CN110144031A - A kind of method of photoinduction organic catalysis lignin graft modification - Google Patents
A kind of method of photoinduction organic catalysis lignin graft modification Download PDFInfo
- Publication number
- CN110144031A CN110144031A CN201910414047.5A CN201910414047A CN110144031A CN 110144031 A CN110144031 A CN 110144031A CN 201910414047 A CN201910414047 A CN 201910414047A CN 110144031 A CN110144031 A CN 110144031A
- Authority
- CN
- China
- Prior art keywords
- lignin
- phenyl
- phenthazine
- naphthalene
- phenoxazine
- 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.)
- Granted
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000004048 modification Effects 0.000 title claims abstract description 19
- 238000012986 modification Methods 0.000 title claims abstract description 19
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 125000005257 alkyl acyl group Chemical group 0.000 claims abstract description 8
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 7
- 229920005601 base polymer Polymers 0.000 claims abstract description 6
- 230000003287 optical effect Effects 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 230000005855 radiation Effects 0.000 claims abstract description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 84
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- 238000004090 dissolution Methods 0.000 claims description 25
- -1 2- bromo isobutyl acylbromide Chemical class 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- 239000004305 biphenyl Substances 0.000 claims description 11
- 235000010290 biphenyl Nutrition 0.000 claims description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 7
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 6
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 6
- QXBUYALKJGBACG-UHFFFAOYSA-N 10-methylphenothiazine Chemical compound C1=CC=C2N(C)C3=CC=CC=C3SC2=C1 QXBUYALKJGBACG-UHFFFAOYSA-N 0.000 claims description 5
- RCBSZGSHSLQLBI-UHFFFAOYSA-N 5,10-diphenylphenazine Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N(C=2C=CC=CC=2)C2=CC=CC=C21 RCBSZGSHSLQLBI-UHFFFAOYSA-N 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- LAVLDGSVWFEKJG-UHFFFAOYSA-N 10-phenylphenoxazine Chemical compound C12=CC=CC=C2OC2=CC=CC=C2N1C1=CC=CC=C1 LAVLDGSVWFEKJG-UHFFFAOYSA-N 0.000 claims description 4
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 claims description 4
- PYNYHMRMZOGVML-UHFFFAOYSA-N 2-bromopropanenitrile Chemical compound CC(Br)C#N PYNYHMRMZOGVML-UHFFFAOYSA-N 0.000 claims description 4
- PDEMFFCYEHCCDT-UHFFFAOYSA-N COC1=CC=C(C=C1)C1=CC=CC=2NC3=CC=CC=C3NC12 Chemical compound COC1=CC=C(C=C1)C1=CC=CC=2NC3=CC=CC=C3NC12 PDEMFFCYEHCCDT-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- NVVCZYAGESORQR-UHFFFAOYSA-N 1-[4-(trifluoromethyl)phenyl]-10H-phenoxazine Chemical compound C1=CC(C(F)(F)F)=CC=C1C1=CC=CC2=C1NC1=CC=CC=C1O2 NVVCZYAGESORQR-UHFFFAOYSA-N 0.000 claims description 2
- BKORERVNQPDBNW-UHFFFAOYSA-N 10-[4-(trifluoromethyl)phenyl]phenoxazine Chemical compound FC(C1=CC=C(C=C1)N1C2=CC=CC=C2OC=2C=CC=CC1=2)(F)F BKORERVNQPDBNW-UHFFFAOYSA-N 0.000 claims description 2
- XUJPZOGJYLQLEO-UHFFFAOYSA-N 2,8-dimethylnonan-2-yl prop-2-enoate Chemical compound C(C=C)(=O)OC(C)(CCCCCC(C)C)C XUJPZOGJYLQLEO-UHFFFAOYSA-N 0.000 claims description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 150000004893 oxazines Chemical class 0.000 claims description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 claims description 2
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 150000002240 furans Chemical class 0.000 claims 1
- ZMVAWNCSXGFEDX-UHFFFAOYSA-N methane hydrobromide Chemical compound Br.C[H] ZMVAWNCSXGFEDX-UHFFFAOYSA-N 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 56
- 239000000243 solution Substances 0.000 description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 42
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 26
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 22
- 229910052794 bromium Inorganic materials 0.000 description 22
- 229920000642 polymer Polymers 0.000 description 22
- 238000001291 vacuum drying Methods 0.000 description 21
- 238000003756 stirring Methods 0.000 description 19
- 238000001914 filtration Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 13
- 239000003708 ampul Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 11
- 229960000583 acetic acid Drugs 0.000 description 11
- 230000001376 precipitating effect Effects 0.000 description 11
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 11
- 238000013019 agitation Methods 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 9
- 229940113088 dimethylacetamide Drugs 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 5
- MXFYYFVVIIWKFE-UHFFFAOYSA-N dicyclohexyl-[2-[2,6-di(propan-2-yloxy)phenyl]phenyl]phosphane Chemical compound CC(C)OC1=CC=CC(OC(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 MXFYYFVVIIWKFE-UHFFFAOYSA-N 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920001732 Lignosulfonate Polymers 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 150000001502 aryl halides Chemical class 0.000 description 3
- OQROAIRCEOBYJA-UHFFFAOYSA-N bromodiphenylmethane Chemical compound C=1C=CC=CC=1C(Br)C1=CC=CC=C1 OQROAIRCEOBYJA-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 2
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ZWPYQVOZFDLKQZ-UHFFFAOYSA-N 1-phenyl-10h-phenoxazine Chemical compound C=12NC3=CC=CC=C3OC2=CC=CC=1C1=CC=CC=C1 ZWPYQVOZFDLKQZ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical class C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 1
- YICILWNDMQTUIY-UHFFFAOYSA-N 2-methylidenepentanamide Chemical compound CCCC(=C)C(N)=O YICILWNDMQTUIY-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- IVURTNNWJAPOML-UHFFFAOYSA-N 5,10-dihydrophenazine Chemical compound C1=CC=C2NC3=CC=CC=C3NC2=C1 IVURTNNWJAPOML-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- FINPLSBBDVRBPA-UHFFFAOYSA-M chloropalladium(1+);dicyclohexyl-[2-[2,6-di(propan-2-yloxy)phenyl]phenyl]phosphane;2-methoxy-2-methylpropane;2-phenylethanamine Chemical compound [Pd+]Cl.COC(C)(C)C.NCCC1=CC=CC=[C-]1.CC(C)OC1=CC=CC(OC(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 FINPLSBBDVRBPA-UHFFFAOYSA-M 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
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- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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Abstract
The invention discloses a kind of methods of photoinduction organic catalysis lignin graft modification, lignin synthesizes lignin macromole evocating agent with alkyl acyl halide initiator for reaction, then in an inert atmosphere, it is mixed with vinyl monomer, catalyst, solvent, atom transfer radical polymerization is carried out under ultraviolet light or visible optical radiation, obtains lignin-base polymer.The invention has the advantages that organic catalyst can be avoided the metal residual in product, photoinduction free radical polymerization has good space-time controlling, and lignin causes various of monomer and is graft-polymerized, and can get the lignin-base polymer of various new structure-controllable.
Description
Technical field
The invention belongs to synthesis of polymer material fields, and in particular to a kind of photoinduction organic catalysis lignin graft modification
Method.
Background technique
Lignin is the second largest biomass resource for being only second to cellulose, can be widely used in bio-based materials field,
Advantageously reduce the consumption of fossil resource and the protection of ecological environment.Currently, there are mainly two types of the methods that lignin is recycled:
1) unmodified lignin is mixed with Material Physics, to improve the thermodynamic property of material itself.But due to structure π-π heap itself
The clustering phenomena of product interaction, the compatibility of storeroom is poor, and the intensity and plasticity of material are bad, significantly limits
The application of industrial circle；2) thermoplasticity of polymer and the compatibility of material will be enhanced after chemistry of lignin's modification.It is wooden
Hydroxyl structure rich in plain structure, such as phenolic aldehyde tree hydroxyl, rouge aliphatic hydroxide radical etc. can be grafted tool on lignin structure
There is the polymer of specific functionality group, synthesis has specific functionality material.
Atom transfer radical polymerization (ATRP) is to prepare the widest modifying and decorating method of lignin-base graft copolymer
One of, by having the macromolecular of clear molecular structure, low dispersibility poly- molecular weight and the grafting density synthesis for controlling grafted chain
Close object.And current ATRP modification lignin generally uses metallic catalyst (Cu+1,Cu+2), the lignin-base polymer of synthesis
In have the problems such as metal residual, have certain cytotoxicity, this significantly limits lignin in fields such as biologic medicals
Application.On the other hand, atom transfer radical polymerization (the Organocatalyzed atom transfer of organic catalysis
Radical polymerization) there is the problems such as high catalytic efficiency, non-metal catalyst remains, draw in polymerization field
The interest of vast researcher is played.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of no metal residual, catalysis
Mild condition, safe and efficient preparation is compared with low polydispersity, high molecular weight, the lignin-base macromolecular function of having preferable thermodynamic property
The method of property material.
In order to solve the above-mentioned technical problem, the invention discloses a kind of sides of photoinduction organic catalysis lignin graft modification
Method includes the following steps:
(1) lignin synthesizes lignin macromole evocating agent with alkyl acyl halide initiator for reaction；
(2) in an inert atmosphere, the lignin macromole evocating agent that step (1) is obtained, vinyl monomer, catalyst,
Solvent mixing, atom transfer radical polymerization is carried out under ultraviolet light or visible optical radiation, obtains lignin-base polymer.
Specifically, above-mentioned reaction synthetic route is as shown in Figure 1；Wherein, the value range of m is 1~600 in product.
Preferably, in step (1), the alkyl acyl halide reagent be 2- bromo isobutyl acylbromide, 2- bromopropionitrile, sulfonic acid chloride, 2,
2- dichloroacetophenone, diphenyl bromomethane or chloroform, each structure are as shown in Figure 2；The lignin be sulfate-reducing conditions,
Lignin, the lignosulfonates, soda lignin of organic solvent dissolution.
Specifically, reaction is completed under triethylamine effect in step (1), wherein hydroxyl and alkyl acyl in the lignin
The reaction molar ratio of halogen initiator is 1:1~3.
Preferably, in step (2), the vinyl monomer is benzyl methacrylate, ethyl methacrylate, methyl
Isobutyl acrylate, methacrylic acid -2- ethylhexyl, lauryl methacrylate, 2- methyl -2- isodecyl acrylate, 2-
Acrylic ester monomers and the propylene such as methyl -2- acrylic acid -2- (2- methoxy ethoxy) ethyl ester, methyl methacrylate
Any one in nitrile, styrene or N-isopropylacrylamide, the above vinyl monomer molecular structure is as shown in Figure 3.
Specifically, in step (2), the catalyst is PC1) 10- phenyl phenthazine, PC2) 4- methoxyphenyl -10- pheno
Thiazine, PC3) the chloro- 10H- phenthazine of 4-, PC4) 1- naphthalene -10H- phenthazine, PC5) 2- naphthalene -10H- phenthazine, PC6) 10-
(pyridine -2-yl) -10H- phenthazine, PC7) 10 methyl phenothiazine, PC8) 10- (4- (trifluoromethyl) phenyl)-phenthazine,
PC9) 10- (4- (itrile group) phenyl) phenthazine, PC10) phenyl benzo [b] phenthazine, PC11) 2- naphthalene -10H- phenoxazine,
PC12) 10- (4- (itrile group) phenyl) phenoxazine, PC13) 10- (4- (trifluoromethyl) phenyl) phenoxazine, PC14) 10- phenyl pheno
Oxazines, PC15) 1- naphthalene -10H- phenoxazine, PC16) 3,7-2 (4- diphenyl) 1- naphthalene -10- phenoxazine, PC17) 3,7-2
(4- diphenyl) 2- naphthalene -10- phenoxazine, PC18) 5,10- diphenyl -5,10- dihydrophenazine, PC19) 5,10-2 (4- methoxy
Base phenyl -) -5,10- dihydrophenazine, PC20) 5,10-2 (4- trifluoromethyl) phenyl) -5,10- dihydrophenazine, PC21) 5,10-2
(4- (itrile group) phenyl) -5,10- dihydrophenazine, PC22) 5,10-2 (2- naphthalene) -5,10- dihydrophenazine, PC23) 5,10-2 (1-
Naphthalene) -5,10- dihydrophenazine, PC24) combination of any one or more in perylene.The above catalyst molecule structure
See Fig. 4 and Fig. 5.
In step (2), the reaction dissolvent is N-N- dimethylformamide, N-N- dimethyl acetamide, methylene chloride, two
Any one in methyl sulfoxide, tetrahydrofuran or ethyl acetate.
Preferably, the lignin macromole evocating agent, vinyl monomer, catalyst reaction molar ratio be 1:10~
500:0.05~0.200.
In step (2), concentration of the vinyl monomer in reaction dissolvent is 0.5-5mol/L.
In step (2), the light source and optical wavelength being catalyzed needed for reacting are selected according to catalyst respectively, specifically: when
When catalyst is 10- phenyl phenthazine (PC1), 10 methyl phenothiazine (PC7), the ultraviolet light of 365nm or 380nm can be used to urge
Change；
When catalyst is 4- methoxyphenyl-lysivane (PC2), the chloro- 10H- phenthazine (PC3) of 4-, 1- naphthalene-
10H- phenthazine (PC4), 2- naphthalene -10H- phenthazine (PC5), 10- (pyridine -2-yl) -10H- phenthazine (PC6), 10- (4-
(trifluoromethyl) phenyl)-phenthazine (PC8), 10- (4- (itrile group) phenyl) phenthazine (PC9), phenyl benzo [b] phenthazine
(PC10), 2- naphthalene -10H- phenoxazine (PC11), 10- (4- (itrile group) phenyl) phenoxazine (PC12), 10- (4- (trifluoromethyl)
When phenyl-phenoxazine (PC13), 10- phenyl phenoxazine (PC14), 1- naphthalene -10H- phenoxazine (PC15), the purple of 365nm is used
Outer photocatalysis；
When catalyst is 5,10- diphenyl -5,10- dihydrophenazine (PC18), 5,10-2 (4- methoxyphenyl -) -5,10-
Dihydrophenazine (PC19), 5,10-2 (4- trifluoromethyl) phenyl) -5,10- dihydrophenazine (PC20), 5,10-2 (4- (itrile group) benzene
Base) -5,10- dihydrophenazine (PC21), 5,10-2 (2- naphthalene) -5,10- dihydrophenazine (PC22), 5,10-2 (1- naphthalene) -5,
10- dihydrophenazine (PC23) 3,7-2 (4- diphenyl) 1- naphthalene -10- phenoxazine (PC16), 3,7-2 (4- diphenyl) 2- naphthalene -
When 10- phenoxazine (PC17), perylene (PC24), it is catalyzed using white led lamps.
The utility model has the advantages that
The invention has the advantages that obtaining macromole evocating agent to hydroxyl modification on lignin, raw material is cheap；Polymerization reaction exists
It is carried out under light source control, can be reacted and be carried out by the switch control of illuminator, and using a variety of organic photochemical catalysts in room temperature
Under, to lignin grafting functional monomer, obtain novel environment friendly polymer material.
Detailed description of the invention
The present invention is done with reference to the accompanying drawings and detailed description and is further illustrated, of the invention is above-mentioned
And/or otherwise advantage will become apparent.
Fig. 1 is the synthetic route chart of lignin-base polymer；
Fig. 2 is different alkyl acyl halide initiator molecule structure charts；
Fig. 3 different vinyl monomer molecular structures；
Fig. 4, Fig. 5 are different catalyst molecule structure charts.
Specific embodiment
According to following embodiments, the present invention may be better understood.
In following embodiment, PC represents organic catalyst.[M]: [I]: [C] indicates vinyl monomer, lignin macromolecular
Halogen atom content, the ratio of catalyst in initiator, bromine atom content refer to mol (Br)/mass (lignin-Br).This hair
In bright, lignin, initiator, vinyl monomer, solvent, fluorescent tube be it is commercially available, wherein sulfate-reducing conditions, molecular weight are
10000g/mol contains 8.0mmol/g phenolic hydroxyl group；The molecular weight of organic solvent lignin is 5000g/mol, is contained
3.16mmol/g phenolic hydroxyl group；Lignosulfonate molecules amount is 8000g/mol, contains 5.24mmol/g phenolic hydroxyl group；Soda is wooden
The molecular weight of element is 10000g/mol, contains 10.24mmol/g phenolic hydroxyl group.The present invention is first with initiator to lignin
(lignin) hydroxyl modification utilizes catalyst later under light control at lignin macromole evocating agent (lignin-Br) on
Synthesize lignin macromolecule polyalcohol.
It wherein, is by the tert-butyl alcohol using the general step that phenthazine and its derivative are synthesized as the catalyst (PC1-10) of substrate
Sodium (134mg, 1.4mmol), phenthazine (199mg, 1mmol), RuPhos Precat (14mg, 0.02mmol) and RuPhos
(8mg, 0.02mmol) is added in the Schlenk bottle containing magnetic stir bar.Three times by bottle substitution gas, in nitrogen protection
It is lower that anhydrous Isosorbide-5-Nitrae-dioxane (1mL) is added, the aryl halide reagent of 1.4mmol is then added.Bottle is placed in 110 DEG C of oil bath
In and stir 6h.Then bottle is cooled to room temperature, uses CH2Cl 2Dilution, with water, salt water washing three times, uses Mg2SO 4It is dry
It is dry, and with column chromatography eluting.Vacuum drying obtains product.
It is to pass through elder generation by phenyl benzo [b-] phenthazine (PC10) of substrate of phenothiazine derivative-benzo [b] phenthazine
By 2,3- dihydroxy naphthlene (8g, 0.05mol)), 1,2, the 4- trichloro-benzenes of 2- amino benzenethiol (6.25g, 0.05mol) and 25mL add
Enter in the round-bottomed flask comprising magnetic stir bar.Reaction mixture is heated to 200 DEG C and keeps 6h at such a temperature, and with steam
The water of vapour trap collection reaction process.When cooling, product is precipitated, and n-hexane and ethanol washing product are successively used in filtering later,
Obtain benzo [b] phenthazine of yellow powder.Phenyl benzo [b-] pheno thiophene is obtained by above-mentioned general step step again later
Piperazine (PC10).
Synthesis is to be dried and removed first by flame by the general step of the catalyst (PC11-17) of substrate of phenoxazine
Water in Schlenk bottles allows in bottle later by substitution gas three times full of nitrogen.Phenoxazine is added into flask again later
(800mg, 4.37mmol), sodium tert-butoxide (840mg, 8.74mmol) and RuPhos (52.4mg, 0.13mmol).Bottle is placed in
In the glove box of inflated with nitrogen, wherein RuPhos Precat (91.77mg, 0.13mmol) and the anhydrous Isosorbide-5-Nitrae-dioxane of 4mL is added
With 8.74mmol aryl halide.Flask is placed in 130 DEG C of oil bath, stirs 48h.Then flask is cooled to room temperature, uses CH2Cl 2Dilution, column chromatography for separation.
3,7-2 (4- diphenyl) 1- naphthalene -10- phenoxazine is to synthesize conventional method by above-mentioned catalyst first to synthesize 1- naphthalene
1- naphthalene -10- phenoxazine (800mg, 2.58mmol) is then dissolved in 80mL chloroform by base -10- phenoxazine.Then will
80mL glacial acetic acid is added in the mixture of stirring.Aluminium foil is thoroughly wound to cover reaction bottle, stops light.In the dark,
Powdered N-bromosuccinimide (944mg, 5.30mmol) is slowly added into 20min.After reacting 2h at room temperature, then will
Solvent in reaction mixture is spin-dried for.Obtained solid is successively used into water, salt water washing three times, then uses MgSO4It is dry, then very
Sky is dry, the intermediate product 3 collected, the bromo- 1- naphthalene -10- phenoxazine of 7- bis-.
The schlenk flask equipped with magnetic stir bar and reflux condenser is dried by flame later, three times displacement gas
Body removes water, carries out nitrogen protection, and the bromo- 1- naphthalene -10- phenoxazine (225mg, 0.48mmol) of 3,7- bis-, 4- connection is then first added
Phenyl boric acid (381.8mg, 1.9mmol), is then dissolved in 20mL THF.By 6mL K2CO 3(2M) injects in solution, then
It is heated to 80 DEG C and stirs 20min.Then, addition is molten dissolved with the 20mL THF of tetrakis triphenylphosphine palladium (93mg, 15%mol)
Liquid is then heated to 100 DEG C and reacts for 24 hours.Once completing, the solvent in reactant is spin-dried for, is re-dissolved in DCM, successively
Three times with water, salt washing, MgSO is then used4It is dry.Collection catalyst is chromatographed finally by column.
It is that 5,10- bis- is sequentially added in Schlenk pipe by the catalyst (PC18-23) of substrate of 5,10- dihydrophenazine
Hydrogen azophenlyene (1.00g, 5.50mmol), sodium tert-butoxide (2.11g, 22.00mmol), RuPhos (103mg, 0.22mmol),
RuPhos pre-catalyst (180mg, 0.22mmol), 22.0mmol aryl halide reagent and 8.00mL1,4- dioxane.It will
Under Schlenk bottles are protected under a nitrogen, 10h is heated at 110 DEG C.After being cooled to room temperature, 200mL is added into reaction mixture
CH 2Cl 2, three times with 200mL distillation water washing.Use MgSO4Dry organic layer, vacuum drying are pure by column chromatography later
Change.
Perylene (PC24) is commercial solvents.
Bromine atom content in lignin is measured by styrene standardization.It is m that specific practice, which is by quality,sStyrene and
Quality is m1Lignin be dissolved in deuterated reagent, pass through1H NMR analysis, determines according to the following formula:
Wherein AlIt is initiator part methyl proton1H NMR integral domain (m, 1.8-2.3), As are one of styrene
Vinyl proton1H NMR integral domain (d, 5.1-5.4), a are the onychostroma subnumbers in initiator, and 104 be point of styrene
Son amount, msAnd mlIt is the quality of styrene and lignin-Br respectively.
For the present invention once in embodiment, degree of polymerization DP represents the quantity of grafting vinyl monomers on lignin, can pass through
Following methods measurement obtains (by taking the lignin macromole evocating agent of 2- bromo isobutyl acylbromide initiator modification as an example):
DP=(m/2)/(n/6)
Wherein, m indicates-CH on vinyl monomer2The integral of proton in nucleus magnetic hydrogen spectrum；It is modified on n expression lignin
Two-CH on 2- bromo isobutyl acylbromide3The integral of proton in nucleus magnetic hydrogen spectrum.
Using the molecular weight and molecualr weight distribution of following detection method detection product:
Using Wyattx volume exclusion chromatography system, it is formulated with SSI 1500 and pumps, Wyatt Optilab rEX detector,
The GPC post detection of Waters Styragel HR；
Analysis condition: mobile phase is tetrahydrofuran, flow velocity 0.7mL/min, 25 DEG C of column temperature, sampling volume 0.7mL；
Sample preparation: taking product 30mg, is diluted to 3mL with tetrahydrofuran solution, (contains 0.22um with disposable filtering head
Organic filter membrane) filtering after sample introduction.
Embodiment 1:
By sulfate-reducing conditions (0.250g ,-OH 2.0mmol), triethylamine (5.0mmol, 0.506g) and 75mL acetic acid second
Ester is added in the 250mL round-bottomed flask of tetrafluoroethene magnetic stir bar, and 30min is stirred in oil bath at room temperature, then in ice bath
Middle cooling, by 2- bromine isobutyl acylbromide (4.0mmol, 0.919g)/2- bromopropionitrile (4.0mmol, 0.532g)/sulfonic acid chloride
(4.0mmol, 0.536g)/2,2- dichloroacetophenone (4.0mmol, 0.752g)/diphenyl bromomethane (4.0mmol, 0.984g)/
Chloroform (4.0mmol, 0.472g), which is dissolved in 10mL ethyl acetate, to be slowly added into round-bottomed flask, and reaction for 24 hours, is added
20mL water/tetrahydrofuran solution.5min is stirred, unreacted 2- bromine isobutyl acylbromide is quenched.Solvent is spin-dried for, with Isosorbide-5-Nitrae-dioxane
Dissolution is precipitated with unsaturated sodium bicarbonate, filtering, water re-using washing.Ether dissolution is used again, and filtering is dry in 40 DEG C of vacuum
It is dry obtain lignin macromole evocating agent (bromine atom content be followed successively by 4.5mmol/g, 4.2mmol/g, 4.2mmol/g,
4.3mmol/g、4.4mmol/g、4.5mmol/g)。
Under nitrogen protection, successively in 6 ampoule bottles be added six kinds synthesis lignin macromole evocating agents (0.4mmol,
0.089g, 0.095g, 0.095g, 0.093g, 0.091g, 0.089g) and 10- phenyl-phenthazine (PC1,22mg,
0.08mmol), methyl methacrylate (20.024g, 200mmol), 18.76mL n,N-dimethylacetamide solution ([M]:
[I]: [C]=500:1:0.2, C=5M) (reaction temperature keeps room temperature to magnetic agitation 6h under 365nm, 16W ultraviolet light
20-30℃).Take 2mL reaction solution.It is diluted with tetrahydrofuran solution, n-hexane precipitating, vacuum drying obtains pure polymer.
The DP of polymer is respectively 440,461,453,435,467,536, PDI be respectively 1.65,1.56,1.30,1.15,1.38,
1.87。
Embodiment 2:
Respectively by organic solvent dissolution lignin (0.632g ,-OH 2.0mmol), lignosulfonates (0.382g ,-
OH2.0mmol), soda lignin (0.195g ,-OH 2.0mmol), triethylamine (5.0mmol, 0.50g) and 75mL ethyl acetate
It is added in the 250mL round-bottomed flask of tetrafluoroethene magnetic stir bar, 30min is stirred in oil bath at room temperature, then in ice bath
It is cooling, 2- bromine isobutyl acylbromide (4.0mmol, 0.92g) is dissolved in 10mL ethyl acetate and is slowly added into round-bottomed flask, is reacted
For 24 hours, 20mL water/tetrahydrofuran solution is added.5min is stirred, unreacted 2- bromine isobutyl acylbromide is quenched.Solvent is spin-dried for, with Isosorbide-5-Nitrae-
Dioxane dissolution, is precipitated with unsaturated sodium bicarbonate, filtering, water re-using washing.Ether dissolution, filtering, 40 are used again
DEG C vacuum drying obtain lignin macromole evocating agent (bromine atom content be followed successively by 2.58mmol/g, 3.12mmol/g,
5.97mmol/g。
Under nitrogen protection, successively in 3 ampoule bottles be added three kinds synthesis lignin macromole evocating agents (0.4mmol,
0.155g, 0.128g, 0.067g) and 10- phenyl-phenthazine (PC1,22mg, 0.08mmol), methyl methacrylate
(20.024g, 200mmol), 18.76mL n,N-dimethylacetamide solution ([M]: [I]: [C]=500:1:0.2) exist
Magnetic agitation 6h under 365nm, 16W ultraviolet light (reaction temperature keeps 20-30 DEG C of room temperature).Take 2mL reaction solution.With tetrahydro furan
Solution of muttering dilution, n-hexane precipitating, vacuum drying obtain pure polymer.Polymer DP is respectively 498,501,516, PDI
Respectively 1.41,1.43,1.57.
Embodiment 3:
By sulfate-reducing conditions (0.250g ,-OH 2.0mmol), triethylamine (5.0mmol, 0.506g) and 75mL acetic acid second
Ester is added in the 250mL round-bottomed flask of tetrafluoroethene magnetic stir bar, and 30min is stirred in oil bath at room temperature, then in ice bath
2- bromine isobutyl acylbromide (4.0mmol, 0.919g) is dissolved in 10mL ethyl acetate and being slowly added into round-bottomed flask by middle cooling,
For 24 hours, 20mL water/tetrahydrofuran solution is added in reaction.5min is stirred, unreacted 2- bromine isobutyl acylbromide is quenched.Solvent is spin-dried for, and is used
Isosorbide-5-Nitrae-dioxane dissolution, is precipitated, filtering with unsaturated sodium bicarbonate, water re-using washing.Ether dissolution is used again, is filtered,
Obtaining lignin macromole evocating agent in 40 DEG C of vacuum drying, (bromine atom content is followed successively by 4.5mmol.
Under nitrogen protection, be successively added in 10 ampoule bottles synthesis lignin macromole evocating agent (0.4mmol,
0.089g), 10- phenyl-phenthazine (PC1,22mg, 0.08mmol) and different monomer (benzyl methacrylates
(200mmol, 35.242g)/ethyl methacrylate (200mmol, 22.828g)/Isobutyl methacrylate (200mmol,
28.440g)/methacrylic acid -2- ethylhexyl (200mmol, 39.660g)/lauryl methacrylate (200mmol,
50.882g)/2- methyl -2- isodecyl acrylate (200mmol, 45.272g)/2- methyl -2- acrylic acid -2- (2- methoxyl group second
Oxygroup) ethyl ester (200mmol, 37.644g)/acrylonitrile (200mmol, 10.612g)/styrene (200mmol, 20.83g)/different
Propylacrylamide (200mmol, 22.632g)) 46.11mL/55.11mL/ is being added in 10 ampoule bottles respectively
The DMAC N,N' dimethyl acetamide solution of 47.16mL/4 0mL/40mL/40mL/43.10mL/46.83mL/17.01mL/17.86mL
([M]: [I]: [C]=500:1:0.2, C=2.5M)) magnetic agitation 6h (protect by reaction temperature under 365nm, 16W ultraviolet light
Hold 20-30 DEG C of room temperature).Take 2mL reaction solution.It is diluted with tetrahydrofuran solution, n-hexane precipitating, vacuum drying obtains pure gather
Close object.The DP of polymer is respectively 469,514,466,510,502,487,452,517,498,456, PDI be respectively 1.31,
1.24、1.37、1.45、1.28、1.27、1.29、1.29、1.34、1.33。
Embodiment 4:
By sulfate-reducing conditions (0.250g ,-OH 2.0mmol), triethylamine (5.0mmol, 0.506g) and 75mL acetic acid second
Ester is added in the 250mL round-bottomed flask of tetrafluoroethene magnetic stir bar, and 30min is stirred in oil bath at room temperature, then in ice bath
2- bromine isobutyl acylbromide (4.0mmol, 0.919g) is dissolved in 10mL ethyl acetate and being slowly added into round-bottomed flask by middle cooling,
For 24 hours, 20mL water/tetrahydrofuran solution is added in reaction.5min is stirred, unreacted 2- bromine isobutyl acylbromide is quenched.Solvent is spin-dried for, and is used
Isosorbide-5-Nitrae-dioxane dissolution, is precipitated, filtering with unsaturated sodium bicarbonate, water re-using washing.Ether dissolution is used again, is filtered,
Obtaining lignin macromole evocating agent in 40 DEG C of vacuum drying, (bromine atom content is followed successively by 4.5mmol/g.
Under nitrogen protection, be successively added in 10 ampoule bottles synthesis lignin macromole evocating agent (0.4mmol,
0.089g), methyl methacrylate (20.024g, 200mmol) and different organic catalyst 10- phenyl-phenthazine
(22mg, 0.08mmol)/10 methyl phenothiazine (17mg, 0.08mmol) (structure is shown in PC1, PC7 in Detailed description of the invention 3) is to anti-
Answer in bottle be added 18.76mL DMAC N,N' dimethyl acetamide solution ([M]: [I]: [C]=500:1:0.2) 365nm/380nm,
Magnetic agitation 6h under 16W ultraviolet light (reaction temperature keeps 20-30 DEG C of room temperature).Take 2mL reaction solution.Use tetrahydrofuran solution
Dilution, n-hexane precipitating, vacuum drying obtain pure polymer.Polymer DP is respectively 419/524,496/503, PDI points
It Wei not 1.45/1.38,1.36/1.52.
Embodiment 5:
By sulfate-reducing conditions (0.250g ,-OH 2.0mmol), triethylamine (5.0mmol, 0.506g) and 75mL acetic acid second
Ester is added in the 250mL round-bottomed flask of tetrafluoroethene magnetic stir bar, and 30min is stirred in oil bath at room temperature, then in ice bath
2- bromine isobutyl acylbromide (4.0mmol, 0.919g) is dissolved in 10mL ethyl acetate and being slowly added into round-bottomed flask by middle cooling,
For 24 hours, 20mL water/tetrahydrofuran solution is added in reaction.5min is stirred, unreacted 2- bromine isobutyl acylbromide is quenched.Solvent is spin-dried for, and is used
Isosorbide-5-Nitrae-dioxane dissolution, is precipitated, filtering with unsaturated sodium bicarbonate, water re-using washing.Ether dissolution is used again, is filtered,
Obtaining lignin macromole evocating agent in 40 DEG C of vacuum drying, (bromine atom content is followed successively by 4.5mmol/g.
Under nitrogen protection, be successively added in 5 ampoule bottles synthesis lignin macromole evocating agent (0.4mmol,
0.089g), methyl methacrylate (20.024g, 200mmol) and different organic catalyst 4- methoxyphenyl -10- phenos
The chloro- 10H- phenthazine (25mg, 0.08mmo) of thiazine (24mg, 0.08mmol)/4-/1- naphthalene -10H- phenthazine (26mg,
0.08mmo)/(2- naphthalene -10H- phenthazine (26mg, 0.08mmol)/10- (pyridine -2-yl) -10H- phenthazine
(0.08mmol, 22mg)/10- (4- trifluoromethyl) phenyl)-phenthazine (0.08mmol, 27mg)/10- (4- (itrile group) phenyl)
Phenthazine (0.08mmol, 24mg), phenyl benzo [b-] phenthazine (0.08mmol, 26mg)) (structure is shown in Detailed description of the invention 3
PC2, PC3, PC4, PC5, PC6, PC8, PC9, PC10) 18.76mL DMAC N,N' dimethyl acetamide solution is being added into reaction flask
([M]: [I]: [C]=500:1:0.2) (reaction temperature keeps room temperature 20- to magnetic agitation 6h under 365nm, 16W ultraviolet light
30℃).Take 2mL reaction solution.It is diluted with tetrahydrofuran solution, n-hexane precipitating, vacuum drying obtains pure polymer.Polymerization
The DP of object is respectively 414,452,487,479,537,528,458,462, PDI be respectively 1.35,1.24,1.43,1.52,
1.40、1.33、1.31。
Embodiment 6:
By sulfate-reducing conditions (0.250g ,-OH 2.0mmol), triethylamine (5.0mmol, 0.506g) and 75mL acetic acid second
Ester is added in the 250mL round-bottomed flask of tetrafluoroethene magnetic stir bar, and 30min is stirred in oil bath at room temperature, then in ice bath
2- bromine isobutyl acylbromide (4.0mmol, 0.919g) is dissolved in 10mL ethyl acetate and being slowly added into round-bottomed flask by middle cooling,
For 24 hours, 20mL water/tetrahydrofuran solution is added in reaction.5min is stirred, unreacted 2- bromine isobutyl acylbromide is quenched.Solvent is spin-dried for, and is used
Isosorbide-5-Nitrae-dioxane dissolution, is precipitated, filtering with unsaturated sodium bicarbonate, water re-using washing.Ether dissolution is used again, is filtered,
Obtaining lignin macromole evocating agent in 40 DEG C of vacuum drying, (bromine atom content is followed successively by 4.5mmol/g.
Under nitrogen protection, be successively added in 5 ampoule bottles synthesis lignin macromole evocating agent (0.4mmol,
0.089g), methyl methacrylate (20.024g, 200mmol) and different organic catalysts (2- naphthalene -10H- phenoxazine
(0.08mmol, 25mg)/10- (4- (itrile group) phenyl) phenoxazine (0.08mmol, 23mg)/10- (4- (trifluoromethyl) phenyl-
Phenoxazine (0.08mmol, 26mg)/10- phenyl phenoxazine (0.08mol, 21mg)/1- naphthalene -10H- phenoxazine (0.08mol,
25mg)) (structure is shown in PC11, PC12, PC13, PC14, PC15 in Detailed description of the invention 3) 18.76mL N, N- are being added into reaction flask
Dimethylacetamide solution ([M]: [I]: [C]=500:1:0.2) magnetic agitation 6h under 365nm, 16W ultraviolet light is (anti-
Temperature is answered to keep 20-30 DEG C of room temperature).Take 2mL reaction solution.It is diluted with tetrahydrofuran solution, n-hexane precipitating, vacuum drying obtains
Pure polymer.The DP of polymer is respectively 468,512,454,478,481, PDI be respectively 1.27,1.74,1.11,
1.24、1.33。
Embodiment 7:
By sulfate-reducing conditions (0.250g ,-OH 2.0mmol), triethylamine (5.0mmol, 0.506g) and 75mL acetic acid second
Ester is added in the 250mL round-bottomed flask of tetrafluoroethene magnetic stir bar, and 30min is stirred in oil bath at room temperature, then in ice bath
2- bromine isobutyl acylbromide (4.0mmol, 0.919g) is dissolved in 10mL ethyl acetate and being slowly added into round-bottomed flask by middle cooling,
For 24 hours, 20mL water/tetrahydrofuran solution is added in reaction.5min is stirred, unreacted 2- bromine isobutyl acylbromide is quenched.Solvent is spin-dried for, and is used
Isosorbide-5-Nitrae-dioxane dissolution, is precipitated, filtering with unsaturated sodium bicarbonate, water re-using washing.Ether dissolution is used again, is filtered,
Obtaining lignin macromole evocating agent in 40 DEG C of vacuum drying, (bromine atom content is followed successively by 4.5mmol/g.
Under nitrogen protection, be successively added in 6 ampoule bottles synthesis lignin macromole evocating agent (0.4mmol,
0.089g), methyl methacrylate (20.024g, 200mmol) and different organic catalysts (5,10- diphenyl -5,10-
Dihydrophenazine (0.08mmol, 27mg)/5,10-2 (4- methoxyphenyl -) -5,10- dihydrophenazine (0.08mmol, 32mg)/5,
10-2 (4- trifluoromethyl) phenyl) -5,10- dihydrophenazine (0.08mol, 38g)/5,10-2 (4- (itrile group) phenyl) -5,10- two
Hydrogen azophenlyene (0.08mmol, 31mg)/5,10-2 (2- naphthalene) -5,10- dihydrophenazine (0.08mmol, 35mg)/5,10-2 (1- naphthalene
Base) -5,10- dihydrophenazine (0.08mmol, 35mg)) (structure is shown in PC18, PC19, PC20, PC21, PC22 in Detailed description of the invention 3,
PC23) into reaction flask be added 18.76mL DMAC N,N' dimethyl acetamide solution ([M]: [I]: [C]=500:1:0.2) exist
16W White LED light irradiates lower magnetic agitation 6h (reaction temperature keeps 20-30 DEG C of room temperature).Take 2mL reaction solution.Use tetrahydrofuran
Solution dilution, n-hexane precipitating, vacuum drying obtain pure polymer.The DP of polymer is respectively 464,512,495,476,
479,463, PDI is respectively 1.41,1.22,1.18,1.36,1.14,1.51.
Embodiment 8:
By sulfate-reducing conditions (0.250g ,-OH 2.0mmol), triethylamine (5.0mmol, 0.506g) and 75mL acetic acid second
Ester is added in the 250mL round-bottomed flask of tetrafluoroethene magnetic stir bar, and 30min is stirred in oil bath at room temperature, then in ice bath
2- bromine isobutyl acylbromide (4.0mmol, 0.919g) is dissolved in 10mL ethyl acetate and being slowly added into round-bottomed flask by middle cooling,
For 24 hours, 20mL water/tetrahydrofuran solution is added in reaction.5min is stirred, unreacted 2- bromine isobutyl acylbromide is quenched.Solvent is spin-dried for, and is used
Isosorbide-5-Nitrae-dioxane dissolution, is precipitated, filtering with unsaturated sodium bicarbonate, water re-using washing.Ether dissolution is used again, is filtered,
Obtaining lignin macromole evocating agent in 40 DEG C of vacuum drying, (bromine atom content is followed successively by 4.5mmol/g.
Under nitrogen protection, successively in 3 ampoule bottles be added six kinds synthesis lignin macromole evocating agents (0.4mmol,
0.089g), methyl methacrylate (20.024g, 200mmol) and different organic catalysts (3,7-2 (4- diphenyl) 1-
Naphthalene -10- phenoxazine (0.08mmol, 49mg), 3,7-2 (4- diphenyl) 2- naphthalene -10- phenoxazine (0.08mmol, 49mg),
Perylene (0.08mol, 20mg)) (structure is shown in PC16, PC17, PC24 in Detailed description of the invention 3) be added into reaction flask
18.76mL DMAC N,N' dimethyl acetamide solution ([M]: [I]: [C]=500:1:0.2) magnetic force under the irradiation of 16W White LED light
Stir 6h (reaction temperature keeps 20-30 DEG C of room temperature).Take 2mL reaction solution.It is diluted with tetrahydrofuran solution, n-hexane precipitating, very
Sky is dried to obtain pure polymer.The DP of polymer is respectively 481,479,471, PDI be respectively 1.38,1.19,1.25.
Embodiment 9:
By sulfate-reducing conditions (0.250g ,-OH 2.0mmol), triethylamine (5.0mmol, 0.506g) and 75mL acetic acid second
Ester is added in the 250mL round-bottomed flask of tetrafluoroethene magnetic stir bar, and 30min is stirred in oil bath at room temperature, then in ice bath
Middle cooling, by 2- bromine isobutyl acylbromide (4.0mmol, 0.919g)/2- bromopropionitrile (4.0mmol, 0.532g)/sulfonic acid chloride
(4.0mmol, 0.536g)/2,2- dichloroacetophenone (4.0mmol, 0.752g)/diphenyl bromomethane (4.0mmol, 0.984g)/
Chloroform (4.0mmol, 0.472g), which is dissolved in 10mL ethyl acetate, to be slowly added into round-bottomed flask, and reaction for 24 hours, is added
20mL water/tetrahydrofuran solution.5min is stirred, unreacted 2- bromine isobutyl acylbromide is quenched.Solvent is spin-dried for, with Isosorbide-5-Nitrae-dioxane
Dissolution is precipitated with unsaturated sodium bicarbonate, filtering, water re-using washing.Ether dissolution is used again, and filtering is dry in 40 DEG C of vacuum
It is dry to obtain lignin macromole evocating agent (bromine atom content is 4.5mmol/g).
Under nitrogen protection, be successively added in 5 ampoule bottles synthesis lignin macromole evocating agent (0.4mmol,
0.089g), 10- phenyl-phenthazine (22mg, 0.08mmol), methyl methacrylate (20.024g, 200mmol), 18.76mL
Different organic solvent (N,N-dimethylformamide/methylene chloride/dimethyl sulfoxide/tetrahydrofuran/ethyl acetate) ([M]:
[I]: [C]=500:1:0.2) (reaction temperature keeps room temperature 20-30 to magnetic agitation 6h under 365nm, 16W ultraviolet light
℃).Take 2mL reaction solution.It is diluted with tetrahydrofuran solution, n-hexane precipitating, vacuum drying obtains pure polymer.Polymer
DP be respectively 487,454,476,459,439, PDI be respectively 1.69,1.43,1.54,1.55,1.20.
Embodiment 10:
By sulfate-reducing conditions (0.250g ,-OH 2.0mmol), triethylamine (5.0mmol, 0.506g) and 75mL acetic acid second
Ester is added in the 250mL round-bottomed flask of tetrafluoroethene magnetic stir bar, and 30min is stirred in oil bath at room temperature, then in ice bath
2- bromine isobutyl acylbromide (4.0mmol, 0.919g) is dissolved in 10mL ethyl acetate and being slowly added into round-bottomed flask by middle cooling,
For 24 hours, 20mL water/tetrahydrofuran solution is added in reaction.5min is stirred, unreacted 2- bromine isobutyl acylbromide is quenched.Solvent is spin-dried for, and is used
Isosorbide-5-Nitrae-dioxane dissolution, is precipitated, filtering with unsaturated sodium bicarbonate, water re-using washing.Ether dissolution is used again, is filtered,
Obtain lignin macromole evocating agent in 40 DEG C of vacuum drying (bromine atom content is 4.5mmol/g).
Under nitrogen protection, the lignin macromole evocating agent (0.4mmol, 0.089g) of synthesis, 10- are added in ampoule bottle
Phenyl-phenthazine (PC1,5.5mg, 0.02mmol), methyl methacrylate (0.400g, 4mmol), 39.59mL N, N- diformazan
Yl acetamide solution ([M]: [I]: [C]=10:1:0.05) magnetic agitation 6h (reaction temperature under 365nm, 16W ultraviolet light
Degree keeps 20-30 DEG C of room temperature).Take 2mL reaction solution.It is diluted with tetrahydrofuran solution, n-hexane precipitating, vacuum drying obtains pure
Polymer.The DP of polymer is 8, PDI 1.11.
Embodiment 11:
By sulfate-reducing conditions (0.250g ,-OH 2.0mmol), triethylamine (5.0mmol, 0.506g) and 75mL acetic acid second
Ester is added in the 250mL round-bottomed flask of tetrafluoroethene magnetic stir bar, and 30min is stirred in oil bath at room temperature, then in ice bath
2- bromine isobutyl acylbromide (4.0mmol, 0.919g) is dissolved in 10mL ethyl acetate and being slowly added into round-bottomed flask by middle cooling,
For 24 hours, 20mL water/tetrahydrofuran solution is added in reaction.5min is stirred, unreacted 2- bromine isobutyl acylbromide is quenched.Solvent is spin-dried for, and is used
Isosorbide-5-Nitrae-dioxane dissolution, is precipitated, filtering with unsaturated sodium bicarbonate, water re-using washing.Ether dissolution is used again, is filtered,
Obtain lignin macromole evocating agent in 40 DEG C of vacuum drying (bromine atom content is 4.5mmol/g).
Under nitrogen protection, the lignin macromole evocating agent (0.4mmol, 0.089g) of synthesis, 10- are added in ampoule bottle
Phenyl-phenthazine (PC1,22mg, 0.08mmol), methyl methacrylate (20.024g, 200mmol), 378.76mL N, N-
(reaction temperature keeps room temperature to magnetic agitation 6h to dimethylacetamide solution (C=0.5M) under 365nm, 16W ultraviolet light
20-30℃).Take 2mL reaction solution.It is diluted with tetrahydrofuran solution, n-hexane precipitating, vacuum drying obtains pure polymer.
The DP of polymer is 475, PDI 1.58.
It is specific real the present invention provides the thinking and method of a kind of method of photoinduction organic catalysis lignin graft modification
Now there are many method of the technical solution and approach, the above is only a preferred embodiment of the present invention, it is noted that for this
For the those of ordinary skill of technical field, without departing from the principle of the present invention, several improvement and profit can also be made
Decorations, these modifications and embellishments should also be considered as the scope of protection of the present invention.Each component part being not known in the present embodiment is available
The prior art is realized.
Claims (9)
1. a kind of method of photoinduction organic catalysis lignin graft modification, which comprises the steps of:
(1) lignin synthesizes lignin macromole evocating agent with alkyl acyl halide initiator for reaction；
(2) in an inert atmosphere, lignin macromole evocating agent, vinyl monomer, catalyst, solvent step (1) obtained
Mixing, atom transfer radical polymerization is carried out under ultraviolet light or visible optical radiation, obtains lignin-base polymer.
2. the method for photoinduction organic catalysis lignin graft modification according to claim 1, which is characterized in that step
(1) in, the alkyl acyl halide initiator is 2- bromo isobutyl acylbromide, 2- bromopropionitrile, sulfonic acid chloride, 2,2- dichloroacetophenone, hexichol
Bromide methane or chloroform；The lignin is lignin, the lignin sulfonic acid of sulfate-reducing conditions, organic solvent dissolution
Salt, soda lignin.
3. the method for photoinduction organic catalysis lignin graft modification according to claim 2, which is characterized in that step
(1) reaction is completed under triethylamine effect in, wherein hydroxyl and alkyl acyl halide initiator reacts molar ratio in the lignin
For 1:1~3.
4. the method for photoinduction organic catalysis lignin graft modification according to claim 1, which is characterized in that step
(2) in, the vinyl monomer is benzyl methacrylate, ethyl methacrylate, Isobutyl methacrylate, methyl-prop
Olefin(e) acid 2- ethylhexyl, lauryl methacrylate, 2- methyl -2- isodecyl acrylate, 2- methyl -2- acrylic acid -2- (2- first
Oxygroup ethyoxyl) acrylic ester monomers and the acrylonitrile, styrene or isopropyl acrylamide such as ethyl ester, methyl methacrylate
In any one.
5. the method for photoinduction organic catalysis lignin graft modification according to claim 1, which is characterized in that step
(2) in, the catalyst is 10- phenyl phenthazine, 4- methoxyphenyl-lysivane, the chloro- 10H- phenthazine of 4-, 1- naphthalene
Base -10H- phenthazine, 2- naphthalene -10H- phenthazine, 10- (pyridine -2-yl) -10H- phenthazine, 10 methyl phenothiazine, 10-
(4- (trifluoromethyl) phenyl) phenthazine, 10- (4- (itrile group) phenyl) phenthazine, phenyl benzo [b] phenthazine, 2- naphthalene-
10H- phenoxazine, 10- (4- (itrile group) phenyl) phenoxazine, 10- (4- (trifluoromethyl) phenyl) phenoxazine, 10- phenyl phenoxazine,
1- naphthalene -10H- phenoxazine, 3,7-2 (4- diphenyl) 1- naphthalene -10- phenoxazine, 3,7-2 (4- diphenyl) 2- naphthalene -10- pheno
Oxazines, 5,10- diphenyl -5,10- dihydrophenazine, 5,10-2 (4- methoxyphenyl -) -5,10- dihydrophenazine, 5,10-2 (4-
Trifluoromethyl) phenyl) -5,10- dihydrophenazine, 5,10-2 (4- (itrile group) phenyl) -5,10- dihydrophenazine, 5,10-2 (2- naphthalene
Base) -5,10- dihydrophenazine, 5,10-2 (1- naphthalene) -5,10- dihydrophenazine, the group of any one or more in perylene
It closes.
6. the method for photoinduction organic catalysis lignin graft modification according to claim 1, which is characterized in that step
(2) in, the solvent is N-N- dimethylformamide, N-N- dimethyl acetamide, methylene chloride, dimethyl sulfoxide, tetrahydro
Any one in furans or ethyl acetate.
7. the method for photoinduction organic catalysis lignin graft modification according to claim 1, which is characterized in that step
(2) in, the lignin macromole evocating agent, vinyl monomer, catalyst reaction molar ratio be 1:10~500:0.05~
0.200。
8. the method for photoinduction organic catalysis lignin graft modification according to claim 1, which is characterized in that step
(2) concentration of vinyl monomer described in a solvent is 0.5-5mol/L.
9. the method for photoinduction organic catalysis lignin graft modification according to claim 1, which is characterized in that step
(2) in, the light source and optical wavelength being catalyzed needed for reacting are selected according to catalyst respectively, specifically:
When catalyst is 10- phenyl phenthazine, 10 methyl phenothiazine, the ultraviolet catalytic of 365nm or 380nm is used；
When catalyst is 4- methoxyphenyl-lysivane, the chloro- 10H- phenthazine of 4-, 1- naphthalene -10H- phenthazine, 2- naphthalene
Base -10H- phenthazine, 10- (pyridine -2-yl) -10H- phenthazine, 10- (4- (trifluoromethyl) phenyl) phenthazine, 10- (4- (nitrile
Base) phenyl) phenthazine, phenyl benzo [b] phenthazine, 2- naphthalene -10H- phenoxazine, 10- (4- (itrile group) phenyl) phenoxazine,
10- (when 4- (trifluoromethyl) phenyl-phenoxazine, 10- phenyl phenoxazine, 1- naphthalene -10H- phenoxazine, uses the ultraviolet of 365nm
Photocatalysis；
When catalyst be 5,10- diphenyl -5,10- dihydrophenazine, 5,10-2 (4- methoxyphenyl -) -5,10- dihydrophenazine,
5,10-2 (4- trifluoromethyl) phenyl) -5,10- dihydrophenazine, 5,10-2 (4- (itrile group) phenyl) -5,10- dihydrophenazine, 5,
10-2 (2- naphthalene) -5,10- dihydrophenazine, 5,10-2 (1- naphthalene) -5,10- dihydrophenazine, 3,7-2 (4- diphenyl) 1- naphthalene
When base -10- phenoxazine, 3,7-2 (4- diphenyl) 2- naphthalene -10- phenoxazine, perylene, it is catalyzed using white led lamps.
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