CN108727515B - Vegetable oleic acid-chitosan-based polyol and method for preparing same under catalysis of free radical photoinitiator - Google Patents
Vegetable oleic acid-chitosan-based polyol and method for preparing same under catalysis of free radical photoinitiator Download PDFInfo
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- CN108727515B CN108727515B CN201810645617.7A CN201810645617A CN108727515B CN 108727515 B CN108727515 B CN 108727515B CN 201810645617 A CN201810645617 A CN 201810645617A CN 108727515 B CN108727515 B CN 108727515B
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 156
- 229920005862 polyol Polymers 0.000 title claims abstract description 81
- 150000003077 polyols Chemical class 0.000 title claims abstract description 81
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 title claims abstract description 35
- 235000013311 vegetables Nutrition 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 16
- 239000012949 free radical photoinitiator Substances 0.000 title claims description 12
- 238000006555 catalytic reaction Methods 0.000 title claims description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 238000002360 preparation method Methods 0.000 claims abstract description 42
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 26
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000005642 Oleic acid Substances 0.000 claims abstract description 26
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 oleic acid ester Chemical class 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 5
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 63
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 52
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 42
- 229920001577 copolymer Polymers 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 26
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 25
- 238000001291 vacuum drying Methods 0.000 claims description 23
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 18
- 239000008158 vegetable oil Substances 0.000 claims description 18
- SHLSSLVZXJBVHE-UHFFFAOYSA-N 3-sulfanylpropan-1-ol Chemical compound OCCCS SHLSSLVZXJBVHE-UHFFFAOYSA-N 0.000 claims description 16
- OCNZHGHKKQOQCZ-CLFAGFIQSA-N [(z)-octadec-9-enoyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC(=O)CCCCCCC\C=C/CCCCCCCC OCNZHGHKKQOQCZ-CLFAGFIQSA-N 0.000 claims description 16
- 238000007789 sealing Methods 0.000 claims description 14
- 235000009518 sodium iodide Nutrition 0.000 claims description 14
- 238000003760 magnetic stirring Methods 0.000 claims description 13
- 229960003656 ricinoleic acid Drugs 0.000 claims description 13
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 13
- 230000006196 deacetylation Effects 0.000 claims description 12
- 238000003381 deacetylation reaction Methods 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 12
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 claims description 10
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 9
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 9
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 9
- 229960004488 linolenic acid Drugs 0.000 claims description 9
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 9
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 8
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 claims description 7
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 7
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 6
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 6
- FETFXNFGOYOOSP-UHFFFAOYSA-N 1-sulfanylpropan-2-ol Chemical compound CC(O)CS FETFXNFGOYOOSP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- ULGGZAVAARQJCS-UHFFFAOYSA-N 11-sulfanylundecan-1-ol Chemical compound OCCCCCCCCCCCS ULGGZAVAARQJCS-UHFFFAOYSA-N 0.000 claims description 5
- QNNVICQPXUUBSN-UHFFFAOYSA-N 2-sulfanylpropan-1-ol Chemical compound CC(S)CO QNNVICQPXUUBSN-UHFFFAOYSA-N 0.000 claims description 5
- MJQWABQELVFQJL-UHFFFAOYSA-N 3-Mercapto-2-butanol Chemical compound CC(O)C(C)S MJQWABQELVFQJL-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 4
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 claims description 4
- YMCOIFVFCYKISC-UHFFFAOYSA-N ethoxy-[2-(2,4,6-trimethylbenzoyl)phenyl]phosphinic acid Chemical compound CCOP(O)(=O)c1ccccc1C(=O)c1c(C)cc(C)cc1C YMCOIFVFCYKISC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003573 thiols Chemical class 0.000 claims description 4
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical group CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012957 2-hydroxy-2-methyl-1-phenylpropanone Substances 0.000 claims description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 claims description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 13
- 239000002028 Biomass Substances 0.000 abstract description 10
- 238000012650 click reaction Methods 0.000 abstract description 5
- 150000002148 esters Chemical group 0.000 abstract description 4
- 239000010773 plant oil Substances 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 50
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 235000020778 linoleic acid Nutrition 0.000 description 29
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- 239000007795 chemical reaction product Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 229960000583 acetic acid Drugs 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 13
- BDTYMGCNULYACO-MAZCIEHSSA-N [(9z,12z)-octadeca-9,12-dienoyl] (9z,12z)-octadeca-9,12-dienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OC(=O)CCCCCCC\C=C/C\C=C/CCCCC BDTYMGCNULYACO-MAZCIEHSSA-N 0.000 description 12
- 150000008064 anhydrides Chemical class 0.000 description 12
- 238000007865 diluting Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000012362 glacial acetic acid Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000006552 photochemical reaction Methods 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229960001051 dimercaprol Drugs 0.000 description 4
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- UGZAJZLUKVKCBM-UHFFFAOYSA-N 6-sulfanylhexan-1-ol Chemical compound OCCCCCCS UGZAJZLUKVKCBM-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 2
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 239000004837 Ultraviolet (UV) light curing adhesive Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000004426 flaxseed Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a vegetable oleic acid-chitosan-based polyol, which has a structural formula shown as a formula (I):
wherein n, k is 0 or 1, m + s is more than 0 and less than 4, and h + m + n + s + t is more than 12 and less than 16; r is C1-C4 straight-chain or straight-chain alkyl. The invention also discloses a preparation method and application of the vegetable oleic acid-chitosan-based polyol. The invention takes vegetable oleic acid-chitosan group as a base material, and utilizes mercaptan-alkene click chemical reaction to carry out ester exchange reaction between amino in chitosan and unsaturated vegetable oleic acid ester; and then, the plant oleic acid-chitosan polyol is prepared by introducing a long chain and a C-S bond through click reaction of a sulfydryl group and a double bond on a long chain of the plant oil under ultraviolet light, and the multifunctional base biomass polyol can be prepared by utilizing not only the plasticity and the antibacterial property of chitosan but also the flexibility of the long chain of unsaturated plant oil.
Description
Technical Field
The invention belongs to the technical field of UV photocatalysis, and particularly relates to vegetable oleic acid-chitosan-based polyol, and a method for preparing the vegetable oleic acid-chitosan-based polyol by catalyzing with a free radical photoinitiator.
Background
It is well known that non-renewable fossil resources such as oil and natural gas constitute the cornerstone of the fuel and chemical industries of the world today. The traditional polyol preparation raw materials are sourced from resources such as petroleum, natural gas and the like, and with the increasing shortage of resources such as petroleum, natural gas and the like and the enhancement of environmental awareness of people, the research on biomass polyol is more and more concerned by people. The biomass is used as a renewable resource, the source of the biomass is very wide, the polyol prepared from the biomass can replace petroleum polyol in the aspect of energy sources, the crisis that petroleum and natural gas are gradually lacking is relieved, a plurality of chemicals or chemical intermediates can be synthesized, and the biomass has the effect of being incapable of replacing in the aspects of environmental protection and overcoming the energy crisis. Therefore, the development of biomass polyols will become an important trend in the world energy and chemical industry.
The main component of the vegetable oil is unsaturated fatty acid such as fatty glyceride, and the carboxyl, ester and double bond of the unsaturated fatty acid can be introduced into hydroxyl group through a certain reaction in structure, generally through epoxidation or ozonization, and then are subjected to hydroxylation reaction with compounds with active hydrogen such as alcohol or acid under the action of a catalyst to introduce the hydroxyl group, so that the polyol with a certain functional group and relative molecular mass is prepared.
The chitosan is a high molecular compound which is second to cellulose in nature and exists in a large amount, and has the characteristics of good biodegradability, biocompatibility, bacteriostasis, film forming property and the like due to a large amount of polar functional groups of amino and hydroxyl on the molecular structure. In addition, the amino and hydroxyl also endow chitosan molecules with stronger reaction activity, and chemical reactions such as hydrolysis, alkylation, acylation, carboxymethylation, sulfonation, nitration, halogenation, oxidation, reduction, condensation, complexation and the like are easy to occur, so that various chitosan derivatives with different properties can be generated.
Thiol-ene click chemistry is in conjunction with thiol-alkyne click chemistry and is referred to as thiol-ene/alkyne click chemistry. The click chemical reaction has the advantages of mild reaction conditions, high yield, high speed, easy separation of products, high selectivity and the like, and can realize atom connection by utilizing a series of efficient and reliable C-S bonding reactions with selectivity to carry out modular preparation of novel high-performance and functional polymers.
In the prior art, a patent CN105669450A discloses a vegetable oil polyol with a high hydroxyl value, a preparation method and application thereof, wherein the vegetable oil polyol is prepared by ring-opening reaction and ester exchange reaction of epoxy vegetable oil and a polyhydroxy compound;
patent CN105669450A discloses a novel polyol derived from vegetable oils by an oxidative process, which invention provides a process for producing vegetable oil derived polyols having increased hydroxyl functionality by reacting vegetable oils with an oxidizing agent in the presence of an organometallic catalyst;
the patent CN103274930A discloses a method for preparing vegetable oil polyalcohol by a continuous method, the method for preparing vegetable oil polyalcohol provided by the invention is continuous operation, and the epoxidation and ring opening two-step reaction are combined into one step in the process, so that the method has the characteristics of simple and easily-controlled preparation process, high safety, short reaction time, low energy consumption and little pollution.
The technologies disclosed in the invention all use vegetable oil as a modified base material to prepare vegetable oil-based polyol, and do not mention vegetable oleic acid-chitosan-based polyol and a preparation method thereof, especially a method for preparing vegetable oleic acid-chitosan-based polyol by click reaction of a product obtained by reacting vegetable oleic acid with chitosan and mercaptan under the condition of ultraviolet light, and the technology is rarely reported.
Therefore, there is a need to develop a vegetable oil acid-chitosan-based polyol to enrich the variety of biomass polyols and to make the biomass polyols multifunctional.
Disclosure of Invention
It is an object of the present invention to provide a vegetable oil acid-chitosan based polyol to address one or more of the above problems.
It is also an object of the present invention to provide a method for preparing the above vegetable oil acid-chitosan based polyol catalyzed by a free radical photoinitiator to solve one or more of the above problems.
According to one aspect of the present invention, there is provided a vegetable oil acid-chitosan-based polyol having a structural formula as shown in formula (i):
wherein n, k is 0 or 1, m + s is more than 0 and less than 4, and h + m + n + s + t is more than 12 and less than 16;
r is C1-C4 straight-chain or straight-chain alkyl.
According to one aspect of the invention, a preparation method for preparing the polyol by catalysis of a free radical photoinitiator is provided, which comprises the following specific steps:
mixing the chitosan grafted plant oleic acid copolymer (shown as a formula (II)) with mercaptan and a free radical photoinitiator, performing reaction under the irradiation of UV light while performing magnetic stirring, then diluting with a first organic solvent, washing with a saturated inorganic salt solution, drying, filtering, finally removing the first organic solvent through a rotary evaporator, placing in a vacuum drying oven, and drying to obtain the plant oleic acid-chitosan-based polyol (shown as a formula (I)) initiated and synthesized by the free radical photoinitiator.
Wherein, the synthetic reaction of the vegetable oleic acid-chitosan polyol is as follows:
wherein n, k is 0 or 1, 0 < m + s < 4, 12 < h + m + n + s + t < 16.
In some embodiments, the vegetable oil acid is at least one of ricinoleic acid, eleostearic acid, linoleic acid, oleic acid.
In some embodiments, the thiol is at least one of 2-mercaptoethanol, 3-mercapto-1-propanol, 2, 3-dimercaptopropanol, 1-mercapto-2-propanol, 2-mercapto-3-propanol, 6-mercaptohex-1-ol, 3-mercapto-2-butanol, 11-mercapto-1-undecanol.
In some embodiments, the free radical photoinitiator is 2-hydroxy-2-methyl-1-phenylpropanone (trade name 1173), 1-hydroxycyclohexylphenylketone (trade name 184), 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone (trade name 907), 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (trade name TPO), ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (trade name TPO-L), 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone (trade name IHT-PI 910), 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone (trade name 659), methyl benzoylformate (trade name MBF).
In some embodiments, the first organic solvent is at least one of acetone, ethyl acetate, tetrahydrofuran, N-dimethylformamide, dichloromethane, isopropanol, methyl butanone.
In some embodiments, the power of the UV light is 100-1000W, the magnetic stirring speed is 100-1000 r/min, and the reaction time is 0-5 h.
In some embodiments, the inorganic salt is at least one of sodium sulfate, magnesium sulfate, sodium chloride, potassium chloride.
In some embodiments, the desiccant is preferably at least one of calcium chloride, phosphorus pentoxide, calcium sulfate, magnesium sulfate.
The preparation method of the chitosan grafted plant oleic acid copolymer comprises the following steps:
the preparation method comprises the steps of carrying out sealing reaction on vegetable oleic acid and acetic anhydride to prepare vegetable oleic anhydride (shown as a formula (IV)), then mixing chitosan (shown as a formula (III)) and sodium iodide solution, dropwise adding vegetable oleic anhydride and pyridine, stirring and mixing uniformly, carrying out constant-temperature reaction, then soaking with a second organic solvent, washing, dehydrating, and finally placing in a vacuum drying oven for drying treatment to obtain the chitosan grafted vegetable oleic acid copolymer.
The synthesis reaction formula of the chitosan grafted vegetable oleic acid (CS-g-VO) copolymer is shown as follows:
wherein n, k is 0 or 1, 0 < m + s < 4, 12 < h + m + n + s + t < 16.
Wherein the viscosity average molecular weight of chitosan is 1.2 × 103～2.5×105The deacetylation degree is more than or equal to 90 percent; the mass ratio of the chitosan to the sodium iodide is 1: 1-1: 6, the molar ratio of the vegetable oleic anhydride to the chitosan is 1: 1-5: 1, and the molar ratio of the pyridine to the vegetable oleic anhydride is 2: 1-6: 1.
In some embodiments, the reaction temperature in the synthesis reaction of the chitosan grafted vegetable oleic acid copolymer is 50-80 ℃, and the reaction time is 6-16 h.
In some embodiments, the second organic solvent is at least one of acetone, diethyl ether, ethanol; the drying temperature is 40-80 ℃, and the drying time is 4-48 h.
The invention takes vegetable oleic acid-chitosan group as a base material, and utilizes mercaptan-alkene click chemical reaction to carry out ester exchange reaction between amino in chitosan and unsaturated vegetable oleic acid ester; and then, the plant oleic acid-chitosan-based polyol is prepared by introducing a long chain and a C-S bond through click reaction of a sulfydryl group and a double bond on a long chain of the plant oil under ultraviolet light, and the multifunctional-based biomass polyol can be prepared by utilizing not only the plasticity and the antibacterial property of chitosan but also the flexibility of the long chain of unsaturated plant oil.
According to a further aspect of the invention, the vegetable oleic acid-chitosan-based polyol is applied to UV light curing materials, adhesives, printing ink and polyurethane materials.
Drawings
FIG. 1 is a comparison graph of IR spectra of linoleic acid and linoleic acid-chitosan based polyol according to an embodiment of the present invention, wherein a and b are linoleic acid and linoleic acid-chitosan based polyol, respectively;
FIG. 2 is a comparison graph of nuclear magnetic hydrogen spectra of linoleic acid and linoleic acid-chitosan-based polyol according to an embodiment of the present invention, wherein a and b are linoleic acid-chitosan-based polyol and linoleic acid, respectively.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1 linoleic acid-Chitosan-based polyol
The preparation method of the linoleic acid-chitosan-based polyalcohol comprises the following specific steps
1) Preparation of chitosan grafted linoleic acid copolymer:
29.85g of linoleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in an oil bath at 125 ℃ for reaction for 4 hours. Removing generated acetic acid and unreacted acetic anhydride under reduced pressure (78 deg.C, 90KPa) to obtain red brown linoleic anhydride liquid, drying, sealing and storing. Weighing viscosity average molecular weight of 1.0 × 105Dissolving 1g of chitosan with the deacetylation degree of 93% in 30mL of 1% (v/v) glacial acetic acid aqueous solution, adding 70mL of methanol, vigorously stirring to enable the solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding linoleic anhydride and pyridine, wherein the reaction molar ratio of linoleic anhydride to chitosan amino is 4:1, and the reaction molar ratio of pyridine to linoleic anhydride is 4:1, and vigorously stirring to enable the mixture to be uniformly mixed; reacting at 80 ℃ for 8h, soaking and washing with acetone for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 ℃ for 24h to obtain the chitosan grafted linoleic acid.
2) Preparation of linoleic acid-chitosan-based polyol:
uniformly mixing the chitosan grafted linoleic acid copolymer obtained in the step 1) with 2-mercaptoethanol and 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) serving as a photoinitiator, placing the mixture in a photochemical reaction instrument with the power of 600W, and carrying out magnetic stirring reaction for 4 hours, wherein the molar ratio of the 2-mercaptoethanol to the chitosan grafted linoleic acid copolymer is 3:1, the amount of the 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) is 1.5% of the total mass of the system, and the stirring speed is 500 r/min. After the reaction is finished, diluting the reaction product with an organic solvent ethyl acetate, washing the reaction product for 3-4 times by using a saturated sodium sulfate solution to remove unreacted 2-mercaptoethanol, drying and filtering phosphorus pentoxide, finally removing the organic solvent by using a rotary evaporator, and drying the organic solvent in a vacuum drying oven to obtain the linoleic acid-chitosan-based polyol.
Example 2 ricinoleic acid-Chitosan-based polyol
The preparation method of the ricinoleic acid-chitosan-based polyol comprises the following specific steps:
1) preparation of chitosan grafted ricinoleic acid copolymer:
29.85g of ricinoleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, the oil bath is heated to 130 ℃, and the reaction is carried out for 3 hours. Reducing pressure (78 deg.C, 90KPa) to remove the generated acetic acid and unreacted acetic anhydride to obtain red brown ricinoleic anhydride liquid, drying, sealing and storing. Weighing the mixture with viscosity-average molecular weight of 1.5 × 105Dissolving 1g of chitosan with deacetylation degree of 91% in 30mL of 1% (v/v) glacial acetic acid aqueous solution, adding 70mL of methanol and vigorously stirring to enable a solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding ricinoleic anhydride and pyridine, wherein the reaction molar ratio of ricinoleic anhydride/chitosan amino is 4:1, and the reaction molar ratio of pyridine to ricinoleic anhydride is 4:1, and vigorously stirring to enable the mixture to be uniformly mixed; reacting at 80 ℃ for 8h, soaking and washing with ethanol for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 ℃ for 24h to obtain chitosan grafted ricinoleic acid.
2) Preparation of ricinoleic acid-chitosan-based polyol:
uniformly mixing the chitosan grafted ricinoleic acid copolymer obtained in the step 1), 3-mercapto-1-propanol and a photoinitiator 1-hydroxycyclohexyl phenyl ketone (184), placing the mixture in a photochemical reaction instrument with the power of 600W, and carrying out magnetic stirring reaction for 4 hours, wherein the molar ratio of the 3-mercapto-1-propanol to the chitosan grafted ricinoleic acid copolymer is 3:1, the amount of the photoinitiator 1-hydroxycyclohexyl phenyl ketone (184) is 1.5% of the total mass of the system, and the stirring speed is 500 r/min. After the reaction is finished, diluting with ethyl acetate serving as a solvent, washing for 3-4 times by using saturated magnesium sulfate solution to remove unreacted 3-mercapto-1-propanol, drying by using anhydrous calcium chloride, filtering, removing the organic solvent by using a rotary evaporator, and drying in a vacuum drying oven to obtain the ricinoleic acid-chitosan-based polyol.
Example 3 Linseed acid-Chitosan based polyol
The preparation method of the linoleic acid-chitosan-based polyol comprises the following specific steps:
1) preparation of chitosan grafted linoleic acid copolymer:
29.85g of linoleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in oil bath at 120 ℃ for reaction for 5 hours. Reducing pressure (78 deg.C, 90KPa) to remove generated acetic acid and unreacted acetic anhydride to obtain reddish brown linolenic anhydride liquid, drying, sealing and storing. Weighing viscosity average molecular weight of 1.0 × 105Dissolving 1g of chitosan with deacetylation degree of 93% in 30mL of 1% (v/v) glacial acetic acid aqueous solution, adding 70mL of methanol, vigorously stirring to enable a solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding linolenic acid and pyridine, wherein the reaction molar ratio of linolenic acid to chitosan amino is 4:1, and the reaction molar ratio of pyridine to linolenic acid is 4:1, and vigorously stirring to enable the linolenic acid and the pyridine to be uniformly mixed; reacting at 80 deg.C for 8h, soaking in acetone, washing for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 deg.C for 24h to obtain chitosan grafted linoleic acid.
2) Preparation of linoleic acid-chitosan based polyol:
uniformly mixing the chitosan grafted linoleic acid copolymer obtained in the step 1) with 3-mercapto-1-propanol and a photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (trade name is 1173), placing the mixture in a photochemical reaction instrument with the power of 600W, and carrying out magnetic stirring reaction for 4 hours, wherein the molar ratio of the 3-mercapto-1-propanol to the chitosan grafted linoleic acid copolymer is 3:1, the amount of the photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (trade name is 1173) is 1.5% of the total mass of the system, and the stirring speed is 500 r/min. After the reaction is finished, diluting the reaction product by using an organic solvent N, N-dimethylformamide, washing the reaction product for 3-4 times by using a saturated sodium sulfate solution to remove unreacted 3-mercapto-1-propanol, drying the reaction product by using calcium sulfate, filtering the reaction product, removing the organic solvent by using a rotary evaporator, and drying the reaction product in a vacuum drying oven to obtain the linoleic acid-chitosan-based polyol.
Example 4 eleostearic acid-chitosan based polyol
The preparation method of the eleostearic acid-chitosan-based polyol comprises the following specific steps:
1) preparation of chitosan grafted eleostearic acid copolymer:
29.85g of eleostearic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in oil bath at 139 ℃ to react for 4 hours. Reducing pressure (78 deg.C, 90KPa) to remove generated acetic acid and unreacted acetic anhydride to obtain red-brown tung oil anhydride liquid, drying, sealing and storing. Weighing the mixture with viscosity-average molecular weight of 1.2 × 105Dissolving 1g of chitosan with the deacetylation degree of 90% in 30mL of 1% (v/v) glacial acetic acid aqueous solution, adding 70mL of methanol, vigorously stirring to enable the solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding eleostearic acid anhydride and pyridine, wherein the molar ratio of the eleostearic acid anhydride to the chitosan amino group in a reaction is 3:1, and the molar ratio of the pyridine to the eleostearic acid anhydride in a reaction is 3:1, and vigorously stirring to enable the mixture to be uniformly mixed; reacting at 70 deg.C for 10h, soaking in acetone, washing for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 50 deg.C for 48h to obtain chitosan grafted eleostearic acid.
2) Preparing eleostearic acid-chitosan-based polyol:
uniformly mixing the chitosan grafted eleostearic acid copolymer obtained in the step 1) with 2-mercapto-3-propanol and a photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173), placing the mixture in a photochemical reaction instrument with the power of 500W, and carrying out magnetic stirring reaction for 3 hours, wherein the molar ratio of the 2-mercapto-3-propanol to the chitosan grafted eleostearic acid copolymer is 3:1, the amount of the photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (1173) is 2% of the total mass of the system, and the stirring speed is 600 r/min. After the reaction is finished, diluting with ethyl acetate serving as a solvent, washing for 3-4 times by using a saturated sodium chloride solution to remove unreacted 2-mercapto-3-propanol, drying by using anhydrous calcium chloride, filtering, removing an organic solvent by using a rotary evaporator, and drying in a vacuum drying oven to obtain the eleostearic acid-chitosan-based polyol.
Example 5 oleic acid-Chitosan-based polyol
The preparation method of the oleic acid-chitosan-based polyol comprises the following specific steps:
1) preparation of chitosan grafted oleic acid copolymer:
29.85g of oleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in an oil bath at 125 ℃ for reaction for 4 hours. Reducing pressure (78 deg.C, 90KPa) to remove the generated acetic acid and unreacted acetic anhydride to obtain reddish brown oleic anhydride liquid, drying, sealing and storing. Weighing viscosity average molecular weight of 3.0 × 105Dissolving 1g of chitosan with deacetylation degree of 91% in 40mL of 1% (v/v) glacial acetic acid aqueous solution, adding 80mL of methanol, vigorously stirring to enable the solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding oleic anhydride and pyridine, wherein the reaction molar ratio of oleic anhydride to chitosan amino is 4:1, and the reaction molar ratio of pyridine to oleic anhydride is 4:1, and vigorously stirring to enable the mixture to be uniformly mixed; reacting at 80 ℃ for 8h, soaking and washing with acetone for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 ℃ for 24h to obtain chitosan grafted oleic acid.
(2) Preparation of oleic acid-chitosan-based polyol: uniformly mixing the chitosan grafted oleic acid copolymer obtained in the step 1) with 2, 3-dimercaprol and a photoinitiator 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (659), placing the mixture in a photochemical reaction instrument with the power of 800W, and carrying out magnetic stirring reaction for 3 hours, wherein the molar ratio of the 2, 3-dimercaprol to the chitosan grafted oleic acid copolymer is 4:1, the amount of the photoinitiator 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (659) is 1.0 percent of the total mass of the system, and the stirring speed is 700 r/min. After the reaction is finished, diluting the obtained product with an organic solvent acetone, washing the obtained product for 3-4 times by using a saturated potassium chloride solution to remove unreacted 2, 3-dimercaptopropanol, drying the obtained product with magnesium sulfate, filtering the obtained product, removing the organic solvent by using a rotary evaporator, and drying the obtained product in a vacuum drying oven to obtain the oleic acid-chitosan-based polyol.
Example 6 oleic acid-Chitosan-based polyol
The preparation method of the oleic acid-chitosan-based polyol comprises the following specific steps:
1) preparation of chitosan grafted oleic acid copolymer:
29.85g of oleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in an oil bath at 125 ℃ for reaction for 4 hours. Reducing pressure (78 deg.C, 90KPa) to remove the generated acetic acid and unreacted acetic anhydride to obtain reddish brown oleic anhydride liquid, drying, sealing and storing. Weighing viscosity average molecular weight of 3.0 × 105Dissolving 1g of chitosan with deacetylation degree of 91% in 40mL of 1% (v/v) glacial acetic acid aqueous solution, adding 80mL of methanol, vigorously stirring to enable the solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding oleic anhydride and pyridine, wherein the molar ratio of oleic anhydride to chitosan amino reaction is 4:1, and the molar ratio of pyridine to oleic anhydride reaction is 4:1, and vigorously stirring to enable the mixture to be uniformly mixed; reacting at 80 ℃ for 8h, soaking and washing with acetone for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 ℃ for 24h to obtain chitosan grafted oleic acid.
2) Preparation of oleic acid-chitosan-based polyol: uniformly mixing the chitosan grafted oleic acid copolymer obtained in the step 1) with 2, 3-dimercaprol and a photoinitiator 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (659), placing the mixture in a photochemical reaction instrument with the power of 800W, and carrying out magnetic stirring reaction for 3 hours, wherein the molar ratio of the 2, 3-dimercaprol to the chitosan grafted oleic acid copolymer is 4:1, the amount of the photoinitiator 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone (659) is 1.0 percent of the total mass of the system, and the stirring speed is 700 r/min. After the reaction is finished, diluting with an organic solvent dichloromethane, washing for 3-4 times by using a saturated potassium chloride solution to remove unreacted 2, 3-dimercaptopropanol, drying by using magnesium sulfate, filtering, removing the organic solvent by using a rotary evaporator, and drying in a vacuum drying oven to obtain the oleic acid-chitosan-based polyol.
Example 7 linoleic acid-Chitosan based polyol
The preparation method of the linoleic acid-chitosan-based polyol comprises the following specific steps:
1) preparation of chitosan grafted linoleic acid copolymer:
29.85g of linoleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in oil bath at 120 ℃ for reaction for 5 hours. Reducing pressure (78 deg.C, 90KPa) to remove generated acetic acid and unreacted acetic anhydride to obtain reddish brown linolenic anhydride liquid, drying, sealing and storing. Weighing viscosity average molecular weight of 1.0 × 105Dissolving 1g of chitosan with deacetylation degree of 93% in 30mL of 1% (v/v) glacial acetic acid aqueous solution, adding 70mL of methanol, vigorously stirring to enable a solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding linolenic acid and pyridine, wherein the reaction molar ratio of linolenic acid to chitosan amino is 4:1, and the reaction molar ratio of pyridine to linolenic acid is 4:1, and vigorously stirring to enable the linolenic acid and the pyridine to be uniformly mixed; reacting at 80 deg.C for 8h, soaking in acetone, washing for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 deg.C for 24h to obtain chitosan grafted linoleic acid.
2) Preparation of linoleic acid-chitosan based polyol:
uniformly mixing the chitosan grafted linoleic acid copolymer obtained in the step 1) with 6-mercaptohexane-1-ol and a photoinitiator 1-hydroxycyclohexyl phenyl ketone (184), placing the mixture in a photochemical reaction instrument with the power of 600W, and carrying out magnetic stirring reaction for 4 hours, wherein the molar ratio of the 6-mercaptohexane-1-ol to the chitosan grafted linoleic acid copolymer is 3:1, the amount of the photoinitiator 1-hydroxycyclohexyl phenyl ketone (184) is 1.5 percent of the total mass of the system, and the stirring speed is 500 r/min. After the reaction is finished, diluting the reaction product with an organic solvent methyl butanone, washing the reaction product for 3-4 times by using a saturated sodium sulfate solution to remove unreacted 6-mercaptohexan-1-ol, drying the reaction product by using calcium sulfate, filtering the reaction product, removing the organic solvent by using a rotary evaporator, and drying the reaction product in a vacuum drying oven to obtain the linoleic acid-chitosan-based polyol.
Example 8 linoleic acid-Chitosan-based polyol
The preparation method of the linoleic acid-chitosan-based polyalcohol comprises the following specific steps
1) Preparation of chitosan grafted linoleic acid copolymer:
29.85g of linoleic acid is weighed and poured into a flask, 20.4g of acetic anhydride is added into the flask, the reaction system is sealed, and the mixture is heated in an oil bath at 125 ℃ for reaction for 4 hours. Removing generated acetic acid and unreacted acetic anhydride under reduced pressure (78 deg.C, 90KPa) to obtain red brown linoleic anhydride liquid, drying, sealing and storing. Weighing viscosity average molecular weight of 1.0 × 105Dissolving 1g of chitosan with the deacetylation degree of 93% in 30mL of 1% (v/v) glacial acetic acid aqueous solution, adding 70mL of methanol, vigorously stirring to enable the solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding linoleic anhydride and pyridine, wherein the reaction molar ratio of linoleic anhydride to chitosan amino is 4:1, and the reaction molar ratio of pyridine to linoleic anhydride is 4:1, and vigorously stirring to enable the mixture to be uniformly mixed; reacting at 80 ℃ for 8h, soaking and washing with acetone for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 ℃ for 24h to obtain the chitosan grafted linoleic acid.
2) Preparation of linoleic acid-chitosan-based polyol:
uniformly mixing the chitosan grafted linoleic acid copolymer obtained in the step 1) with 1-mercapto-2-propanol and a photoinitiator ethyl 2,4, 6-trimethylbenzoylphenylphosphonate (TPO-L), placing the mixture in a photochemical reaction instrument with the power of 600W, and carrying out magnetic stirring reaction for 4 hours, wherein the molar ratio of the 1-mercapto-2-propanol to the chitosan grafted linoleic acid copolymer is 3:1, 2,4, 6-trimethylbenzoylphenylphosphonate ethyl (TPO-L), the amount of the 1-mercapto-2-propanol to the total mass of the system is 1.5%, and the stirring speed is 500 r/min. After the reaction is finished, diluting the reaction product with an organic solvent ethyl acetate, washing the reaction product for 3-4 times by using a saturated sodium sulfate solution to remove unreacted 1-mercapto-2-propanol, drying the reaction product by using phosphorus pentoxide, filtering the reaction product, removing the organic solvent by using a rotary evaporator, and drying the reaction product in a vacuum drying oven to obtain the linoleic acid-chitosan-based polyol.
Example 9 ricinoleic acid-Chitosan-based polyol
The preparation method of the ricinoleic acid-chitosan-based polyol comprises the following specific steps:
1) preparation of chitosan grafted ricinoleic acid copolymer:
29.85g ricinoleic acid was weighed into a flask, and 20.4g ricinoleic acid was added to the flaskAcetic anhydride, sealing the reaction system, heating in oil bath at 130 ℃, and reacting for 3 h. Reducing pressure (78 deg.C, 90KPa) to remove the generated acetic acid and unreacted acetic anhydride to obtain red brown ricinoleic anhydride liquid, drying, sealing and storing. Weighing the mixture with viscosity-average molecular weight of 1.5 × 105Dissolving 1g of chitosan with deacetylation degree of 91% in 30mL of 1% (v/v) glacial acetic acid aqueous solution, adding 70mL of methanol and vigorously stirring to enable a solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding ricinoleic anhydride and pyridine, wherein the reaction molar ratio of ricinoleic anhydride/chitosan amino is 4:1, and the reaction molar ratio of pyridine to ricinoleic anhydride is 4:1, and vigorously stirring to enable the mixture to be uniformly mixed; reacting at 80 ℃ for 8h, soaking and washing with ethanol for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 ℃ for 24h to obtain chitosan grafted ricinoleic acid.
2) Preparation of ricinoleic acid-chitosan-based polyol:
uniformly mixing the chitosan grafted ricinoleic acid copolymer obtained in the step 1), 11-mercapto-1-undecanol and a photoinitiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), placing the mixture in a photochemical reaction instrument with the power of 600W, and carrying out magnetic stirring reaction for 4 hours, wherein the molar ratio of the 11-mercapto-1-undecanol to the chitosan grafted ricinoleic acid copolymer is 3:1, the amount of the photoinitiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) is 1.5% of the total mass of the system, and the stirring speed is 500 r/min. After the reaction is finished, diluting the reaction product with ethyl acetate serving as a solvent, washing the reaction product for 3-4 times by using saturated magnesium sulfate solution to remove unreacted 11-mercapto-1-undecanol, drying the reaction product by using anhydrous calcium chloride, filtering the reaction product, removing the organic solvent by using a rotary evaporator, and drying the organic solvent in a vacuum drying oven to obtain the ricinoleic acid-chitosan-based polyol.
Example 10 linoleic acid-Chitosan-based polyol
The preparation method of the linoleic acid-chitosan-based polyalcohol comprises the following specific steps
1) Preparation of chitosan grafted linoleic acid copolymer:
weighing 29.85g of linoleic acid, pouring into a flask, adding 20.4g of acetic anhydride into the flask, sealing the reaction system, heating in an oil bath at 125 ℃,and reacting for 4 h. Removing generated acetic acid and unreacted acetic anhydride under reduced pressure (78 deg.C, 90KPa) to obtain red brown linoleic anhydride liquid, drying, sealing and storing. Weighing viscosity average molecular weight of 1.0 × 105Dissolving 1g of chitosan with the deacetylation degree of 93% in 30mL of 1% (v/v) glacial acetic acid aqueous solution, adding 70mL of methanol, vigorously stirring to enable the solution system to be in a clear and uniform state, adding 2g of sodium iodide, mixing, dropwise adding linoleic anhydride and pyridine, wherein the reaction molar ratio of linoleic anhydride to chitosan amino is 4:1, and the reaction molar ratio of pyridine to linoleic anhydride is 4:1, and vigorously stirring to enable the mixture to be uniformly mixed; reacting at 80 ℃ for 8h, soaking and washing with acetone for 3 times, dehydrating with diethyl ether, washing with ethanol for 3 times, and vacuum drying at 60 ℃ for 24h to obtain the chitosan grafted linoleic acid.
2) Preparation of linoleic acid-chitosan-based polyol:
uniformly mixing the chitosan grafted linoleic acid copolymer obtained in the step 1) with 3-mercapto-2-butanol and a photoinitiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), placing the mixture in a photochemical reaction instrument with the power of 600W, and carrying out magnetic stirring reaction for 4 hours, wherein the molar ratio of the 3-mercapto-2-butanol to the chitosan grafted linoleic acid copolymer is 3:1, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO), the amount of the chitosan grafted linoleic acid copolymer is 1.5% of the total mass of the system, and the stirring speed is 500 r/min. After the reaction is finished, diluting with an organic solvent isopropanol, washing for 3-4 times by using a saturated sodium sulfate solution to remove unreacted 3-mercapto-2-butanol, drying by using phosphorus pentoxide, filtering, removing the organic solvent by using a rotary evaporator, and drying in a vacuum drying oven to obtain the linoleic acid-chitosan-based polyol.
The products prepared in examples 1 to 5 were subjected to structural identification using an AVATAR 360FT-IR Fourier Infrared spectrometer manufactured by Nicolet corporation, USA, and a Bruker AV 600 nuclear magnetic resonance spectrometer manufactured by Bruker Biospin AG, Switzerland, and the results were as follows:
the characterization result of example 1 is shown in fig. 1 and fig. 2, wherein a in fig. 1 represents the infrared spectrum of linoleic acid, b represents the infrared spectrum of linoleic acid-chitosan-based polyol, and as can be seen from fig. 1, the absorption peak at 3016cm-1 of spectrum a is the stretching vibration peak of unsaturated double bond in long chain of soybean oil; and the stretching vibration peak at 3016cm-1 in the spectrogram b disappears, and a wide and strong absorption peak appears at 3405cm-1, which is the stretching vibration absorption peak of-OH, and indicates that the linoleic acid is grafted by chitosan.
In fig. 2, a and b are nuclear magnetic resonance hydrogen spectrograms of linoleic acid-chitosan-based polyol and linoleic acid, characteristic peaks with chemical shifts of 5.3-5.5ppm in a spectrogram b are C ═ C double bonds in a soybean oil long chain, characteristic peaks of double bonds at the position in the spectrogram a disappear, new absorption peaks appear at positions with chemical shifts of 2.5-2.7 ppm, 2.7-2.8 ppm and 3.7-3.8ppm in the spectrogram a, 2.5-2.7 ppm belong to hydrogen on a tertiary carbon connected with thiol, and 2.7-2.8 ppm and 3.7-3.8ppm are respectively two methylene groups on 2-mercaptoethanol, namely the characteristic peaks of the two methylene groups in thiol molecules grafted on the soybean oil double bonds through click reaction.
The characteristic peaks obtained in examples 2 to 10 are the same as those in example 1, and are not described herein again.
The detection result shows that the linoleic acid-chitosan-based polyol can be prepared by using the photoinitiator as the catalyst through click reaction under the condition of UV light.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (9)
1. The vegetable oleic acid-chitosan-based polyol is characterized in that chitosan-based vegetable oleic acid is used as a base material, is mixed with mercaptan and a free radical photoinitiator, and is obtained by reacting for 0-5h and more than 0h under the irradiation of UV light with the power of 100-1000W, and the structural formula of the polyol is shown as the formula (I):
(Ⅰ)
wherein n, k =0 or 1, 0 < m + s < 4, 12 < h + m + n + s + t < 16;
r is C1-C4 alkyl;
the free radical photoinitiator is 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, 6-trimethyl benzoyl phenyl phosphonic acid ethyl ester, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-acetone and methyl benzoylformate.
2. The preparation method of the vegetable oil acid-chitosan-based polyol as claimed in claim 1 by using a free radical photoinitiator for catalysis is characterized by comprising the following steps:
mixing the chitosan grafted vegetable oleic acid copolymer with mercaptan and a free radical photoinitiator, reacting for 0-5h to more than 0h under the irradiation of UV light with the power of 100-1000W, and stirring to obtain the vegetable oleic acid-chitosan based polyol as claimed in claim 1.
3. The method according to claim 2, wherein the vegetable oil acid is at least one of ricinoleic acid, eleostearic acid, linoleic acid, and linolenic acid.
4. The method according to claim 3, wherein the thiol is at least one of 2-mercaptoethanol, 3-mercapto-1-propanol, 2, 3-dimercaptopropanol, 1-mercapto-2-propanol, 2-mercapto-3-propanol, 6-mercaptohex-1-ol, 3-mercapto-2-butanol, and 11-mercapto-1-undecanol.
5. The method according to claim 4, wherein the radical photoinitiator is 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylmethanone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, or mixtures thereof, At least one of methyl benzoylformate.
6. The preparation method according to claim 5, wherein the power of the UV light is 100-1000W, magnetic stirring is adopted for stirring, the stirring speed is 100-1000 r/min, and the reaction time is 0-5h and more than 0 h.
7. The method according to claim 6, wherein the chitosan-grafted vegetable oleic acid copolymer is prepared by: the preparation method comprises the steps of carrying out sealing reaction on vegetable oleic acid and acetic anhydride to prepare vegetable oleic anhydride, then mixing chitosan and sodium iodide solution, dropwise adding vegetable oleic anhydride and pyridine, stirring and mixing uniformly, carrying out constant-temperature reaction, then soaking in a second organic solvent, washing, dehydrating, and finally placing in a vacuum drying oven for drying treatment to obtain the chitosan grafted vegetable oleic acid copolymer.
8. The method according to claim 7, wherein the viscosity-average molecular weight of the chitosan is 1.2X 103~2.5×105The deacetylation degree is more than or equal to 90 percent; the mass ratio of the chitosan to the sodium iodide is 1: 1-1: 6, the molar ratio of the vegetable oleic anhydride to the chitosan is 1: 1-5: 1, and the molar ratio of the pyridine to the vegetable oleic anhydride is 2: 1-6: 1.
9. The preparation method according to any one of claims 2 to 8, wherein the reaction temperature in the synthesis reaction of the chitosan grafted vegetable oleic acid copolymer is 50 ℃ to 80 ℃, and the reaction time is 6 to 16 hours.
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