolymer. 100g of toluene diisocyanate (a mixture of 80% by mass of 2, 4-toluene diisocyanate and 20% by mass of 2, 6-toluene diisocyanate) and 0.20g of dibutyltin dilaurate were added to 11.49g of isoliquiritigenin under the protection of nitrogen, and stirred at 70 ℃ to stabilize NCO value, thereby obtaining an antioxidant compound. 100g of deionized water, 12.38g of glycerol, 5.46g of polycaprolactone triol (molecular weight 900), 3.26g of polyoxyethylene and polyoxypropylene block polymer (L-62), 3.89g of polyoxyethylene sorbitan fatty acid ester, 6.84g of C8-10 fatty alcohol polyoxyethylene ether and 2.03g of polydimethylsiloxane are uniformly mixed at 20 ℃ to obtain a mixed chain extender B material. Mixing 100g of prepolymer with 26.60g of antioxidant compound, mechanically stirring uniformly at 650rpm for 4min to obtain material A, mechanically stirring 50g of material A and 67.5g of material B at 15 ℃ for free foaming at 1500rpm for 20s, and curing to obtain the antioxidant polyurethane sponge material.
Application example 3
Under the protection of nitrogen, 15.57g of isophorone diisocyanate is added into 50.00g of anhydrous polyethylene glycol 1, 6-hexanediol neopentyl glycol ester diol (molecular weight is 1500), and after stirring uniformly, 0.20g of dibutyltin dilaurate is added into the mixture, and stirring reaction is carried out at 75 ℃ until the NCO value is stable, thus obtaining the prepolymer. 100g of isophorone diisocyanate and 0.25g of dibutyltin dilaurate were added to 6.17g of curcumin powder under nitrogen protection, and stirred at 70 ℃ to react until NCO value was stable, to obtain an antioxidant compound. Mixing 100g of prepolymer with 20.85g of antioxidant compound, mechanically stirring uniformly at 500rpm for 5min, then removing bubbles at 80 ℃ in vacuum for 30min, adding 3.86g of 2, 4-trimethyl-1, 3-pentanediol, 2.97g of 3-aminopropyl triethoxysilane, 0.20g of polydimethylsiloxane and 0.07g of potassium isooctanoate, mechanically stirring for 5min at 2000rpm, and curing to obtain the polyurethane elastic material with antioxidant function.
Application example 4
Under the protection of nitrogen, adding 12.35g of diphenylmethane diisocyanate into 50.00g of anhydrous polypropylene oxide ether glycol (with the molecular weight of 3000), stirring uniformly, adding 0.10g of stannous octoate into the mixture, and stirring the mixture at 70 ℃ for reaction until the NCO value is stable to obtain a prepolymer; under the protection of nitrogen, adding 100g of diphenylmethane diisocyanate and 0.08g of stannous octoate into 6.17g of aloe-emodin powder, stirring at 70 ℃ for reaction until the NCO value is stable, and obtaining an antioxidant compound; mixing 100g of prepolymer with 13.26g of antioxidant compound, mechanically stirring uniformly at 500rpm for 5min, then removing bubbles in vacuum at 70 ℃ for 30min, adding 5.96g of 1, 6-hexamethylenediamine, mechanically stirring to form, and curing at 1000rpm to obtain the polyurethane elastic material with antioxidant function.
Application example 5
Under the protection of nitrogen, adding 25.20g of toluene diisocyanate (a mixture of 80 mass percent of 2, 4-toluene diisocyanate and 20 mass percent of 2, 6-toluene diisocyanate) and 0.01g of stannous octoate into 100.00g of anhydrous polycaprolactone polyol, and stirring at 70 ℃ to react until the NCO value is stable to obtain a prepolymer; under the protection of nitrogen, 12.81g of isoliquiritigenin is dissolved in 300ml of dry DMF solution, 22.25g of toluene diisocyanate and 0.31g of dibutyltin dilaurate are added, and stirring reaction is carried out at 70 ℃ until NCO value is stable, thus obtaining an antioxidant compound; 10.25g of prepolymer and 70ml of antioxidant compound were mixed and stirred uniformly, and then 12.96g of 1, 4-butanediol was added thereto and stirred at 70℃for 15 hours. And then precipitating the reaction solution in 1L of diethyl ether, washing the reaction solution for 2 to 3 times by using diethyl ether, collecting the precipitate, and drying the precipitate in vacuum until the weight is constant to obtain the polyurethane material with the antioxidant function.
Application example 6
Under the protection of nitrogen, 16.76g of theaflavin is dissolved in 50mL of toluene solution, 22.25g of diphenylmethane diisocyanate and 0.12g of dibutyltin dilaurate are added, and stirring reaction is carried out at 70 ℃ until NCO value is stable, thus obtaining an antioxidant compound; under the protection of nitrogen, 15.46g of diphenylmethane diisocyanate, 0.01g of stannous octoate, 16g of antioxidant compound, 20.56g of 1, 4-butanediol and 120mL of toluene solution are added into 100.00g of anhydrous polycaprolactone polyol, stirred and reacted at 40 ℃ until reaching a certain viscosity smear, and then air blast drying is carried out at 80 ℃ for 24 hours, thus obtaining the polyurethane coating material with the antioxidant function.
The radical scavenging rates of the antioxidant compounds of examples 1 to 6 were evaluated. Briefly, 4mL of ABTS diammonium salt stock solution (7.4 mmol/L) and 4mL of potassium persulfate stock solution (3.7 mmol/L) were mixed and left at room temperature for 12 hours, and the mixture was diluted 10 times with absolute ethanol to obtain an ABTS.+ free radical working solution. 1000 mu L of a sample-absolute ethanol solution (1 mg/mL) is placed in a 12-well plate, 300 mu L of ABTS working solution is added into each well, the reaction is carried out at room temperature in a dark place for 60min, and then an enzyme-labeled instrument is used for detecting the absorbance at 734 nm.
TABLE 1 free radical scavenging Rate of antioxidant Compounds of examples 1-6
The polyurethane materials prepared in application examples 1 to 6 were subjected to a radical scavenging test and a cell viability test under oxidative stress conditions. Samples were 1cm x 0.2cm squares, radical scavenging experiments were as above, cell experiments test methods reference (adv. Healthcare mate. 2019,8,1900582). Briefly, the cell experiments were performed by subjecting a sample of a general polyurethane elastomer, a general polyurethane sponge, and materials of application examples 1 to 6 to ultraviolet sterilization, then placing the sample in a 24-well plate, and respectively planting HUVEC cells on the surface of the sample, culturing 1 ten thousand cells per well at 37℃for 24 hours, and then adding H per well 2 O 2 The final concentration of the solution was 1mmol/L, and the culture was continued at 37℃for 48 hours, followed by measurement of the relative proliferation rate of cells by the CCK-8 method. The results of the free radical scavenging experiments and cell viability tests under oxidative stress conditions are shown in Table 2.
TABLE 2 Properties of antioxidant polyurethane materials of application examples 1 to 6
The above results show that the antioxidant compounds of examples 1 to 6 have higher antioxidant activity than the common isocyanate, and the antioxidant compounds of examples 1 to 6 prepared by the antioxidant compounds of the invention have better free radical scavenging ability than the commercial polyurethane materials, i.e. the antioxidant activity of the polyurethane materials of examples 1 to 6 is higher, and the relative proliferation rate of cells under oxidative stress conditions is higher, which means that the antioxidant compounds of the invention can effectively improve the survival and proliferation ability of cells under oxidative stress environment, so the antioxidant compounds of the invention have higher application value.
From the above examples, the present invention provides an antioxidant compound, the preparation raw materials comprising a functional agent, isocyanate and a catalyst; the functional reagent is alcohol containing a phenolic hydroxyl structure or amine containing a phenolic hydroxyl structure. The phenolic hydroxyl is introduced into the molecular structure of isocyanate, so that the compound has higher antioxidant activity and shows excellent free radical scavenging activity. Antioxidant compounds have wide application in the synthesis of polyurethane materials. The experimental results show that: the free radical clearance of the antioxidant compound is 70.67 +/-1.98% -85.29 +/-0.86%; the ABTS plus free radical clearance of the antioxidant polyurethane material is 82.58 plus or minus 5.62 percent to 100 plus or minus 0.95 percent.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. An antioxidant compound is prepared from functional reagent, isocyanate and catalyst;
the functional reagent is alcohol containing a phenolic hydroxyl structure or amine containing a phenolic hydroxyl structure.
2. The antioxidant compound of claim 1, wherein the functional agent, isocyanate and catalyst are dosed in a molar ratio of 1: (3-35): (0 to 0.1).
3. The antioxidant compound of claim 1, wherein the functional agent is selected from one or more of chrysophanol, rhein, emodin, aloe-emodin, physcion, aloin, curcumin, theaflavin, isoorientin, esculentin, orientin, glycyrrhizin, isoliquiritigenin, astragalin, epicatechin, gallocatechin, epigallocatechin, catechin-3-gallate, epicatechin-3-gallate, gallocatechin gallate, epigallocatechin gallate and para-aminophenol.
4. The antioxidant compound according to claim 1, wherein the isocyanate is a di-and/or polyisocyanate;
the diisocyanate is selected from one or more of isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, 1, 5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 3' -dimethyl-4, 4' -biphenyl diisocyanate, 1, 3-dimethyl isocyanate cyclohexane and dicyclohexylmethane 4,4' -diisocyanate;
the polyisocyanate is selected from one or more of triphenylmethane triisocyanate, 1, 3-bis (3-isocyanato-4-methylphenyl) -1, 3-diazacyclo-2, 4-butanedione, 1,3, 5-tris (3-isocyanatotolyl) -1,3, 5-triazine-2, 4, 6-trione, a tolylene diisocyanate-trimethylolpropane adduct, hexamethylene diisocyanate trimer, hexamethylene diisocyanate dimer, hexamethylene diisocyanate biuret and isophorone diisocyanate trimer.
5. The antioxidant compound of claim 1, wherein the catalyst is selected from one or more of bismuth isooctanoate, potassium isooctanoate, stannous octoate, dibutyltin dilaurate, triethylenediamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 1, 4-dimethylpiperazine, triethylenediamine, bis (dimethylaminoethyl) ether, dimethylcyclohexylamine, and pentamethyldiethylenetriamine.
6. A process for the preparation of the antioxidant compound of any one of claims 1 to 5, comprising the steps of:
mixing and reacting a functional reagent, isocyanate and a catalyst in the presence or absence of an organic solvent to obtain an antioxidant compound;
the organic solvent is selected from one or more of toluene, acetone, dichloromethane, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, dioxane, cyclohexane, acetonitrile and chloroform.
7. The process according to claim 6, wherein the temperature of the reaction is 40 to 120 ℃.
8. The application of antioxidant compounds in preparing antioxidant and free radical scavenging materials;
the antioxidant compound is the antioxidant compound according to any one of claims 1 to 5.
9. Use according to claim 8, characterized in that the oxidation-resistant, scavenging free-base material is in particular an oxidation-resistant polyurethane sponge, an antioxidant polyurethane adhesive, an oxidation-resistant polyurethane elastomer or an oxidation-resistant polyurethane coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310095712.5A CN115991662A (en) | 2023-02-10 | 2023-02-10 | Antioxidant compound and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310095712.5A CN115991662A (en) | 2023-02-10 | 2023-02-10 | Antioxidant compound and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115991662A true CN115991662A (en) | 2023-04-21 |
Family
ID=85994967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310095712.5A Pending CN115991662A (en) | 2023-02-10 | 2023-02-10 | Antioxidant compound and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115991662A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111675820A (en) * | 2020-06-18 | 2020-09-18 | 山东师范大学 | Surface-grafted curcumin modified degradable polyurethane composite material and preparation method and application thereof |
| CN112250821A (en) * | 2020-10-22 | 2021-01-22 | 杨振全 | Artificial heart valve material and preparation method thereof |
| CN114044875A (en) * | 2021-11-04 | 2022-02-15 | 万华化学集团股份有限公司 | Thermoplastic polyurethane elastomer and preparation method and application thereof |
| CN115215988A (en) * | 2022-08-16 | 2022-10-21 | 重庆科技学院 | Multifunctional polyurethane and preparation method and application thereof |
| CN115322332A (en) * | 2022-08-31 | 2022-11-11 | 江苏富琪森新材料有限公司 | Fluorescent bio-based polyurethane capable of being rapidly self-repaired and preparation method thereof |
-
2023
- 2023-02-10 CN CN202310095712.5A patent/CN115991662A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111675820A (en) * | 2020-06-18 | 2020-09-18 | 山东师范大学 | Surface-grafted curcumin modified degradable polyurethane composite material and preparation method and application thereof |
| CN112250821A (en) * | 2020-10-22 | 2021-01-22 | 杨振全 | Artificial heart valve material and preparation method thereof |
| CN114044875A (en) * | 2021-11-04 | 2022-02-15 | 万华化学集团股份有限公司 | Thermoplastic polyurethane elastomer and preparation method and application thereof |
| CN115215988A (en) * | 2022-08-16 | 2022-10-21 | 重庆科技学院 | Multifunctional polyurethane and preparation method and application thereof |
| CN115322332A (en) * | 2022-08-31 | 2022-11-11 | 江苏富琪森新材料有限公司 | Fluorescent bio-based polyurethane capable of being rapidly self-repaired and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103030770B (en) | Environment-friendly flame-retardant polyurethane emulsion and preparation method thereof | |
| CN105153393B (en) | Hydrophilic and bio-safety foam of polymers, its preparation method and application | |
| Shababdoust et al. | Controlled curcumin release from nanofibers based on amphiphilic-block segmented polyurethanes | |
| Feng et al. | Tough and biodegradable polyurethane-curcumin composited hydrogel with antioxidant, antibacterial and antitumor properties | |
| CN109749694B (en) | Medical polyurethane adhesive and preparation method thereof | |
| US20110086940A1 (en) | Silicone-Urethane Copolymers | |
| EP3727198A1 (en) | Soft tissue implant pocket | |
| EP1877461B1 (en) | Modification of thermoplastic polymers | |
| CN104520345A (en) | High strength polyisobutylene polyurethanes | |
| CN112126036A (en) | Disulfide bond-based biodegradable cross-linked self-repairing polyurethane and preparation method thereof | |
| CN102127204A (en) | Preparation method of novel antibiotic anticoagulant polyurethane material | |
| EP2821423B1 (en) | Polyurethane | |
| CN106589290A (en) | High-biocompatibility phosphorylcholine-modified polyurethane material and prepration method thereof | |
| Tamer et al. | Lysine-derived, pH-sensitive and biodegradable poly (beta-aminoester urethane) networks and their local drug delivery behaviour | |
| CN102030882A (en) | Method for preparing biodegradable polyurethane material with pH responsiveness | |
| Paula et al. | Development of light-degradable poly (urethane-urea) hydrogel films | |
| CN102526810A (en) | Artificial skin alternative material and preparation method thereof | |
| CN115991662A (en) | Antioxidant compound and preparation method and application thereof | |
| EP2673310B1 (en) | Tissue adhesive based on nitrogen-modified aspartates | |
| CN108070067A (en) | A kind of preparation method of Cross-linkable coating antibacterial polyurethane | |
| EP4083158A1 (en) | Polyurethane structural adhesive | |
| WO2013104564A1 (en) | Beta-amino acid ester and the use thereof | |
| Paula et al. | ROS-degradable PEG-based wound dressing films with drug release and antibacterial properties | |
| EP3545040B1 (en) | Polyurethane, method of preparation, and article comprising the polyurethane | |
| CN114015015B (en) | Polyurethane, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |