CN110144031B - Method for grafting and modifying lignin by photoinduction organic catalysis - Google Patents
Method for grafting and modifying lignin by photoinduction organic catalysis Download PDFInfo
- Publication number
- CN110144031B CN110144031B CN201910414047.5A CN201910414047A CN110144031B CN 110144031 B CN110144031 B CN 110144031B CN 201910414047 A CN201910414047 A CN 201910414047A CN 110144031 B CN110144031 B CN 110144031B
- Authority
- CN
- China
- Prior art keywords
- lignin
- phenothiazine
- naphthyl
- phenyl
- dihydrophenazine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005610 lignin Polymers 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 75
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 58
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 29
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 27
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical group CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 19
- -1 1-naphthyl-10H-phenothiazine Chemical compound 0.000 claims description 17
- 229950000688 phenothiazine Drugs 0.000 claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 150000002825 nitriles Chemical class 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 13
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- WSEFYHOJDVVORU-UHFFFAOYSA-N 10-phenylphenothiazine Chemical group C12=CC=CC=C2SC2=CC=CC=C2N1C1=CC=CC=C1 WSEFYHOJDVVORU-UHFFFAOYSA-N 0.000 claims description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- 239000004305 biphenyl Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- 230000003197 catalytic effect Effects 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 125000005257 alkyl acyl group Chemical group 0.000 claims description 6
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 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
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- JQSNKCDXBDOVMU-UHFFFAOYSA-N 1-naphthalen-1-yl-5,10-dihydrophenazine Chemical compound C1=CC=CC2=C(C=CC=C12)C1=CC=CC=2NC3=CC=CC=C3NC1=2 JQSNKCDXBDOVMU-UHFFFAOYSA-N 0.000 claims description 5
- RLAXVXKHKURYFZ-UHFFFAOYSA-N 1-naphthalen-2-yl-10H-phenoxazine Chemical compound C1=C(C=CC2=CC=CC=C12)C1=CC=CC=2OC3=CC=CC=C3NC12 RLAXVXKHKURYFZ-UHFFFAOYSA-N 0.000 claims description 5
- QXBUYALKJGBACG-UHFFFAOYSA-N 10-methylphenothiazine Chemical compound C1=CC=C2N(C)C3=CC=CC=C3SC2=C1 QXBUYALKJGBACG-UHFFFAOYSA-N 0.000 claims description 5
- NZOYBWLCZWTECI-UHFFFAOYSA-N 4-chloro-10h-phenothiazine Chemical compound N1C2=CC=CC=C2SC2=C1C=CC=C2Cl NZOYBWLCZWTECI-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
- 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 5
- 229960001701 chloroform Drugs 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- UOHKISLIYZMUGE-UHFFFAOYSA-N 1-naphthalen-1-yl-10H-phenoxazine Chemical compound C1(=CC=CC2=CC=CC=C12)C1=CC=CC=2OC3=CC=CC=C3NC1=2 UOHKISLIYZMUGE-UHFFFAOYSA-N 0.000 claims description 4
- DMTAVUBDKPDIQZ-UHFFFAOYSA-N 1-phenyl-12H-benzo[b]phenothiazine Chemical compound C1(=CC=CC=C1)C1=CC=CC=2SC=3C=C4C(=CC=3NC1=2)C=CC=C4 DMTAVUBDKPDIQZ-UHFFFAOYSA-N 0.000 claims description 4
- NSKCIYCOJUZRKT-UHFFFAOYSA-N 10-[4-(trifluoromethyl)phenyl]phenothiazine Chemical compound C1=CC(C(F)(F)F)=CC=C1N1C2=CC=CC=C2SC2=CC=CC=C21 NSKCIYCOJUZRKT-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
- CVKBLFQXQAXSAQ-UHFFFAOYSA-N C1=C(C=CC2=CC=CC=C12)C1=CC=CC=2SC3=CC=CC=C3NC1=2 Chemical compound C1=C(C=CC2=CC=CC=C12)C1=CC=CC=2SC3=CC=CC=C3NC1=2 CVKBLFQXQAXSAQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001732 Lignosulfonate Polymers 0.000 claims description 4
- OQROAIRCEOBYJA-UHFFFAOYSA-N bromodiphenylmethane Chemical compound C=1C=CC=CC=1C(Br)C1=CC=CC=C1 OQROAIRCEOBYJA-UHFFFAOYSA-N 0.000 claims description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- LAVLDGSVWFEKJG-UHFFFAOYSA-N 10-phenylphenoxazine Chemical compound C12=CC=CC=C2OC2=CC=CC=C2N1C1=CC=CC=C1 LAVLDGSVWFEKJG-UHFFFAOYSA-N 0.000 claims description 3
- UZDMSTZDTLPULS-UHFFFAOYSA-N 10-pyridin-2-ylphenothiazine Chemical compound C12=CC=CC=C2SC2=CC=CC=C2N1C1=CC=CC=N1 UZDMSTZDTLPULS-UHFFFAOYSA-N 0.000 claims description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound 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
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 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
- 230000009471 action Effects 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- JTPUMZTWMWIVPA-UHFFFAOYSA-O Isopropamide Chemical compound C=1C=CC=CC=1C(C(N)=O)(CC[N+](C)(C(C)C)C(C)C)C1=CC=CC=C1 JTPUMZTWMWIVPA-UHFFFAOYSA-O 0.000 claims 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 1
- 229960001737 isopropamide Drugs 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000010559 graft polymerization reaction Methods 0.000 abstract 1
- 238000010526 radical polymerization reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 39
- 239000000243 solution Substances 0.000 description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 238000001291 vacuum drying Methods 0.000 description 24
- 238000003756 stirring Methods 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000011541 reaction mixture Substances 0.000 description 14
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 13
- 238000007865 diluting Methods 0.000 description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 12
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 230000001376 precipitating effect Effects 0.000 description 11
- 238000010791 quenching Methods 0.000 description 11
- 230000000171 quenching effect Effects 0.000 description 11
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 11
- 229920005611 kraft lignin Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 6
- 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
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000001246 bromo group Chemical group Br* 0.000 description 4
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- 238000006116 polymerization reaction Methods 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- JGGSOWGJMBNDHS-UHFFFAOYSA-N 10-phenyl-5h-phenazine Chemical compound C12=CC=CC=C2NC2=CC=CC=C2N1C1=CC=CC=C1 JGGSOWGJMBNDHS-UHFFFAOYSA-N 0.000 description 3
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
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- 230000002194 synthesizing effect Effects 0.000 description 3
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 2
- IVURTNNWJAPOML-UHFFFAOYSA-N 5,10-dihydrophenazine Chemical compound C1=CC=C2NC3=CC=CC=C3NC2=C1 IVURTNNWJAPOML-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- 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
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Abstract
The invention discloses a method for grafting and modifying lignin by photoinduction organic catalysis. The invention has the advantages that the organic catalyst can avoid metal residue in the product, the photoinduced free radical polymerization has good space-time controllability, and lignin initiates graft polymerization of various monomers, so that various novel lignin-based polymers with controllable structures can be obtained.
Description
Technical Field
The invention belongs to the field of synthesis of high polymer materials, and particularly relates to a method for grafting modification of photoinduced organic catalytic lignin.
Background
The lignin is the second largest biomass resource next to cellulose, can be widely applied to the field of bio-based materials, and is beneficial to reducing consumption of fossil resources and protecting ecological environment. Currently, there are two main methods for recycling lignin: 1) the unmodified lignin is physically mixed with the material to improve the thermodynamic properties of the material itself. But due to the aggregation phenomenon of pi-pi stacking interaction of the structure, the compatibility among materials is poor, and the strength and plasticity of the material are poor, so that the application in the industrial field is greatly limited; 2) the chemical modification of lignin can enhance the thermoplasticity and material compatibility of the polymer. The lignin structure contains abundant hydroxyl structures, such as phenolic resin hydroxyl, aliphatic resin hydroxyl and the like, and a polymer with special functional groups can be grafted on the lignin structure to synthesize a material with special functionality.
Atom Transfer Radical Polymerization (ATRP) is one of the most extensive modification methods for preparing lignin-based graft copolymers, and is used for synthesizing macromolecular polymers with definite molecular structures and low dispersity by controlling the molecular weight and the grafting density of grafted chains. The existing ATRP modified lignin generally adopts a metal catalyst (Cu)+1,Cu+2) The synthesized lignin-based polymer has the problems of metal residue and the like, and has certain cytotoxicity, so that the application of lignin in the fields of biological medicine and the like is greatly limited. On the other hand, the organic catalyzed atom transfer radical polymerization (Organocatalyzed atom transfer polymerization) has the problems of high catalytic efficiency, no metal catalyst residue and the like, and has attracted the interest of the researchers in the polymerization field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for safely and efficiently preparing a lignin-based macromolecular functional material with low dispersity, high molecular weight and good thermodynamic performance without metal residues and mild catalytic conditions.
In order to solve the technical problem, the invention discloses a method for grafting and modifying photoinduced organic catalytic lignin, which comprises the following steps:
(1) reacting lignin with alkyl acyl halide initiator to synthesize lignin macroinitiator;
(2) and (2) mixing the lignin macroinitiator obtained in the step (1), an ethylene monomer, a catalyst and a solvent in an inert atmosphere, and carrying out atom transfer radical polymerization under ultraviolet light or visible light radiation to obtain the lignin-based polymer.
Specifically, the synthetic route of the reaction is shown in figure 1; wherein the value range of m in the product is 1-600.
Preferably, in the step (1), the alkyl acyl halide reagent is 2-bromoisobutyryl bromide, 2-bromopropionitrile, sulfonyl chloride, 2-dichloroacetophenone, diphenyl bromomethane or trichloromethane, and each structure is shown in fig. 2; the lignin is sulfate lignin, organic solvent-dissolved lignin, lignosulfonate, and soda lignin.
Specifically, the reaction in the step (1) is completed under the action of triethylamine, wherein the reaction molar ratio of hydroxyl groups in the lignin to alkyl acyl halide initiators is 1:1 to 3.
Preferably, in the step (2), the vinyl monomer is any one of benzyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, isodecyl 2-methyl-2-acrylate, 2-methyl-2- (2-methoxyethoxy) ethyl acrylate, methyl methacrylate and other acrylate monomers, and acrylonitrile, styrene or isopropyl acrylamide, and the molecular structure of the vinyl monomer is as shown in fig. 3.
Specifically, in the step (2), the catalyst is PC1) 10-phenylphenothiazine, PC2) 4-methoxyphenyl-10-phenothiazine, PC3) 4-chloro-10H-phenothiazine, PC4) 1-naphthyl-10H-phenothiazine, PC5) 2-naphthyl-10H-phenothiazine, PC6)10- (pyridin-2-yl) -10H-phenothiazine, PC7) 10-methylphenothiazine, PC8)10- (4- (trifluoromethyl) phenyl) -phenothiazine, PC9)10- (4- (nitrile) phenyl) phenothiazine, PC10) phenylbenzo [ b ] phenothiazine, PC11) 2-naphthyl-10H-phenoxazine, PC12)10- (4- (nitrile) phenyl) phenoxazine, PC13)10- (4- (trifluoromethyl) phenyl) phenoxazine, or a mixture thereof, PC14) 10-phenylphenazine, PC15) 1-naphthyl-10H-phenoxazine, PC16)3,7-2 (4-diphenyl) 1-naphthyl-10-phenoxazine, PC17)3,7-2 (4-diphenyl) 2-naphthyl-10-phenoxazine, PC18)5, 10-diphenyl-5, 10-dihydrophenazine, PC19)5,10-2 (4-methoxyphenyl-) -5, 10-dihydrophenazine, PC20)5,10-2 (4-trifluoromethyl) phenyl) -5, 10-dihydrophenazine, PC21)5,10-2(4- (nitrile) phenyl) -5, 10-dihydrophenazine, PC22)5,10-2 (2-naphthyl) -5, 10-dihydrophenazine, PC23)5,10-2 (1-naphthyl) -5, 10-dihydrophenazine, PC24) perylene. The above catalyst molecular structure is shown in fig. 4 and 5.
In the step (2), the reaction solvent is any one of N-N-dimethylformamide, N-N-dimethylacetamide, dichloromethane, dimethyl sulfoxide, tetrahydrofuran or ethyl acetate.
Preferably, the reaction molar ratio of the lignin macroinitiator, the ethylene monomer and the catalyst is 1: 10-500: 0.05-0.200.
In the step (2), the concentration of the ethylene monomer in the reaction solvent is 0.5-5 mol/L.
In the step (2), the light source and the light wavelength of the catalysis needed by the reaction are respectively selected according to the catalyst, and specifically, the method comprises the following steps: when the catalyst is 10-phenylphenothiazine (PC1) or 10-methylphenothiazine (PC7), 365nm or 380nm ultraviolet light can be used for catalysis;
when the catalyst is 4-methoxyphenyl-10-phenothiazine (PC2), 4-chloro-10H-phenothiazine (PC3), 1-naphthyl-10H-phenothiazine (PC4), 2-naphthyl-10H-phenothiazine (PC5), 10- (pyridine-2-yl) -10H-phenothiazine (PC6), 10- (4- (trifluoromethyl) phenyl) -phenothiazine (PC8), 10- (4- (nitrile) phenyl) phenothiazine (PC9), phenylbenzo [ b ] phenothiazine (PC10), 2-naphthyl-10H-phenoxazine (PC11), 10- (4- (nitrile) phenyl) phenoxazine (PC12), 10- (4- (trifluoromethyl) phenyl-phenoxazine (PC13), Catalyzing with 365nm ultraviolet light when using 10-phenylphenazine (PC14) and 1-naphthyl-10H-phenoxazine (PC 15);
when the 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- (nitrile) phenyl) -5, 10-dihydrophenazine (PC21), 5,10-2 (2-naphthyl) -5, 10-dihydrophenazine (PC22), 5,10-2 (1-naphthyl) -5, 10-dihydrophenazine (PC23)3,7-2 (4-diphenyl) 1-naphthyl-10-phenazine (PC16), 3,7-2 (4-diphenyl) 2-naphthyl-10-phenazine (PC17), Perylene (PC24) was catalyzed using a white LED lamp.
Has the advantages that:
the invention has the advantages that the hydroxyl on the lignin is modified to obtain the macroinitiator, and the raw materials are cheap; the polymerization reaction is carried out under the control of a light source, can be carried out through the on-off control reaction of a light source lamp, and is carried out by grafting a functional monomer on lignin at room temperature by utilizing various organic photocatalysts to obtain the novel environment-friendly polymer material.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a scheme for the synthesis of lignin-based polymers;
FIG. 2 is a diagram of different alkyl acid halide initiator molecule structures;
FIG. 3 is a molecular structure diagram of various vinylic monomers;
fig. 4 and 5 are structural diagrams of different catalyst molecules.
Detailed Description
The invention will be better understood from the following examples.
In the following examples, PC stands for organic catalyst. The [ M ]: [ I ]: [ C ] represents the ratio of the halogen atom content to the catalyst in the vinyl monomer and the lignin macroinitiator, and the bromine atom content is mol (Br)/mass (lignin-Br). In the invention, lignin, an initiator, an ethylene monomer, a solvent and a lamp tube are all sold in the market, wherein the molecular weight of the sulfate lignin is 10000g/mol, and the sulfate lignin contains 8.0mmol/g phenolic hydroxyl; the molecular weight of the organic solvent lignin is 5000g/mol, and the organic solvent lignin contains 3.16mmol/g phenolic hydroxyl; the lignosulfonate has a molecular weight of 8000g/mol and contains 5.24mmol/g phenolic hydroxyl; the molecular weight of soda lignin is 10000g/mol, and the soda lignin contains 10.24mmol/g phenolic hydroxyl. The invention firstly utilizes an initiator to modify hydroxyl groups on lignin (lignin) into lignin macroinitiator (lignin-Br), and then utilizes a catalyst to synthesize a lignin macromolecular polymer under the control of illumination.
Wherein, the general steps for synthesizing the catalyst (PC1-10) taking phenothiazine and derivatives thereof as substrates are that sodium tert-butoxide (134mg, 1.4mmol), phenothiazine (199mg, 1mmol),RuPhos Precat (14mg, 0.02mmol) and RuPhos (8mg, 0.02mmol) were added to a Schlenk flask containing a magnetic stirrer. The vial was purged three times and anhydrous 1, 4-dioxane (1mL) was added under nitrogen followed by 1.4mmol of aryl halide reagent. The vial was placed in an oil bath at 110 ℃ and stirred for 6 h. The vial was then cooled to room temperature with CH2Cl2Diluting, washing with water, brine three times, and adding Mg2SO4Dried and purified by column chromatography. Vacuum drying to obtain the product.
Phenylbenzo [ b- ] phenothiazine (PC10) using the phenothiazine derivative-benzo [ b ] phenothiazine as substrate was prepared by first adding 2, 3-dihydroxynaphthalene (8g, 0.05mol)), 2-aminophenethiol (6.25g, 0.05mol) and 25mL of 1,2, 4-trichlorobenzene to a round bottom flask containing a magnetic stirrer. The reaction mixture was heated to 200 ℃ and held at this temperature for 6h, and the water of reaction was collected with a steam trap. When the mixture is cooled, a product is separated out and filtered, and then the product is washed by n-hexane and ethanol in sequence to obtain yellow powdery benzo [ b ] phenothiazine. The general procedure described above was followed to give phenylbenzo [ b- ] phenothiazine (PC 10).
The general procedure for the synthesis of a phenoxazine-based catalyst (PC11-17) was to first remove the water from the Schlenk flask by flame drying, and then to fill the flask with nitrogen by displacing the gas three times. The flask was then charged with phenoxazine (800mg, 4.37mmol), sodium t-butoxide (840mg, 8.74mmol) and RuPhos (52.4mg, 0.13 mmol). The bottle was placed in a nitrogen-filled glove box to which RuPhos Precat (91.77mg, 0.13mmol) and 4mL of anhydrous 1, 4-dioxane and 8.74mmol of aryl halide were added. The flask was placed in an oil bath at 130 ℃ and stirred for 48 h. The flask was then cooled to room temperature using CH2Cl2Diluting, and performing column chromatography separation.
The 3,7-2 (4-diphenyl) 1-naphthyl-10-phenoxazine is prepared by the general method of catalyst synthesis, firstly synthesizing 1-naphthyl-10-phenoxazine, and then dissolving 1-naphthyl-10-phenoxazine (800mg, 2.58mmol) in 80mL chloroform. Then 80mL of glacial acetic acid was added to the stirred mixture. The aluminum foil was wrapped thoroughly to cover the reaction vial, blocking light. Slowly adding in dark within 20minPowdered N-bromosuccinimide (944mg, 5.30 mmol). After 2h at room temperature, the solvent was again spin dried from the reaction mixture. The solid obtained was washed three times with water, brine and then MgSO4Drying, vacuum drying and collecting the intermediate product 3, 7-dibromo-1-naphthalene-10-phenoxazine.
A schlenk flask equipped with a magnetic stirrer and a reflux condenser was then flame-dried, three times with gas displacement removal, nitrogen blanketed, and then 3, 7-dibromo-1-naphthalene-10-phenoxazine (225mg, 0.48 mmol), 4-biphenylboronic acid (381.8mg, 1.9mmol) was added and dissolved in 20mL THF. Mixing 6mL of K2CO3(2M) was poured into the solution, then heated to 80 ℃ and stirred for 20 min. Then, a solution of tetrakis (triphenylphosphine) palladium (93mg, 15% mol) in 20mL THF was added, followed by heating to 100 ℃ and reaction for 24 h. Once complete, the solvent was spun dry, redissolved in DCM, washed three times with water, brine, and then MgSO4And (5) drying. Finally, the catalyst is collected by column chromatography.
The catalyst (PC18-23) with 5, 10-dihydrophenazine as substrate was prepared by adding 5, 10-dihydrophenazine (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 in sequence to a Schlenk tube. A Schlenk flask was heated at 110 ℃ for 10h under nitrogen. After cooling to room temperature, 200mL of CH was added to the reaction mixture2Cl2And washed three times with 200mL of distilled water. With MgSO4The organic layer was dried, dried in vacuo, and then purified by column chromatography.
Perylene (PC24) is a commercially available solvent.
And measuring the content of bromine atoms in the lignin by a styrene calibration method. The specific method is that the mass is msStyrene and mass m1Is dissolved in a deuterization reagent by1H NMR analysis, determined according to the following formula:
wherein A islBeing part of methyl protons of initiator1H NMR integral region (m,1.8-2.3), As is a vinyl proton of styrene1H NMR integral region (d,5.1-5.4), a is the number of methyl protons in the initiator, 104 is the molecular weight of styrene, msAnd mlThe mass of styrene and lignin-Br, respectively.
In the following examples of the present invention, the degree of polymerization DP represents the amount of vinyl monomer grafted onto lignin, and can be measured by the following method (taking lignin macroinitiator modified with 2-bromoisobutyryl bromide initiator as an example):
DP＝(m/2)/(n/6)
wherein m represents-CH on the vinyl monomer2-integration of protons in nuclear magnetic hydrogen spectra; n represents two-CH on lignin modified 2-bromo isobutyryl bromide3-integration of protons in nuclear magnetic hydrogen spectra.
The following detection methods were used to detect the molecular weight and molecular weight distribution of the product:
employing a Wyattx size exclusion chromatography system, a GPC column configured with an SSI 1500 pump, a Wyatt Optilab rEX detector, a Waters Styragel HR;
analysis conditions were as follows: the mobile phase is tetrahydrofuran, the flow rate is 0.7mL/min, the column temperature is 25 ℃, and the sample injection volume is 0.7 mL;
sample preparation: 30mg of the product was taken, diluted to 3mL with tetrahydrofuran solution, filtered through a disposable filter head (containing 0.22um organic filter membrane) and injected.
Example 1:
lignin sulfate (0.250g, -OH2.0mmol), triethylamine (5.0mmol,0.506g) and 75mL ethyl acetate were added to a 250mL round bottom flask with a magnetic stir bar of tetrafluoroethylene, stirred in an oil bath at room temperature for 30min, then cooled in an ice bath and 2-bromoisobutyryl bromide (4.0mmol,0.919 g)/2-bromopropionitrile (4.0mmol,0.532 g)/sulfonyl chloride (4.0mmol,0.536g)/2, 2-dichloroacetophenone (4.0mmol,0.752 g)/diphenylbromomethane (4.0mmol,0.984 g)/trichloromethane (4.0mmol,0.472g) dissolved in 10mL ethyl acetate was slowly added to the round bottom flask, reacted for 24h and 20mL of water/tetrahydrofuran solution was added. Stirring for 5min and quenching the unreacted 2-bromoisobutyryl bromide. The solvent was spun dry, dissolved in 1, 4-dioxane, precipitated with unsaturated sodium bicarbonate, filtered and washed repeatedly with water. Dissolving with diethyl ether, filtering, and vacuum drying at 40 deg.C to obtain lignin macroinitiator (bromine atom content of 4.5mmol/g, 4.2mmol/g, 4.3mmol/g, 4.4mmol/g, 4.5 mmol/g).
Six kinds of synthesized lignin macroinitiators (0.4mmol,0.089g, 0.095g, 0.093g, 0.091g, 0.089g) and 10-phenyl-phenothiazine (PC1,22mg,0.08mmol), methyl methacrylate (20.024g, 200mmol), 18.76mL of N, N-dimethylacetamide solution ([ M ]: I: [ C ]: 500:1:0.2, C ═ 5M) were added to 6 ampoules in this order under nitrogen protection, and magnetically stirred for 6 hours under 365nm and 16W uv irradiation (reaction temperature was kept at room temperature 20-30 ℃). 2mL of the reaction mixture was taken. Diluting with tetrahydrofuran solution, precipitating with n-hexane, and vacuum drying to obtain pure polymer. The DP of the polymer was 440, 461, 453, 435, 467, 536, PDI was 1.65, 1.56, 1.30, 1.15, 1.38, 1.87, respectively.
Example 2:
separately, lignin (0.632g, -OH2.0mmol) dissolved in organic solvent, lignosulfonate (0.382g, -OH2.0mmol), soda lignin (0.195g, -OH2.0mmol), triethylamine (5.0mmol,0.50 g) and 75mL ethyl acetate were added to a 250mL round-bottomed flask with a tetrafluoroethylene magnetic stirrer, stirred in an oil bath at room temperature for 30min, then cooled in an ice bath, 2-bromoisobutyryl bromide (4.0mmol,0.92g) dissolved in 10mL ethyl acetate was slowly added to the round-bottomed flask, reacted for 24h, and 20mL of water/tetrahydrofuran solution was added. Stirring for 5min and quenching the unreacted 2-bromoisobutyryl bromide. The solvent was spun dry, dissolved in 1, 4-dioxane, precipitated with unsaturated sodium bicarbonate, filtered and washed repeatedly with water. Dissolving with diethyl ether, filtering, and vacuum drying at 40 deg.C to obtain lignin macroinitiator (bromine atom content of 2.58mmol/g, 3.12mmol/g, and 5.97mmol/g in sequence).
Three synthetic lignin macroinitiators (0.4mmol,0.155g, 0.128g, 0.067g) and 10-phenyl-phenothiazine (PC1,22mg,0.08mmol), methyl methacrylate (20.024g, 200mmol), 18.76mL of N, N-dimethylacetamide solution ([ M ]: I: [ C ]: 500:1:0.2) were added in sequence to 3 ampoules under nitrogen protection and magnetically stirred for 6h (reaction temperature maintained at room temperature 20-30 ℃ C.) under 365nm and 16W UV irradiation. 2mL of the reaction mixture was taken. Diluting with tetrahydrofuran solution, precipitating with n-hexane, and vacuum drying to obtain pure polymer. The polymers DP were 498, 501, 516, respectively, and the PDI were 1.41, 1.43, 1.57, respectively.
Example 3:
the kraft lignin (0.250g, -OH2.0mmol), triethylamine (5.0mmol,0.506g) and 75mL ethyl acetate were added to a 250mL round bottom flask with a magnetic stir bar of tetrafluoroethylene, stirred in an oil bath at room temperature for 30min, then cooled in an ice bath, 2-bromoisobutyryl bromide (4.0mmol,0.919g) was dissolved in 10mL ethyl acetate and slowly added to the round bottom flask, reacted for 24h and 20mL water/tetrahydrofuran solution was added. Stirring for 5min and quenching the unreacted 2-bromoisobutyryl bromide. The solvent was spun dry, dissolved in 1, 4-dioxane, precipitated with unsaturated sodium bicarbonate, filtered and washed repeatedly with water. Dissolving with diethyl ether, filtering, and vacuum drying at 40 deg.C to obtain lignin macroinitiator (bromine atom content is 4.5mmol in sequence).
Under nitrogen protection, synthetic lignin macroinitiator (0.4mmol,0.089g), 10-phenyl-phenothiazine (PC1,22mg,0.08mmol) and the different monomers benzyl methacrylate (200mmol,35.242 g)/ethyl methacrylate (200mmol,22.828 g)/isobutyl methacrylate (200mmol,28.440 g)/2-ethylhexyl methacrylate (200mmol,39.660 g)/lauryl methacrylate (200mmol,50.882 g)/2-methyl-2-isodecyl acrylate (200mmol,45.272 g)/2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester (200mmol,37.644 g)/acrylonitrile (200mmol,10.612 g)/styrene (200 mmol) were added in succession to 10 ampoules, 20.83 g)/isopropylacrylamide (200mmol,22.632g)) in 10 ampoules 46.11mL/55.11mL/47.16 mL/40mL/43.10mL/46.83mL/17.01mL/17.86mL of a solution of N, N-dimethylacetamide ([ M ]: I: [ C ]: 500:1:0.2, C ═ 2.5M)) was stirred magnetically at 365nm under 16W uv light for 6h (reaction temperature maintained at room temperature 20-30 ℃). 2mL of the reaction mixture was taken. Diluting with tetrahydrofuran solution, precipitating with n-hexane, and vacuum drying to obtain pure polymer. The DP of the polymer was 469, 514, 466, 510, 502, 487, 452, 517, 498, 456, respectively, and the PDI was 1.31, 1.24, 1.37, 1.45, 1.28, 1.27, 1.29, 1.34, 1.33, respectively.
Example 4:
the kraft lignin (0.250g, -OH2.0mmol), triethylamine (5.0mmol,0.506g) and 75mL ethyl acetate were added to a 250mL round bottom flask with a magnetic stir bar of tetrafluoroethylene, stirred in an oil bath at room temperature for 30min, then cooled in an ice bath, 2-bromoisobutyryl bromide (4.0mmol,0.919g) was dissolved in 10mL ethyl acetate and slowly added to the round bottom flask, reacted for 24h and 20mL water/tetrahydrofuran solution was added. Stirring for 5min and quenching the unreacted 2-bromoisobutyryl bromide. The solvent was spun dry, dissolved in 1, 4-dioxane, precipitated with unsaturated sodium bicarbonate, filtered and washed repeatedly with water. Dissolving with diethyl ether, filtering, and vacuum drying at 40 deg.C to obtain lignin macroinitiator (bromine atom content is 4.5mmol/g in sequence).
Under the protection of nitrogen, synthetic lignin macroinitiator (0.4mmol,0.089g), methyl methacrylate (20.024g, 200mmol) and different organic catalysts 10-phenyl-phenothiazine (22mg, 0.08 mmol)/10-methylphenothiazine (17mg,0.08mmol) (structure is shown in PC1, PC7 in the attached figure 3) were added into 10 ampoules in sequence, 18.76mL of N, N-dimethylacetamide solution ([ M ]: [ I ]: [ C ]: 500:1:0.2) was added into the reaction flask, and magnetic stirring was carried out at 365nm/380nm under the irradiation of 16W ultraviolet light for 6h (the reaction temperature was kept at room temperature 20-30 ℃). 2mL of the reaction mixture was taken. Diluting with tetrahydrofuran solution, precipitating with n-hexane, and vacuum drying to obtain pure polymer. The polymers DP were 419/524, 496/503, respectively, and the PDI was 1.45/1.38, 1.36/1.52, respectively.
Example 5:
the kraft lignin (0.250g, -OH2.0mmol), triethylamine (5.0mmol,0.506g) and 75mL ethyl acetate were added to a 250mL round bottom flask with a magnetic stir bar of tetrafluoroethylene, stirred in an oil bath at room temperature for 30min, then cooled in an ice bath, 2-bromoisobutyryl bromide (4.0mmol,0.919g) was dissolved in 10mL ethyl acetate and slowly added to the round bottom flask, reacted for 24h and 20mL water/tetrahydrofuran solution was added. Stirring for 5min and quenching the unreacted 2-bromoisobutyryl bromide. The solvent was spun dry, dissolved in 1, 4-dioxane, precipitated with unsaturated sodium bicarbonate, filtered and washed repeatedly with water. Dissolving with diethyl ether, filtering, and vacuum drying at 40 deg.C to obtain lignin macroinitiator (bromine atom content is 4.5mmol/g in sequence).
Under the protection of nitrogen, 5 ampoules were charged with the synthetic lignin macroinitiator (0.4mmol,0.089g), methyl methacrylate (20.024g, 200mmol) and the different organic catalysts 4-methoxyphenyl-10-phenothiazine (24mg,0.08 mmol)/4-chloro-10H-phenothiazine (25mg,0.08 mmol)/1-naphthyl-10H-phenothiazine (26mg,0.08 mmol)/2-naphthyl-10H-phenothiazine (26mg,0.08mmol)/10- (pyridin-2-yl) -10H-phenothiazine (0.08mmol,22mg)/10- (4-trifluoromethyl) phenyl) -phenothiazine (0.08mmol,27mg)/10- (4- (nitrile) phenyl) phenothiazine (0.08 mmol), 24mg), phenylbenzo [ b- ] phenothiazine (0.08mmol,26mg)) (the structure is shown in PC2, PC3, PC4, PC5, PC6, PC8, PC9, PC10 in the figure description 3) 18.76mL of N, N-dimethylacetamide solution (M: I: C: 500:1:0.2) is added into a reaction flask and stirred magnetically for 6h under 365nm and 16W ultraviolet irradiation (the reaction temperature is kept at room temperature for 20-30 ℃). 2mL of the reaction mixture was taken. Diluting with tetrahydrofuran solution, precipitating with n-hexane, and vacuum drying to obtain pure polymer. The DP of the polymer was 414, 452, 487, 479, 537, 528, 458, 462, respectively, and the PDI was 1.35, 1.24, 1.43, 1.52, 1.40, 1.33, 1.31, respectively.
Example 6:
the kraft lignin (0.250g, -OH2.0mmol), triethylamine (5.0mmol,0.506g) and 75mL ethyl acetate were added to a 250mL round bottom flask with a magnetic stir bar of tetrafluoroethylene, stirred in an oil bath at room temperature for 30min, then cooled in an ice bath, 2-bromoisobutyryl bromide (4.0mmol,0.919g) was dissolved in 10mL ethyl acetate and slowly added to the round bottom flask, reacted for 24h and 20mL water/tetrahydrofuran solution was added. Stirring for 5min and quenching the unreacted 2-bromoisobutyryl bromide. The solvent was spun dry, dissolved in 1, 4-dioxane, precipitated with unsaturated sodium bicarbonate, filtered and washed repeatedly with water. Dissolving with diethyl ether, filtering, and vacuum drying at 40 deg.C to obtain lignin macroinitiator (bromine atom content is 4.5mmol/g in sequence).
Under the protection of nitrogen, synthetic lignin macroinitiator (0.4mmol,0.089g), methyl methacrylate (20.024g, 200mmol) and different organic catalysts (2-naphthyl-10H-phenoxazine (0.08mmol,25mg)/10- (4- (nitrile group) phenyl) phenoxazine (0.08mmol,23mg)/10- (4- (trifluoromethyl) phenyl-phenoxazine (0.08mmol,26 mg)/10-phenylphenoxazine (0.08mol,21 mg)/1-naphthyl-10H-phenoxazine (0.08mol,25mg)) (structures are shown in the attached figure 3, PC11, PC12, PC13, PC14, PC15) were added into 5 ampoules in sequence, 18.76mL of N, N-dimethylacetamide solution ([ M ]: I: 500:1:0.2) at nm 365nm was added into the reaction flask, Stirring magnetically for 6h under 16W ultraviolet irradiation (the reaction temperature is kept at room temperature of 20-30 ℃). 2mL of the reaction mixture was taken. Diluting with tetrahydrofuran solution, precipitating with n-hexane, and vacuum drying to obtain pure polymer. The DP of the polymer was 468, 512, 454, 478, 481, respectively, and the PDI was 1.27, 1.74, 1.11, 1.24, 1.33, respectively.
Example 7:
the kraft lignin (0.250g, -OH2.0mmol), triethylamine (5.0mmol,0.506g) and 75mL ethyl acetate were added to a 250mL round bottom flask with a magnetic stir bar of tetrafluoroethylene, stirred in an oil bath at room temperature for 30min, then cooled in an ice bath, 2-bromoisobutyryl bromide (4.0mmol,0.919g) was dissolved in 10mL ethyl acetate and slowly added to the round bottom flask, reacted for 24h and 20mL water/tetrahydrofuran solution was added. Stirring for 5min and quenching the unreacted 2-bromoisobutyryl bromide. The solvent was spun dry, dissolved in 1, 4-dioxane, precipitated with unsaturated sodium bicarbonate, filtered and washed repeatedly with water. Dissolving with diethyl ether, filtering, and vacuum drying at 40 deg.C to obtain lignin macroinitiator (bromine atom content is 4.5mmol/g in sequence).
Under the protection of nitrogen, 6 ampoules were charged in succession with the synthetic lignin macroinitiator (0.4mmol,0.089g), methyl methacrylate (20.024g, 200mmol) and the 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- (nitrile) phenyl) -5, 10-dihydrophenazine (0.08mmol,31mg)/5,10-2 (2-naphthyl) -5, 10-dihydrophenazine (0.08mmol,35mg)/5,10-2 (1-naphthyl) -5, 10-dihydrophenazine (0.08mmol,35mg)) (structure shown in figure 3 PC18, PC19, PC20, PC21, PC22, PC23) 18.76mL of N, N-dimethylacetamide solution (M: I: C: 500:1:0.2) was added to a reaction flask and magnetically stirred for 6h under 16W of white LED light (reaction temperature was kept at room temperature 20-30 ℃). 2mL of the reaction mixture was taken. Diluting with tetrahydrofuran solution, precipitating with n-hexane, and vacuum drying to obtain pure polymer. The DP of the polymer was 464, 512, 495, 476, 479, 463, and the PDI was 1.41, 1.22, 1.18, 1.36, 1.14, 1.51, respectively.
Example 8:
the kraft lignin (0.250g, -OH2.0mmol), triethylamine (5.0mmol,0.506g) and 75mL ethyl acetate were added to a 250mL round bottom flask with a magnetic stir bar of tetrafluoroethylene, stirred in an oil bath at room temperature for 30min, then cooled in an ice bath, 2-bromoisobutyryl bromide (4.0mmol,0.919g) was dissolved in 10mL ethyl acetate and slowly added to the round bottom flask, reacted for 24h and 20mL water/tetrahydrofuran solution was added. Stirring for 5min and quenching the unreacted 2-bromoisobutyryl bromide. The solvent was spun dry, dissolved in 1, 4-dioxane, precipitated with unsaturated sodium bicarbonate, filtered and washed repeatedly with water. Dissolving with diethyl ether, filtering, and vacuum drying at 40 deg.C to obtain lignin macroinitiator (bromine atom content is 4.5mmol/g in sequence).
Under the protection of nitrogen, six synthetic lignin macroinitiators (0.4mmol,0.089g), methyl methacrylate (20.024g, 200mmol) and different organic catalysts (3,7-2 (4-diphenyl) 1-naphthyl-10-phenoxazine (0.08mmol,49mg), 3,7-2 (4-diphenyl) 2-naphthyl-10-phenoxazine (0.08mmol,49mg) and perylene (0.08mol,20mg)) are added into 3 ampoules in sequence (the structures are shown in the description of the figure 3, PC16, PC17 and PC24) 18.76mL of N, N-dimethylacetamide solution (M: I: C: 500:1:0.2) is added into the reaction flask and stirred under 16W white LED magnetic force for 6h (the reaction temperature is kept at room temperature for 20-30 ℃). 2mL of the reaction mixture was taken. Diluting with tetrahydrofuran solution, precipitating with n-hexane, and vacuum drying to obtain pure polymer. The DP of the polymer was 481, 479, 471, respectively, and the PDI was 1.38, 1.19, 1.25, respectively.
Example 9:
lignin sulfate (0.250g, -OH2.0mmol), triethylamine (5.0mmol,0.506g) and 75mL ethyl acetate were added to a 250mL round bottom flask with a magnetic stir bar of tetrafluoroethylene, stirred in an oil bath at room temperature for 30min, then cooled in an ice bath and 2-bromoisobutyryl bromide (4.0mmol,0.919 g)/2-bromopropionitrile (4.0mmol,0.532 g)/sulfonyl chloride (4.0mmol,0.536g)/2, 2-dichloroacetophenone (4.0mmol,0.752 g)/diphenylbromomethane (4.0mmol,0.984 g)/trichloromethane (4.0mmol,0.472g) dissolved in 10mL ethyl acetate was slowly added to the round bottom flask, reacted for 24h and 20mL of water/tetrahydrofuran solution was added. Stirring for 5min and quenching the unreacted 2-bromoisobutyryl bromide. The solvent was spun dry, dissolved in 1, 4-dioxane, precipitated with unsaturated sodium bicarbonate, filtered and washed repeatedly with water. Dissolving with diethyl ether, filtering, and vacuum drying at 40 deg.C to obtain lignin macroinitiator (bromine atom content of 4.5 mmol/g).
Under the protection of nitrogen, the synthesized lignin macroinitiator (0.4mmol,0.089g), 10-phenyl-phenothiazine (22mg, 0.08mmol), methyl methacrylate (20.024g, 200mmol), 18.76mL of different organic solvents (N, N-dimethylformamide/dichloromethane/dimethyl sulfoxide/tetrahydrofuran/ethyl acetate) (M: I: C: 500:1:0.2) were added in sequence to 5 ampoules and stirred magnetically for 6h under the irradiation of 365nm 16W ultraviolet light (the reaction temperature was kept at 20-30 ℃). 2mL of the reaction mixture was taken. Diluting with tetrahydrofuran solution, precipitating with n-hexane, and vacuum drying to obtain pure polymer. The DP of the polymer was 487, 454, 476, 459, 439, respectively, and the PDI was 1.69, 1.43, 1.54, 1.55, 1.20, respectively.
Example 10:
the kraft lignin (0.250g, -OH2.0mmol), triethylamine (5.0mmol,0.506g) and 75mL ethyl acetate were added to a 250mL round bottom flask with a magnetic stir bar of tetrafluoroethylene, stirred in an oil bath at room temperature for 30min, then cooled in an ice bath, 2-bromoisobutyryl bromide (4.0mmol,0.919g) was dissolved in 10mL ethyl acetate and slowly added to the round bottom flask, reacted for 24h and 20mL water/tetrahydrofuran solution was added. Stirring for 5min and quenching the unreacted 2-bromoisobutyryl bromide. The solvent was spun dry, dissolved in 1, 4-dioxane, precipitated with unsaturated sodium bicarbonate, filtered and washed repeatedly with water. Dissolving with diethyl ether, filtering, and vacuum drying at 40 deg.C to obtain lignin macroinitiator (bromine atom content of 4.5 mmol/g).
Under the protection of nitrogen, an ampoule was charged with a synthetic lignin macroinitiator (0.4mmol,0.089g), 10-phenyl-phenothiazine (PC1,5.5mg, 0.02mmol), methyl methacrylate (0.400g, 4mmol), 39.59mL of N, N-dimethylacetamide solution ([ M ]: I: [ C ]: 10:1:0.05) and magnetically stirred under 16W UV irradiation at 365nm for 6h (the reaction temperature was maintained at room temperature 20-30 ℃). 2mL of the reaction mixture was taken. Diluting with tetrahydrofuran solution, precipitating with n-hexane, and vacuum drying to obtain pure polymer. The DP of the polymer was 8 and the PDI was 1.11.
Example 11:
the kraft lignin (0.250g, -OH2.0mmol), triethylamine (5.0mmol,0.506g) and 75mL ethyl acetate were added to a 250mL round bottom flask with a magnetic stir bar of tetrafluoroethylene, stirred in an oil bath at room temperature for 30min, then cooled in an ice bath, 2-bromoisobutyryl bromide (4.0mmol,0.919g) was dissolved in 10mL ethyl acetate and slowly added to the round bottom flask, reacted for 24h and 20mL water/tetrahydrofuran solution was added. Stirring for 5min and quenching the unreacted 2-bromoisobutyryl bromide. The solvent was spun dry, dissolved in 1, 4-dioxane, precipitated with unsaturated sodium bicarbonate, filtered and washed repeatedly with water. Dissolving with diethyl ether, filtering, and vacuum drying at 40 deg.C to obtain lignin macroinitiator (bromine atom content of 4.5 mmol/g).
Under nitrogen protection, an ampoule was charged with the synthetic lignin macroinitiator (0.4mmol,0.089g), 10-phenyl-phenothiazine (PC1,22mg,0.08mmol), methyl methacrylate (20.024g, 200mmol), 378.76mL of N, N-dimethylacetamide solution (C ═ 0.5M) was magnetically stirred for 6h under 16W uv irradiation at 365nm (reaction temperature was maintained at room temperature 20-30 ℃). 2mL of the reaction mixture was taken. Diluting with tetrahydrofuran solution, precipitating with n-hexane, and vacuum drying to obtain pure polymer. The DP of the polymer was 475 and the PDI was 1.58.
The invention provides a method and a concept for a method for photoinduced organic catalytic lignin grafting modification, and a method and a way for realizing the technical scheme are many, the above description is only a preferred embodiment of the invention, and it should be noted that, for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the invention, and the improvements and decorations should also be regarded as the protection scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (8)
1. A method for grafting and modifying lignin by photoinduction and organic catalysis is characterized by comprising the following steps:
(1) reacting lignin with alkyl acyl halide initiator to synthesize lignin macroinitiator;
(2) mixing the lignin macroinitiator obtained in the step (1), an ethylene monomer, a catalyst and a solvent in an inert atmosphere, and carrying out atom transfer radical polymerization under ultraviolet light or visible light radiation to obtain a lignin-based polymer;
in the step (2), the catalyst is 10-phenylphenothiazine, 4-methoxyphenyl-10-phenothiazine, 4-chloro-10H-phenothiazine, 1-naphthyl-10H-phenothiazine, 2-naphthyl-10H-phenothiazine, 10- (pyridin-2-yl) -10H-phenothiazine, 10-methylphenothiazine, 10- (4- (trifluoromethyl) phenyl) phenothiazine, 10- (4- (nitrile) phenyl) phenothiazine, phenylbenzo [ b ] phenothiazine, 2-naphthyl-10H-phenoxazine, 10- (4- (nitrile) phenyl) phenoxazine, 10- (4- (trifluoromethyl) phenyl) phenoxazine, 10-phenylphenoxazine, or a mixture thereof, 1-naphthyl-10H-phenoxazine, 3,7-2 (4-diphenyl) 1-naphthyl-10-phenoxazine, 3,7-2 (4-diphenyl) 2-naphthyl-10-phenoxazine, 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- (nitrile) phenyl) -5, 10-dihydrophenazine, 5,10-2 (2-naphthyl) -5, 10-dihydrophenazine, 5,10-2 (1-naphthyl) -5, 10-dihydrophenazine and perylene.
2. The method for grafting and modifying photoinduced organic catalytic lignin according to claim 1, wherein in the step (1), the alkyl acyl halide initiator is 2-bromoisobutyryl bromide, 2-bromopropionitrile, sulfonyl chloride, 2-dichloroacetophenone, diphenyl bromomethane or trichloromethane; the lignin is sulfate lignin, organic solvent-dissolved lignin, lignosulfonate, and soda lignin.
3. The method for photo-induced organic catalytic lignin grafting modification according to claim 2, wherein the reaction in step (1) is completed under the action of triethylamine, wherein the reaction molar ratio of hydroxyl groups in the lignin to the alkyl acyl halide initiator is 1:1 to 3.
4. The method of claim 1, wherein in the step (2), the vinyl monomer is any one of benzyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, isodecyl 2-methyl-2-acrylate, 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester, methyl methacrylate, acrylonitrile, styrene or isopropamide.
5. The method for photo-induced organic catalytic lignin grafting modification according to claim 1, wherein in the step (2), the solvent is any one of N, N-dimethylformamide, N-dimethylacetamide, dichloromethane, dimethyl sulfoxide, tetrahydrofuran or ethyl acetate.
6. The method for grafting and modifying the lignin by photoinduced organic catalysis according to claim 1, wherein in the step (2), the reaction molar ratio of the lignin macroinitiator, the ethylene monomer and the catalyst is 1: 10-500: 0.05-0.200.
7. The method for photo-induced organic catalytic lignin grafting modification according to claim 1, wherein the concentration of the ethylene monomer in the solvent in the step (2) is 0.5-5 mol/L.
8. The method for grafting and modifying photoinduced organic catalytic lignin according to claim 1, wherein in the step (2), the light source and the light wavelength required for catalysis of the reaction are respectively selected according to the catalyst, and specifically:
when the catalyst is 10-phenyl phenothiazine or 10-methyl phenothiazine, 365nm or 380nm ultraviolet light is used for catalysis;
when the catalyst is 4-methoxyphenyl-10-phenothiazine, 4-chloro-10H-phenothiazine, 1-naphthyl-10H-phenothiazine, 2-naphthyl-10H-phenothiazine, 10- (pyridine-2-yl) -10H-phenothiazine, 10- (4- (trifluoromethyl) phenyl) phenothiazine, 10- (4- (nitrile) phenyl) phenothiazine, when phenylbenzo [ b ] phenothiazine, 2-naphthyl-10H-phenoxazine, 10- (4- (nitrile) phenyl) phenoxazine, 10- (4- (trifluoromethyl) phenyl-phenoxazine, 10-phenylphenoxazine, 1-naphthyl-10H-phenoxazine, using 365nm ultraviolet light for catalysis;
when the catalyst is 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- (nitrile) phenyl) -5, 10-dihydrophenazine, 5,10-2 (2-naphthyl) -5, 10-dihydrophenazine, 5,10-2 (1-naphthyl) -5, 10-dihydrophenazine, 3,7-2 (4-diphenyl) 1-naphthyl-10-phenazine, 3,7-2 (4-diphenyl) 2-naphthyl-10-phenazine, perylene, catalyzed using a white LED lamp.
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Inventor after: Kang Peng Inventor after: He Wei Inventor after: Liu Chengkou Inventor after: Shi Shengpeng Inventor after: Cai Tao Inventor after: Guo Kai Inventor after: Zhai Jinglin Inventor after: Hu Xin Inventor after: Zhu Ning Inventor after: Fang Zheng Inventor after: Yin Fan Inventor before: Guo Kai Inventor before: Zhai Jinglin Inventor before: Hu Xin Inventor before: Zhu Ning Inventor before: Fang Zheng Inventor before: Yin Fan Inventor before: He Wei Inventor before: Liu Chengkou |
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Effective date of registration: 20220309 Address after: 100000 22 Chaoyangmen North Street, Chaoyang District, Beijing. Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Address before: 210000 Puzhu South Road, Pukou District, Nanjing, Jiangsu 30 Patentee before: Nanjing Tech University |