CN114773510A - Biological-mediated RAFT polymerization method - Google Patents
Biological-mediated RAFT polymerization method Download PDFInfo
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- CN114773510A CN114773510A CN202210232483.2A CN202210232483A CN114773510A CN 114773510 A CN114773510 A CN 114773510A CN 202210232483 A CN202210232483 A CN 202210232483A CN 114773510 A CN114773510 A CN 114773510A
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- xanthate
- biologically
- polymerisation process
- raft polymerisation
- mediated raft
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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
- 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
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- 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
- 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
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P11/00—Preparation of sulfur-containing organic compounds
Abstract
The invention discloses a biologically-mediated RAFT polymerization method, which is characterized by comprising the following steps: adding reduced coenzyme into a system containing thiocarbonyl sulfide and vinyl monomer, and incubating to obtain the polymer. The method of the invention is to add reduced coenzyme to a system containing thiocarbonyl sulphide and vinyl monomer, which is capable of directly reducing thiocarbonyl sulphide to free radical species, thereby initiating and maintaining RAFT polymerisation reactions. According to the biologically-mediated RAFT polymerization method, exogenous free radical substances are not required to be supplemented, so that the irreversible free radical termination reaction can be effectively inhibited, and the controllability of RAFT polymerization is improved. The biologically-mediated RAFT polymerization method disclosed by the invention does not need to provide any external stimulus, so that the method has the advantages of high efficiency, simplicity and convenience in operation, low cost and the like.
Description
Technical Field
The invention relates to the field of biochemistry, in particular to a biologically mediated RAFT polymerization method.
Background
In RAFT polymerisation, continued replenishment of initiating free radicals is required due to the presence of irreversible free radical termination reactions. Existing RAFT polymerisation initiation pathways include: 1) heating or redox activating a radical initiator; 2) electrochemically reducing a redox mediator; 3) carrying out ultrasonic treatment on the solvent; 4) enzymatic reaction; and 5) photochemically activating the thiocarbonyl sulfide. Where pathways 1-4 all rely on the supplementation of exogenous free radicals, they will also react with living free radicals in the system while initiating and maintaining RAFT polymerization leading to irreversible chain termination reactions; route 5 is a direct reduction of thiocarbonyl sulfide to free radical species using photochemical means, which is effective in suppressing irreversible chain termination reactions due to the absence of exogenous free radicals, but still requires the provision of external stimuli.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for controllably synthesizing a polymer, which is a biologically mediated RAFT polymerization method, and has the advantages of high efficiency, simple and convenient operation and low cost without supplementing exogenous free radical substances or providing any external stimulus.
The purpose of the invention is realized by adopting the following technical scheme:
a biologically mediated RAFT polymerisation process comprising the steps of: adding reduced coenzyme into a system containing thiocarbonyl sulfide and vinyl monomer, and incubating to obtain the polymer.
Preferably, the reduced coenzyme comprises NADH (nicotinamide adenine dinucleotide, reduced coenzyme I) or NADPH (nicotinamide adenine dinucleotide phosphate, reduced coenzyme II).
Preferably, the vinyl monomer includes at least one of styrene, vinyl ester, vinyl amide, acrylic acid ester, methacrylic acid ester, acrylamide, methacrylamide, and acrylonitrile.
More preferably, the acrylate comprises methyl acrylate and/or ethyl acrylate.
More preferably, the methacrylate comprises at least one of methyl 2-methacrylate, ethyl 2-methacrylate, ferrocenyl methyl methacrylate.
Preferably, the thiocarbonyl sulfide includes at least one of xanthate, dithiobenzoate, dithiocarbamate, trithiocarbonate.
More preferably, the xanthate comprises at least one of potassium ethyl xanthate, sodium ethyl xanthate, potassium isopropyl xanthate, sodium isopropyl xanthate, potassium butyl xanthate, sodium butyl xanthate, potassium cyclohexyl xanthate, sodium cyclohexyl xanthate.
More preferably, the dithiobenzoate comprises at least one of 2- (thiobenzoylthio) propionic acid, 2-mercapto-S-thiobenzoylacetic acid, 4-cyano-4- (phenylthiothiothio) pentanoic acid N-succinimidyl ester, 4-cyano-4- (thiobenzoyl) pentanoic acid.
More preferably, the trithiocarbonate comprises 4-cyano-4- [ (dodecylsulfanylthiocarbonyl) sulfanyl ] pentanoic acid and/or 2- (dodecyltrithiocarbonate) -2-methylpropionic acid.
The beneficial effects of the invention are as follows:
1. the method of the invention is to add reduced coenzyme to a system containing thiocarbonyl sulphide and vinyl monomer, which is capable of directly reducing thiocarbonyl sulphide to free radical species, thereby initiating and maintaining RAFT polymerisation reactions.
2. According to the biologically-mediated RAFT polymerization method, exogenous free radical substances are not required to be supplemented, so that the irreversible free radical termination reaction can be effectively inhibited, and the controllability of RAFT polymerization is improved.
3. The biologically mediated RAFT polymerization method does not need to provide any external stimulus, so the method has the advantages of high efficiency, simple and convenient operation, low cost and the like.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, without inventive effort, further drawings may be derived from the following figures.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a polymer of the surface of a substrate prepared in example 1 of the present invention.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but the present invention should not be construed as being limited to the implementable scope of the present invention.
The invention relates to a principle of a biology-mediated RAFT polymerization method, which comprises the following steps:
reduced coenzymes reduce thiocarbonyl sulfides to produce an anionic moiety and a radical moiety, wherein the radical moiety continues to react with vinyl monomers to ultimately form a polymer. The polymerization mechanism is shown in the following formula,
the starting materials, reagents or apparatuses used in the following examples are, unless otherwise specified, either commercially available from conventional sources or can be obtained by known methods.
The invention is further described with reference to the following examples.
Example 1:
a biologically mediated RAFT polymerisation process comprising the steps of:
0.5mM thiocarbonylsulfide 4-cyano-4- (thiobenzoyl) pentanoic acid (CPAD) was immobilised on the surface of gold via its carboxyl function, and then the substrate was soaked in an aqueous solution containing 7.5% N, N-Dimethylformamide (DMF) with 0.15mM ferrocenylmethyl methacrylate (FcMMA, as a monomer) and 0.75mM NADH and incubated at 37 ℃ for 1.5 h.
After the reaction was completed, the polymer on the surface of the substrate was observed by a Scanning Electron Microscope (SEM), as shown in fig. 1. As can be seen in FIG. 1, there is a large amount of polymer present on the surface of the substrate and their morphology is relatively uniform. Therefore, the biologically mediated RAFT polymerization method can be used for controllable and efficient synthesis of polymers.
Example 2
A biologically mediated RAFT polymerisation process comprising the steps of:
0.5mM potassium ethylxanthate was immobilized on the gold surface through its carboxyl functional group, and then the substrate was immersed in an aqueous solution containing 0.15mM methyl acrylate and 0.75mM NADPH containing 7.5% DMF and incubated at 37 ℃ for 1.5 h.
Example 3
A biologically mediated RAFT polymerisation process comprising the steps of:
0.5mM of 2- (thiobenzoylthio) propionic acid was immobilized on the gold surface via its carboxyl function, and then the substrate was immersed in an aqueous solution containing 0.15mM of styrene and 0.75mM of NADH containing 7.5% of DMF and incubated at 37 ℃ for 1.5 h.
Example 4
A biologically mediated RAFT polymerisation process comprising the steps of:
0.5mM of 2-mercapto-S-thiobenzoylacetic acid was immobilized on the gold surface via its carboxyl functional group, and then the substrate was immersed in an aqueous solution containing 0.15mM of styrene and 0.75mM of NADH and containing 7.5% of DMF and incubated at 37 ℃ for 1.5 h.
Example 5
A biologically mediated RAFT polymerisation process comprising the steps of:
0.5mM of 4-cyano-4- [ (dodecylsulfanylthiocarbonyl) sulfanyl ] pentanoic acid is immobilized via its carboxyl function on the gold surface, and the substrate is then immersed in an aqueous solution containing 0.15mM of styrene and 0.75mM of NADH in 7.5% DMF and incubated at 37 ℃ for 1.5 h.
Example 6
A biologically mediated RAFT polymerisation process comprising the steps of:
0.5mM 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid was immobilized on the gold surface by its carboxyl function, and then the substrate was immersed in an aqueous solution containing 0.15mM styrene and 0.75mM NADH containing 7.5% DMF and incubated at 37 ℃ for 1.5 h.
Example 7
A biologically mediated RAFT polymerisation process comprising the steps of:
0.5mM N-succinimidyl 4-cyano-4- (phenylthiothiothio) valerate were immobilised via its carboxyl function on the gold surface, and the substrate was then soaked in an aqueous solution containing 0.15mM styrene and 0.75mM NADH in 7.5% DMF and incubated at 37 ℃ for 1.5 h.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A biologically mediated RAFT polymerisation process comprising the steps of: adding reduced coenzyme into a system containing thiocarbonyl sulfide and vinyl monomer, and incubating to obtain the polymer.
2. A biologically mediated RAFT polymerisation process according to claim 1, wherein said reduced coenzyme comprises NADH (nicotinamide adenine dinucleotide) or NADPH (nicotinamide adenine dinucleotide phosphate).
3. A biologically-mediated RAFT polymerisation process according to claim 1, wherein said vinyl monomer comprises at least one of styrene, vinyl ester, vinyl amide, acrylic acid, acrylic ester, methacrylic ester, acrylamide, methacrylamide and acrylonitrile.
4. A biologically-mediated RAFT polymerisation process according to claim 3, wherein said acrylate comprises methyl acrylate and/or ethyl acrylate.
5. A biologically-mediated RAFT polymerisation method according to claim 3, wherein said methacrylate ester comprises at least one of methyl 2-methacrylate, ethyl 2-methacrylate, ferrocenylmethyl methacrylate.
6. A biologically mediated RAFT polymerisation process according to claim 1, wherein said thiocarbonyl sulphide comprises at least one of xanthate, dithiobenzoate, dithiocarbamate, trithiocarbonate.
7. A biologically mediated RAFT polymerisation process according to claim 6, wherein said xanthate comprises at least one of potassium ethyl xanthate, sodium ethyl xanthate, potassium isopropyl xanthate, sodium isopropyl xanthate, potassium butyl xanthate, sodium butyl xanthate, potassium cyclohexyl xanthate, sodium cyclohexyl xanthate.
8. A biologically mediated RAFT polymerisation process according to claim 6, wherein said dithiobenzoate ester comprises at least one of 2- (thiobenzoylthio) propionic acid, 2-mercapto-S-thiobenzoylacetic acid, N-succinimidyl 4-cyano-4- (phenylthiothiothiothio) pentanoate, 4-cyano-4- (thiobenzoyl) pentanoic acid; the trithiocarbonate includes 4-cyano-4- [ (dodecylsulfanylthiocarbonyl) sulfanyl ] pentanoic acid and/or 2- (dodecyltrithiocarbonate) -2-methylpropionic acid.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693749A (en) * | 2009-10-22 | 2010-04-14 | 浙江大学 | Method for preparing dissaving vinyl or propenyl amide polymer |
| CN102971348A (en) * | 2010-05-06 | 2013-03-13 | 康奈尔大学 | Tunable LCST polymers and methods of preparation |
| US20150255690A1 (en) * | 2014-03-04 | 2015-09-10 | Nanoco Technologies Ltd. | Methods for fabricating quantum dot polymer films |
| CN110407968A (en) * | 2019-04-04 | 2019-11-05 | 华东理工大学 | A kind of novel RAFT reagent and its preparation method and application based on black phosphorus |
| US20200024372A1 (en) * | 2018-07-23 | 2020-01-23 | Carnegie Mellon University | Enzyme-assisted atrp procedures |
| US20200339713A1 (en) * | 2019-02-14 | 2020-10-29 | Drexel University | Oxygen Tolerant and Room Temperature RAFT through Alkylborane Initiation |
-
2022
- 2022-03-09 CN CN202210232483.2A patent/CN114773510A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693749A (en) * | 2009-10-22 | 2010-04-14 | 浙江大学 | Method for preparing dissaving vinyl or propenyl amide polymer |
| CN102971348A (en) * | 2010-05-06 | 2013-03-13 | 康奈尔大学 | Tunable LCST polymers and methods of preparation |
| US20150255690A1 (en) * | 2014-03-04 | 2015-09-10 | Nanoco Technologies Ltd. | Methods for fabricating quantum dot polymer films |
| US20200024372A1 (en) * | 2018-07-23 | 2020-01-23 | Carnegie Mellon University | Enzyme-assisted atrp procedures |
| US20200339713A1 (en) * | 2019-02-14 | 2020-10-29 | Drexel University | Oxygen Tolerant and Room Temperature RAFT through Alkylborane Initiation |
| CN110407968A (en) * | 2019-04-04 | 2019-11-05 | 华东理工大学 | A kind of novel RAFT reagent and its preparation method and application based on black phosphorus |
Non-Patent Citations (3)
| Title |
|---|
| QIONG HU，等: "Bioinspired Electro-RAFT Polymerization for Electrochemical Sensing of Nucleic Acids", 《ACS APPL. MATER. INTERFACES》, vol. 13, pages 54794 - 54800 * |
| SANG WEI，等: "Coenzyme-Catalyzed Electro-RAFT Polymerization", 《ACS MACRO LETT.》, vol. 6, pages 1337 - 1341 * |
| 钟玉鹏 等: "以黄原酸钾为链转移剂的甲基丙烯酸甲酯可逆加成断裂链转移聚合", 《高分子材料科学与工程》, vol. 31, no. 11, pages 15 - 18 * |
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