CN116162097A - Atom transfer radical polymerization photocatalyst based on bipyridine thiadiazole quaternary ammonium salt derivative, and preparation method and application thereof - Google Patents
Atom transfer radical polymerization photocatalyst based on bipyridine thiadiazole quaternary ammonium salt derivative, and preparation method and application thereof Download PDFInfo
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- CN116162097A CN116162097A CN202211562366.9A CN202211562366A CN116162097A CN 116162097 A CN116162097 A CN 116162097A CN 202211562366 A CN202211562366 A CN 202211562366A CN 116162097 A CN116162097 A CN 116162097A
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- radical polymerization
- atom transfer
- transfer radical
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- 238000010560 atom transfer radical polymerization reaction Methods 0.000 title claims abstract description 28
- -1 bipyridine thiadiazole quaternary ammonium salt Chemical class 0.000 title claims abstract description 22
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims abstract description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims abstract description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000499 gel Substances 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002998 adhesive polymer Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 3
- 208000012839 conversion disease Diseases 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- BKTKLDMYHTUESO-UHFFFAOYSA-N ethyl 2-bromo-2-phenylacetate Chemical compound CCOC(=O)C(Br)C1=CC=CC=C1 BKTKLDMYHTUESO-UHFFFAOYSA-N 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GAWFOTLSFWVPFU-UHFFFAOYSA-N 2-bromo-2-methylpropanoic acid ethene Chemical compound BrC(C(=O)O)(C)C.C=C GAWFOTLSFWVPFU-UHFFFAOYSA-N 0.000 description 1
- 241000272814 Anser sp. Species 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- OAEGRYMCJYIXQT-UHFFFAOYSA-N dithiooxamide Chemical compound NC(=S)C(N)=S OAEGRYMCJYIXQT-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010505 homolytic fission reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical class C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- BGUWFUQJCDRPTL-UHFFFAOYSA-N pyridine-4-carbaldehyde Chemical compound O=CC1=CC=NC=C1 BGUWFUQJCDRPTL-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
-
- 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
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polymerization Catalysts (AREA)
Abstract
The invention provides a bipyridine thiadiazole quaternary ammonium salt derivative-based atom transfer radical polymerization photocatalyst, a preparation method and application thereof. The catalyst is a bipyridine thiadiazole quaternary ammonium salt derivative, and the bipyridine thiadiazole derivative has a structure shown in a formula (I): wherein R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, benzyl, p-methylbenzyl or p-tert-butylbenzyl. The catalyst is prepared by a simple organic synthesis reaction, and has a photocatalysis effect on atom transfer radical polymerization of various monomers. The preparation method provided by the invention is simple and organicStarting from the raw materials, the preparation method is simple and convenient, the catalytic loading amount is low, the reaction conversion rate is higher, and the trial monomer range is wide.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and relates to an atom transfer radical polymerization catalyst, a preparation method and application thereof.
Background
Compared with the traditional free radical polymerization, the atom transfer radical polymerization is a novel active polymerization method, has the advantages of controllable reaction process, controllable product molecular weight, narrow molecular weight distribution, modifiable polymer chain ends and the like, and has wide application in the fine synthesis and structure control of polymer materials such as plastics, resins, gels and the like. In order to overcome the defects of high biotoxicity and difficult removal of the traditional copper and iridium catalysts, the atomic transfer radical polymerization technology has appeared, and various pure organic photocatalysts with good light control performance, low catalytic loading and easy removal have been developed successively.
In the traditional free radical polymerization reaction, the chain initiation process can generate a large amount of free radicals, so that the reaction rate is high, the automatic acceleration process and a large amount of chain transfer and double radical termination exist, the reaction process is uncontrollable, the molecular weight of the obtained polymer is not customizable, and the molecular weight distribution is wide. Atom transfer radical polymerization refers to homolytic cleavage of the carbon-halogen bond of the initiator by the action of a catalyst, and the concentration of active species is kept low by the balance of active species-dormant species, thus reducing the occurrence of chain transfer and double radical termination.
The replacement of noble metals with pure organic compounds as atom transfer radical polymerization photocatalysts presents certain challenges. As molecules of the atom transfer radical polymerization photocatalyst, appropriate oxidation-reduction potential is needed to maintain active species-dormant species balance; the catalyst has a larger molar absorptivity so as to reduce the loading of the catalyst; good solubility is required to accommodate a variety of monomer and solvent systems; a certain stability is required to maintain good polymerization control.
Recent studies have focused on photocatalysts that polymerize phenothiazines, phenoxazines, dihydrophenazines, and oxygen-doped aromatic ring-like molecules as atom transfer radicals. The catalyst has higher raw material cost and more complex preparation process. The molar absorptivity is improved, the wavelength of light required by the reaction is increased, and the stability and universality of the catalyst are improved, so that the method is an important direction for future catalyst research.
Disclosure of Invention
The invention aims to provide an efficient atom transfer radical polymerization photocatalyst and application thereof.
The atom transfer radical polymerization photocatalyst provided by the invention is a bipyridyl thiadiazole salt derivative, and has a structure shown in a formula (I):
wherein R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, benzyl, p-methylbenzyl, p-tert-butylbenzyl and the like.
The invention also provides a preparation method of the atom transfer radical polymerization photocatalyst based on the bipyridine thiadiazole quaternary ammonium salt derivative, which is to mix the catalyst, the initiator, the monomer and the solvent, and irradiate for a period of time at a wavelength of 360-480nm to obtain the polymer.
Further, the monomers used for catalyzing the atom transfer radical polymerization are (II-1) to (II-
13 One or more of the monomers:
in a preferred embodiment, the initiator used to catalyze the atom transfer radical polymerization is (III)
1) One or more of the bromine initiators described in (III-5) are mixed:
in a preferred embodiment, the catalyst is used in an amount of 10 to 1000ppm (relative to the monomer) for atom transfer radical polymerization.
In a preferred embodiment, the solvent system for the reaction is one or a mixture of several of water, dichloromethane, acetonitrile, ethanol, methanol, tetrahydrofuran, and dimethyl sulfoxide.
In a preferred embodiment, the polymer is used for preparing plastics, resins, gels, adhesives and other polymer materials.
In a preferred embodiment, the organic solvent is one or more of dichloromethane, ethanol, methanol, tetrahydrofuran, ethyl acetate and water.
The invention also provides an application of the atom transfer radical polymerization photocatalyst based on the bipyridine thiadiazole quaternary ammonium salt derivative, which is an application in the preparation of plastic, resin, gel and adhesive polymer materials.
The raw materials of the invention are all pure organic compounds, and the invention has wide sources, easily available raw materials, low price, simple synthesis and convenient preparation. The invention describes that the prepared photocatalyst has low load, good polymerization control and easy removal after reaction.
Example 1
This example 1 provides a general method for the preparation of the quaternary ammonium bipyridyl thiadiazole derivatives mentioned herein. The method comprises the following specific steps:
(1) To a 100mL three-necked flask were successively added 640mg (5.3 mmol) of dithiooxamide, 880mg (10.6 mmol) of pyridine-4-carbaldehyde and 50mL of anhydrous DMF. After stirring well, heating and refluxing overnight under the protection of argon. After the reaction is finished, the mixture is cooled to room temperature, and a large amount of brown yellow precipitates are precipitated in the system. And (3) filtering under reduced pressure to collect a filter cake, and then repeatedly washing the collected filter cake with acetone and water. Finally, 785mg of yellow powder was obtained by suction filtration and drying, and the yield was 52%.
(2) 250mg (0.84 mmol) of the yellow powder obtained in the previous step and 7.5mL of methyl p-toluenesulfonate were successively added to a 20mL round bottom flask. The reaction was stirred at room temperature for 2 days, and after the completion of the reaction, a yellowish green turbid solution was obtained. The cloudy system was then poured into 100mL of ethyl acetate and the yellow precipitate was collected.
(3) The yellow precipitate was dissolved in 10mL of deionized water and gradually added dropwise to 100mL of acetone to re-precipitate a yellowish green precipitate. Finally, the product is subjected to vacuum drying treatment after the re-precipitation operation is fully carried out, 363mg of goose yellow powder is obtained, and the yield is 60%.1H NMR (400 MHz, DMSO-d 6): delta 9.15 (d, J=6.7 Hz, 4H), 8.75 (d, J=6.7 Hz, 4H), 7.47 (d, 8.0Hz, 4H), 7.10 (d, 8.0Hz, 4H), 4.40 (s, 6H), and 2.28 (s, 6H) ppm;13C NMR (101 MHz, DMSO-d 6): delta 165.1,154.9,146.6,145.5,145.0,138.0,128.1,125.4,123.7,47.9,and 20.7ppm; HRMS (esi+) calcd for C16H14N4s22+m/z 163.0324; found m/z 163.0329.
For other types of substituted bipyridyl thiadiazole quaternary ammonium salts, such methods can also be used. On the basis of the yellow precipitate prepared in step (1), the following method was used:
example 2
This example 2 provides a method and application for atom transfer radical polymerization of acrylic monomers with such catalysts.
The atom transfer radical polymerization method provided in this embodiment uses methyl dipyridothiadiazole quaternary ammonium salt as a catalyst and methyl methacrylate as a monomer, and the specific steps for preparing the polymer are as follows:
(1) 13.2mg (0.02 mmol) of the quaternary ammonium salt of methyl dipyridothiadiazole and 48.6mg (0.2 mmol) of ethyl alpha-bromophenylacetate are added to 4ml of DMSO, kept protected from light, and dissolved by shaking or ultrasound, and then 2ml (2.0 g,20 mmol) of methyl methacrylate are added to the solution. The solution was transferred to a 20ml quartz schlenk tube, sealed and subjected to three freeze-thaw cycles to remove oxygen from the reaction system. The irradiation was continued for 12 hours using a violet LED lamp. After the reaction was completed, the resulting polymer solution was diluted with 4ml of methylene chloride, and then the solution was added dropwise to 100ml of methanol under stirring to precipitate a polymer. After stirring for 2 hours, filtration was carried out, and then the resulting polymer was dried at 40℃for 24 hours to obtain 1.78g (89%) of polymethyl methacrylate.
Example 3
This example 3 provides a method and application for atom transfer radical polymerization of styrenic monomers with such catalysts.
The atom transfer radical polymerization method provided in this embodiment uses methyl dipyridothiadiazole quaternary ammonium salt as a catalyst and styrene as a monomer, and the specific steps for preparing the polymer are as follows:
(1) 14.9mg (0.02 mmol) of dihexyl dipyridothiadiazole quaternary salt and 48.6mg (0.2 mmol) of ethyl alpha-bromophenylacetate are added to 4ml of methylene chloride, kept protected from light, and dissolved by shaking or ultrasound, and then 2ml (2.0 g,20 mmol) of styrene are added to the solution. The solution was transferred to a 20ml quartz schlenk tube, sealed and subjected to three freeze-thaw cycles to remove oxygen from the reaction system. The irradiation was continued for 12 hours using a violet LED lamp. After the reaction was completed, the resulting polymer solution was diluted with 4ml of methylene chloride, and then the solution was added dropwise to 100ml of methanol under stirring to precipitate a polymer. After stirring for 2 hours, filtration was carried out, and then the resulting polymer was dried at 40℃for 24 hours to obtain 1.44g (72%) of polystyrene.
Example 4
This example 4 provides a method and application for the atom transfer radical polymerization of an aqueous phase with such a catalyst.
The atom transfer radical polymerization method provided in this embodiment uses methyl dipyridothiadiazole quaternary ammonium salt as a catalyst and PEGA480 as a monomer, and the specific steps for preparing the polymer are as follows:
(1) 13.2mg (0.02 mmol) of dimethyl bipyridyl thiadiazole quaternary amine salt and 42.2mg (0.2 mmol) of ethylene bromoisobutyrate were added to 5ml of water, kept protected from light, and then 5ml (5.0 g,10.2 mmol) of PEGA480 was added to the solution. The solution was transferred to a 20ml quartz schlenk tube, sealed and subjected to three freeze-thaw cycles to remove oxygen from the reaction system. The irradiation was continued for 12 hours using a violet LED lamp. After the completion of the reaction, the resulting polymer solution was diluted with 10ml of deionized water, extracted three times with 10ml of methylene chloride, the resulting methylene chloride was combined, and after removing methylene chloride by rotary evaporation, the resulting polymer was dried at 40℃for 24 hours to give 3.68g (73%) of poly PEGA480.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. An atom transfer radical polymerization photocatalyst based on a bipyridine thiadiazole quaternary ammonium salt derivative is characterized in that the catalyst is a bipyridine thiadiazole quaternary ammonium salt derivative, and the bipyridine thiadiazole derivative has a structure shown in a formula (I):
wherein R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, benzyl, p-methylbenzyl or p-tert-butylbenzyl.
2. The method for preparing an atom transfer radical polymerization photocatalyst based on a bipyridyl thiadiazole quaternary ammonium salt derivative according to claim 1, wherein a catalyst, an initiator, a monomer and a solvent are mixed and irradiated with light at a wavelength of 360-480nm for a period of time to obtain a polymer.
3. The process according to claim 1, wherein the monomers used for the catalytic atom transfer radical polymerization are one or a mixture of the following (II-1) to (II-13):
4. the process according to claim 2, wherein the initiator used for the catalytic atom transfer radical polymerization is one or a mixture of the bromine initiators of (III-1) to (III-5):
5. the process according to claim 2, wherein the catalyst is used in an amount of 10 to 1000ppm relative to the monomer in the atom transfer radical polymerization.
6. The preparation method according to claim 2, wherein the solvent system for the reaction is one or a mixture of several of water, dichloromethane, acetonitrile, ethanol, methanol, tetrahydrofuran and dimethyl sulfoxide.
7. The method of claim 2, wherein the catalyst, initiator, monomer, and solvent are mixed and irradiated at a wavelength of 360-480nm for a period of time to obtain the polymer.
8. The preparation method according to claim 2, wherein the solvent is one or more of dichloromethane, ethanol, methanol, tetrahydrofuran, ethyl acetate and water.
9. The application of the atom transfer radical polymerization photocatalyst based on the bipyridine thiadiazole quaternary ammonium salt derivative is characterized by being applied to the preparation of plastic, resin, gel and adhesive polymer materials.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211562366.9A CN116162097A (en) | 2022-12-07 | 2022-12-07 | Atom transfer radical polymerization photocatalyst based on bipyridine thiadiazole quaternary ammonium salt derivative, and preparation method and application thereof |
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|---|---|---|---|
| CN202211562366.9A CN116162097A (en) | 2022-12-07 | 2022-12-07 | Atom transfer radical polymerization photocatalyst based on bipyridine thiadiazole quaternary ammonium salt derivative, and preparation method and application thereof |
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| CN1210111A (en) * | 1997-09-03 | 1999-03-10 | 北京燕山石油化工公司研究院 | Removal of catalyst from polymer by atom transferred free radical polymerization |
| CN112778444A (en) * | 2021-01-25 | 2021-05-11 | 南京工业大学 | Method for preparing polyolefin by photoinduced organic catalysis |
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| CN1210111A (en) * | 1997-09-03 | 1999-03-10 | 北京燕山石油化工公司研究院 | Removal of catalyst from polymer by atom transferred free radical polymerization |
| CN112778444A (en) * | 2021-01-25 | 2021-05-11 | 南京工业大学 | Method for preparing polyolefin by photoinduced organic catalysis |
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| BOHAN TANG, 等: "Transforming a Fluorochrome to an Efficient Photocatalyst for Oxidative Hydroxylation: A Supramolecular Dimerization Strategy Based on Host-Enhanced Charge Transfer", 《ANGEW. CHEM. INT. ED.》, vol. 60, 17 March 2021 (2021-03-17), pages 9384 - 9388 * |
| JIAWANG ZHOU，等: "Choosing sides: unusual ultrafast charge transfer pathways in an asymmetric electron-accepting cyclophane that binds an electron donor", 《CHEM. SCI.》, vol. 10, 11 March 2019 (2019-03-11), pages 4282 * |
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