CN108586647A - A kind of method that the atom transfer radical polymerization of novel photocatalyst prepares polymer - Google Patents
A kind of method that the atom transfer radical polymerization of novel photocatalyst prepares polymer Download PDFInfo
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- CN108586647A CN108586647A CN201810453532.9A CN201810453532A CN108586647A CN 108586647 A CN108586647 A CN 108586647A CN 201810453532 A CN201810453532 A CN 201810453532A CN 108586647 A CN108586647 A CN 108586647A
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- 238000010560 atom transfer radical polymerization reaction Methods 0.000 title claims abstract description 18
- 229920000642 polymer Polymers 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 9
- 239000011941 photocatalyst Substances 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 9
- 239000003863 metallic catalyst Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 150000003254 radicals Chemical class 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 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
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 5
- -1 2- isobutyl bromides methyl esters Chemical class 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical group Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 150000005045 1,10-phenanthrolines Chemical class 0.000 claims 1
- XZKFBZOAIGFZSU-UHFFFAOYSA-N 1-bromo-4-methylpentane Chemical class CC(C)CCCBr XZKFBZOAIGFZSU-UHFFFAOYSA-N 0.000 claims 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical class CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000012458 free base Substances 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 150000003956 methylamines Chemical class 0.000 claims 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims 1
- 229960001124 trientine Drugs 0.000 claims 1
- HMQFJYLWNWIYKQ-UHFFFAOYSA-N 1,4-diphenylbutadiyne Chemical group C1=CC=CC=C1C#CC#CC1=CC=CC=C1 HMQFJYLWNWIYKQ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000620 organic polymer Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000010526 radical polymerization reaction Methods 0.000 description 6
- 230000005855 radiation Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229920001400 block copolymer Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 3
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004442 gravimetric analysis Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 230000001902 propagating effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical class ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+2].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 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 229950010007 dimantine Drugs 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000006897 homolysis reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000001795 light effect Effects 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NRQNMMBQPIGPTB-UHFFFAOYSA-N methylaluminum Chemical compound [CH3].[Al] NRQNMMBQPIGPTB-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/42—Nitriles
- C08F120/44—Acrylonitrile
-
- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
Abstract
The invention discloses a kind of graphite phase carbon nitride (g C3N4Poly- application of (Isosorbide-5-Nitrae diphenyl diacetylene) photochemical catalyst in photoinduction atom transfer radical polymerization of)/nanometer, the system is by polymerizable monomer, metallic catalyst, ligand, atom transferred free radical initiator, g C3N4Poly- (Isosorbide-5-Nitrae diphenyl diacetylene) photochemical catalyst of/nanometer and solvent composition, belong to organic polymer preparing technical field.The present invention not only realizes " activity "/controllable free-radical polymerisation under conditions of room temperature is visible light-initiated, but also can realize quick startup and termination to polymerisation by the on and off of light source.
Description
Technical field
The method that the atom transfer radical polymerization of novel photocatalyst of the present invention prepares polymer, belongs to polymer chemistry
Field, and in particular to one kind is by the photoinduction atom transfer that g-C3N4/ nanometers poly- (Isosorbide-5-Nitraes-diphenyl diacetylene) are photochemical catalyst
The method that free radical polymerization prepares polymer.
Background technology
Atom transfer radical polymerization is China doctor Wang Jinshan residing in American in Krzysztof professor's Matyjaszewski classes
Topic group is found that atom transfer radical polymerization for the first time when being engaged in post-doctoral research（Wang, J.-S.; Matyjaszewski,
K. Controlled/"living" radical polymerization. atom transfer radical
polymerization in the presence of transition-metal complexes. J. Am. Chem.
Soc. 1995, 117 (20): 5614-5615.）.The same period, Kyoto Univ Japan Mitsuo professors Sawamoto etc. also send out
Article of the table about the active free radical polymerization of metal catalytic（Kato, M.; Kamigaito, M.; Sawamoto, M.;
Higashimura, T. Polymerization of Methyl Methacrylate with the Carbon
Tetrachloride/Dichlorotris-(triphenylphosphine) ruthenium (II)/Methylaluminum
Bis(2,6-di-tert-butylphenoxide) Initiating System: Possibility of Living
Radical Polymerization. Macromolecules 1995, 28 (5): 1721-1723.）.
Atom transfer radical polymerization（ATRP）It is by Propagating Radical and alkyl halide（R-X）Or macromolecular halogenation
Object（Suspend mode kind）Between reversible dynamic equilibrium realize.The transition metal complex M of suspend mode kind and activator-low-oxidation-statet m/
L（Mt mThe transition metal material in oxidation state m is represented, L is ligand）Intermittence activation forms Propagating Radical（Pn·）And passivation
Agent-high oxidation state transition metal complex X-Mt m+1/ L, active rate constant are kact.Simultaneously passivator and Propagating Radical with
Back reaction（kdeact）Re-form suspend mode kind and activator.
Light initiation polymerization was constantly subjected to the concern of scholars in recent years because of its good potential economy and ecological effect.Sense
Photopolymer becomes basic material, such as coating, adhesive, ink, printing plate, optical waveguide in many application fields
With microelectronics etc..
It is by increasing the reactivity of metallic catalyst to reduce the dosage of catalyst to use the purpose of light initiation polymerization.
The luminous effect of ATRP was proposed in 2000 by Guan and Smart for the first time, and 2,2- dichloroacetophenones are utilized under the irradiation of visible light
As initiator, CuCl/2,2 '-bipyridyls carry out the living polymerization of methyl methacrylate (MMA) as catalyst（Guan
Z, Smart B. A Remarkable Visible Light Effect on Atom-Transfer Radical
Polymerization. Macromolecules, 2000, 33(18): 6904-6906）.They have found to use above-mentioned body
System, polymerization efficiency are greatly improved.Although the influence of light radiation is not clear, they propose in radiation of visible light
Lower C-Cl homolysis in R-Cl/CuCl complex compounds.Under the same conditions, Kwak and Matyjaszewski is to above-mentioned system
Mechanism is probed into, it is found that light irradiation has the duration of activation very important influence（Kwak Y,
Matyjaszewski K. Photoirradiated Atom Transfer Radical Polymerization with an
Alkyl Dithiocarbamate at Ambient Temperature. Macromolecules, 2010, 43(12):
5180-5183）.
In photoinduction atom transition free radical polymerization reaction, photochemical catalyst plays the role of highly important.Photochemical catalyst
The chemical substance of catalytic action can be exactly played under the excitation of photon.
g-C3N4Poly- (Isosorbide-5-Nitrae-diphenyl diacetylene) photochemical catalyst of/nanometer is prepared simply, and detailed process is as follows：Nanometer it is poly- (1,
4- diphenyl diacetylenes) it is prepared according to document（Ghosh S, Kouamé NA, Ramos L, Remita S, Dazzi A,
Deniset-Besseau A, Beaunier P, Goubard F, Aubert P-H, Remita H. Conducting
polymer nanostructures for photocatalysis under visible light. Nature
Materials. 2015, 14(5): 505-511.）.A certain number of nanometers poly- (1,4- diphenyl diacetylenes) are added to
Contain g-C3N4Ethanol solution, overnight.Composite catalyst g-C is collected in filtering3N4/ nanometer is poly- (1,4- diphenyl diacetylenes).
The present invention provides a kind of g-C simple in structure, at low cost3N4Poly- (1,4- diphenyl diacetylenes) photocatalysis of/nanometer
Agent realizes g-C3N4The atom transfer radical polymerization of poly- (1,4- diphenyl diacetylenes) the photoinduction polymerisable monomer of/nanometer.
Invention content
The purpose of the present invention is to provide one kind by g-C3N4/ nanometer poly- (1,4- diphenyl diacetylenes) is photochemical catalyst
The method that photoinduction atom transfer radical polymerization prepares polymer.Graphite phase carbon nitride（g-C3N4）It is a kind of unique 2D layers
Shape nonmetallic materials, band structure are very suitable for the production hydrogen in photochemical catalyzing and the crucial half-reaction step of production oxygen two,
The advantages that having both simple synthetic method, good thermal stability simultaneously, therefore be generally considered as the light with broad prospect of application and urged
Change material, has in fields such as photocatalysis Decomposition aquatic products hydrogen, artificial photosynthesis, organic pollutant degradation and carbon dioxide reductions
Important researching value.However current g-C3N4The puzzlement for the problems such as energy gap is wider is still suffered from light-catalyzed reaction.It adopts
The g-C synthesized with pyrolysismethod3N4Usually there is wider energy gap（~2.7 eV）, it is only capable of absorbing very least a portion of in visible light
Short-wavelength light.How its band structure is regulated and controled, and then widen the absorbability of visible light, makes full use of that account for solar energy total
Energy>40 visible light part becomes one of the research hotspot in the field.It is poly-（1,4- diphenyl diacetylenes）（PDPB）It is a kind of
One-dimensional conjugated polymer has good electrochemistry, electrical and optical properties.It is prepared using hexagonal phase template
NanoPDPB fibers have very narrow energy gaps.Under the irradiation of sunlight, nanoPDPB equally will produce conduction band electron
（e-）And valence band hole（h+）.Under light illumination, ground state is energized into the triplet state of minimum energy.By conductive nanoPDPB fibers with
g-C3N4, g-C can be solved3N4The wider problem of energy gap.
The used technical solution of the present invention is the system by polymerizable monomer, metallic catalyst, ligand, atom turn
Move radical initiator, g-C3N4Poly- (Isosorbide-5-Nitrae-diphenyl diacetylene) photochemical catalyst of/nanometer and solvent composition, in radiation of visible light
Lower carry out atom transfer radical polymerization.Obtain the feature of the active polymerization of polymer.Moreover, the polymerization prepared in the system
Object can successfully carry out chain extending reaction, prepare block copolymer.
The specific operating procedure of photoinduction active atomic transferring free-radical polymerization is as follows：In 50 clean mL there-necked flasks
Atom transferred free radical initiator, metallic catalyst, polymerisable monomer, ligand, photocatalysis are sequentially added according to certain proportioning
Agent g-C3N4/ nanometer poly- (Isosorbide-5-Nitrae-diphenyl diacetylene) and solvent, and stirrer is added.The oxygen being passed through in nitrogen removing solution.
There-necked flask placement is subjected to polymerisation under visible light illumination, temperature is constant at 25 DEG C or so.After reaction by solution by
It is added drop-wise in a large amount of methanol solutions and repeatedly precipitates, and be continuously agitated.Sediment detaches after standing overnight through filtering, then by gained
Polymer is put into drying in normal-temperature vacuum drying, until weighing after constant weight, and calculates polymerization conversion.Obtained polymer can
Directly carry out gel permeation chromatography（GPC）Test molecule amount（Mn,GPC）And molecular weight distribution（Mw/Mn）.
Chain extending reaction
The chain extending reaction of the light-catalysed ATRP systems of room temperature：Using purified polymer as macromole evocating agent, by specific
Polymerisable monomer methyl methacrylate, metallic catalyst, ligand, photochemical catalyst g-C is added in molar ratio3N4Poly- (the 1,4- of/nanometer
Diphenyl diacetylene), solvent and clean stirrer, after macromole evocating agent is completely dissolved, letting nitrogen in and deoxidizing.Then by three mouthfuls
Bottle, which is placed under radiation of visible light, to be reacted, and the post-processing of polymerisation is consistent with operating procedure described above.
Specific embodiment
Embodiment 1
By methyl acrylate（100 mmol, 8.609 g）, 2- bromopropionitriles（1 mmol, 0.134 g）, copper bromide（0.01
mmol, 0.0022 g）, N, N, N', N'', N''- five methyl diethylentriamines（0.02 mmol, 0.0034 g）、g-C3N4/
Nanometer poly- (1,4- diphenyl diacetylenes)（0.5 mg）, 20 ml acetonitriles mixed in there-necked flask, nitrogen charging deoxygenation.Control reactant
Be temperature be 25 DEG C, under visible light illumination react a period of time after, obtained polymethyl acrylate is repeatedly sunk in methyl alcohol
Drop, is then dried under vacuum to constant weight, obtains white powder.Sample conversion ratio uses gravimetric analysis.Molecular weight and molecular weight point
Cloth is tested using gel permeation chromatograph.Light irradiates 24 hours, and methyl acrylate conversion ratio is up to 43.6%, gel infiltration color
Spectrum measures the molecular weight of polymethyl acrylate（Mn,GPC）=5200, Mw/Mn=1.36.Under the conditions of mixture ratios, polymer molecule
Amount is linearly increasing with the growth of conversion ratio.It will obtain polymethyl acrylate and carry out chain extension experiment as macromole evocating agent, obtain
It is to block copolymer amount（Mn,GPC）=16100, Mw/Mn=1.51.
Embodiment 2
By acrylonitrile（150 mmol, 7.95 g）, α-bromo-acid ethyl ester（1 mmol, 0.243 g）, copper bromide（0.01
mmol, 0.0022 g）, three-(N, N- dimethylaminoethyl) amine（0.02 mmol, 0.0046 g）、g-C3N4/ nanometer is poly-
(1,4- diphenyl diacetylenes)（1 mg）, 20 ml acetonitriles mixed in there-necked flask, nitrogen charging deoxygenation.Controlling temperature of reaction system is
25 DEG C, after reacting a period of time under visible light illumination, obtained polyacrylonitrile is repeatedly settled in methyl alcohol, then vacuum is dry
It is dry to constant weight, obtain white polypropylene nitrile powder.Sample conversion ratio uses gravimetric analysis.Molecular weight and molecular weight distribution use
Gel permeation chromatograph is tested.Light irradiates 48 hours, and for acrylonitrile conversion rate up to 58.9%, gel permeation chromatography measures poly- third
The molecular weight of alkene nitrile（Mn,GPC）=4900, PDI=1.41.Under the conditions of mixture ratios, polymer molecular weight with conversion ratio growth
And it is linearly increasing.It will obtain polyacrylonitrile and carry out chain extension experiment as macromole evocating agent, obtaining block copolymer amount is
（Mn,GPC）=15200, Mw/Mn=1.49.
Embodiment 3
By acrylamide（100 mmol, 7.1 g）, 2- bromopropionitriles（1 mmol, 0.134 g）, copper bromide（0.01 mmol,
0.0022 g）, N, Dymanthine（0.02 mmol, 0.006 g）、g-C3N4/ nanometer is poly- (1,4- diphenyl diacetylenes)
（2 mg）, 20 ml ethanol/waters（V/V=1：1）It is mixed in there-necked flask, nitrogen charging deoxygenation.It is 25 DEG C to control temperature of reaction system,
After reacting a period of time under radiation of visible light, obtained polyacrylamide is repeatedly settled in acetone, is then dried under vacuum to
Constant weight obtains polyacrylamide.Sample conversion ratio uses gravimetric analysis.Molecular weight and molecular weight distribution use gel infiltration color
Spectrometer is tested.Light irradiates 36 hours, and for acrylamide conversion ratio up to 50.8%, gel permeation chromatography measures polyacrylamide
Molecular weight（Mn,GPC）=5100, PDI=1.48.Under the conditions of mixture ratios, polymer molecular weight is linear with the growth of conversion ratio
Increase.It will obtain polyacrylamide and carry out chain extension experiment as macromole evocating agent, obtaining block copolymer amount is
（Mn,GPC）=15600, Mw/Mn=1.55.
Claims (8)
1. a kind of g-C3N4/ nanometer poly- (1,4- diphenyl diacetylenes) is the photoinduction atom transfer radical polymerization of photochemical catalyst
The method for preparing polymer, which is characterized in that the system is by polymerizable monomer, metallic catalyst, ligand, atom transfer freedom
Base initiator, g-C3N4Poly- (Isosorbide-5-Nitrae-diphenyl diacetylene) photochemical catalyst of/nanometer and solvent composition, carry out under visible light illumination
Atom transfer radical polymerization.
2. according to the polymerisable monomer described in claim 1, it is characterised in that the polymerisable monomer be methyl acrylate,
One kind in methyl methacrylate, acrylonitrile, acrylamide, hydroxy-ethyl acrylate.
3. according to the metallic catalyst described in claim 1, it is characterised in that the metallic catalyst is copper bromide, bromination
One kind in iron.
4. according to the ligand described in claim 1, it is characterised in that the ligand is N, N, N', N'', N''- pentamethyls two
Ethylenetriamine, three (2- pyridines) methyl amines, 1,1,4,7,10,10- hexamethyls trien, three-(N, N- diformazan ammonia
Base ethyl) amine, bis- (1,10- phenanthrolines), tetrabutylammonium bromide, N, one kind in N- bis- (2- picolines) octadecylamine.
5. according to the atom transferred free radical initiator described in claim 1, it is characterised in that the atom transfer is free
Base initiator is one kind in 2- isobutyl bromides methyl esters, 2- bromopropionitriles, 2- isobutyl ethyl bromides, α-bromo-acid ethyl ester.
6. according to the method described in claim 1, it is characterised in that the polymerizable monomer, atom transferred free radical draw
Agent is sent out, the molar ratio of metallic catalyst, ligand is（50-1000）：（1-2）：（0.001-1）：（0.0002-3）.
7. according to the method described in claim 1, it is characterised in that the photochemical catalyst g-C3N4Poly- (the 1,4- hexichol of/nanometer
Base diacetylene) amount be（5-25）mg.
8. according to the solvent described in claim 1, it is characterised in that the solvent is acetonitrile, dimethyl sulfoxide, N, N- diformazans
Base formamide.
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| CN111072825A (en) * | 2020-01-10 | 2020-04-28 | 西北大学 | Carbon nitride catalyzed atom transfer radical polymerization method |
| CN116199810A (en) * | 2023-03-16 | 2023-06-02 | 福州大学 | Heterogeneous photocatalytic controllable active free radical polymerization method |
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| CN111072825A (en) * | 2020-01-10 | 2020-04-28 | 西北大学 | Carbon nitride catalyzed atom transfer radical polymerization method |
| CN116199810A (en) * | 2023-03-16 | 2023-06-02 | 福州大学 | Heterogeneous photocatalytic controllable active free radical polymerization method |
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