CN110003371B - Ultraviolet light induced atom transfer free radical polymerization method - Google Patents
Ultraviolet light induced atom transfer free radical polymerization method Download PDFInfo
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- CN110003371B CN110003371B CN201910300779.1A CN201910300779A CN110003371B CN 110003371 B CN110003371 B CN 110003371B CN 201910300779 A CN201910300779 A CN 201910300779A CN 110003371 B CN110003371 B CN 110003371B
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- ultraviolet light
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- methacrylate
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000010526 radical polymerization reaction Methods 0.000 title description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- -1 butyl acrylate ester Chemical class 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- IOLQWGVDEFWYNP-UHFFFAOYSA-N ethyl 2-bromo-2-methylpropanoate Chemical group CCOC(=O)C(C)(C)Br IOLQWGVDEFWYNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- BKTKLDMYHTUESO-UHFFFAOYSA-N ethyl 2-bromo-2-phenylacetate Chemical compound CCOC(=O)C(Br)C1=CC=CC=C1 BKTKLDMYHTUESO-UHFFFAOYSA-N 0.000 claims description 3
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 2
- UYHNDEQBDLNIJY-UHFFFAOYSA-N 2,2-diaminoethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(N)N UYHNDEQBDLNIJY-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 2
- YFDSDPIBEUFTMI-UHFFFAOYSA-N tribromoethanol Chemical compound OCC(Br)(Br)Br YFDSDPIBEUFTMI-UHFFFAOYSA-N 0.000 claims 1
- 229950004616 tribromoethanol Drugs 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000012620 biological material Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000010550 living polymerization reaction Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Abstract
本发明公开了一种紫外光诱导原子转移自由基的聚合方法，包括以下步骤：将催化剂、引发剂和丙烯酸酯系单体溶于溶剂中，置于惰性气体环境中反应，在磁力搅拌下室温紫外光照射条件下聚合，以四氢呋喃溶解聚合物，在甲醇中沉淀，分离干燥后得到聚合物。本发明涉及的聚合过程简单，且不使用金属催化剂，得到的聚合物中无金属残留，在精细化工、智能载药以及生物材料领域有巨大的应用潜力。The invention discloses a polymerization method for ultraviolet light-induced atom transfer radical, comprising the following steps: dissolving a catalyst, an initiator and an acrylate monomer in a solvent, placing it in an inert gas environment to react, and stirring at room temperature under magnetic force The polymer was polymerized under ultraviolet light irradiation, the polymer was dissolved in tetrahydrofuran, precipitated in methanol, separated and dried to obtain the polymer. The polymerization process involved in the invention is simple, no metal catalyst is used, and the obtained polymer has no metal residue, and has great application potential in the fields of fine chemicals, intelligent drug loading and biological materials.
Description
Technical Field
The invention belongs to the technical field of polymerization, and particularly relates to a polymerization method for transferring free radicals by ultraviolet-induced atoms.
Background
The free radical polymerization has the advantages of wide monomer, various synthesis processes, simple and convenient operation, low industrial cost and the like, can be applied to the polymerization and copolymerization of functional monomers, and more than 60 percent of polymers are produced by the free radical polymerization. Living polymerization, which is free radical polymerization, has been the focus of research. The living radical polymerization is used for preparing polymers (composition, size distribution, shape, sequence distribution and regularity) with precise primary structures, the molecular weight of the polymers can be designed and predicted, and the polymers with narrow molecular weight distribution are obtained.
The main methods of the existing living free radical polymerization include an initiation transfer terminator method, a stable nitroxide free radical regulation polymerization method, an atom transfer free radical polymerization method and a reversible addition-fragmentation chain transfer polymerization method. The polymer obtained by the initiation transfer terminator method has wide molecular weight distribution, can generate free radicals at high temperature by stabilizing oxynitride used in nitroxide free radical regulation and control polymerization, has high energy consumption, and is less in the variety of applicable monomers; the disulfide derivatives of the chain transfer reagent of reversible addition-fragmentation chain transfer polymerization have high toxicity, complex preparation process, difficult removal and conversion, expensive reagent and difficult obtainment; the transition metal complex catalyst used in atom transfer radical polymerization is not consumed in the polymerization process, is difficult to purify, and the application of the polymer is limited by metal residues.
Disclosure of Invention
In view of the above, the present invention provides an ultraviolet light-induced atom transfer radical polymerization method, which uses small organic molecules as a catalyst to obtain a polymer with high monomer conversion rate (over 60%), a molecular weight meeting a theoretical value, and a narrow molecular weight distribution (< 1.4).
In order to achieve the technical purpose, the invention is specifically realized by the following technical scheme:
a polymerization method of ultraviolet light-induced atom transfer radicals comprises the following steps: dissolving a catalyst, an initiator and an acrylate monomer in a solvent, placing the solvent in an inert gas environment for reaction, polymerizing under the condition of magnetic stirring and room-temperature ultraviolet irradiation, dissolving a polymer by tetrahydrofuran, precipitating in methanol, separating and drying to obtain the polymer.
Further, the molar ratio of the acrylate monomer to the initiator to the catalyst is 100:1: 1-100: 1:3.
Further, the catalyst is selected from organic small-molecule triaryl ammonium hexafluorophosphate (TSPF 6).
Further, the initiator is selected from atom transfer radical polymerization initiators such as ethyl 2-bromoisobutyrate and ethyl alpha-bromophenylacetate.
Further, the acrylate monomer is selected from methyl methacrylate, diaminoethyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, trifluoroethyl methacrylate, acrylonitrile, butyl acrylate, butyl methacrylate, lauryl methacrylate or benzyl methacrylate.
Further, the solvent is selected from propylene carbonate, tetrahydrofuran, NN-dimethylformamide, NN-dimethylacetamide, toluene, dichloromethane, trichloromethane or dimethyl sulfoxide.
The process of the invention can be used for the synthesis of homopolymers and also for the synthesis of copolymers (block, random, graft, alternating).
The invention has the beneficial effects that:
1) the method is based on cheap and easily-obtained organic catalyst, does not use metal catalyst, and the obtained polymer has no metal residue and has huge application potential in the fields of fine chemical engineering, intelligent drug loading and biological materials.
2) The method is based on living radical polymerization, and the obtained polymer has the characteristic of living polymerization, and the obtained polymer has high monomer conversion rate (more than 60 percent), molecular weight according with theoretical value and narrow molecular weight distribution (< 1.4).
3) The catalyst of the invention has low toxicity (no odor and no color), high solubility, mild reaction conditions (room temperature).
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A non-metal organic catalyst for ultraviolet light induced atom transfer radical polymerization, which has the following structural formula:
a polymerization method of ultraviolet light-induced atom transfer radicals comprises the following steps:
adding methyl methacrylate, ethyl 2-bromoisobutyrate and triaryl sulfonamide hexafluorophosphate (8000: 80: 240) into a reaction tube (50% of propylene carbonate), adding magnetons, introducing inert gas (nitrogen or argon) for 3 minutes, closing a piston of the reaction tube, magnetically stirring at room temperature, irradiating by ultraviolet light to initiate methyl methacrylate polymerization, opening the reaction tube after 6 hours, dissolving a polymer by tetrahydrofuran, precipitating in methanol, separating and drying to obtain a polymer, weighing to obtain the conversion rate of 60%, wherein the theoretical molecular weight of the polymer is 6000. The molecular weight of the polymer was 6500 as determined by gel permeation chromatography, and the molecular weight distribution was 1.33.
Example 2
A polymerization method of ultraviolet light-induced atom transfer radicals comprises the following steps:
adding methyl methacrylate, alpha-bromophenylacetic acid ethyl ester and triaryl sulfonamide hexafluorophosphate (8000: 80: 240) into a reaction tube (50% of propylene carbonate), adding magnetons, introducing inert gas (nitrogen or argon) for 3 minutes, closing a piston of the reaction tube, initiating polymerization of methyl methacrylate at room temperature by magnetic stirring and ultraviolet irradiation, opening the reaction tube after 4 hours, dissolving a polymer by tetrahydrofuran, precipitating in methanol, separating and drying to obtain the polymer, weighing to obtain the conversion rate of 55%, wherein the theoretical molecular weight of the polymer is 5500. The molecular weight of the polymer was 6400 by gel permeation chromatography, and the molecular weight distribution was 1.33.
Example 3
A polymerization method of ultraviolet light-induced atom transfer radicals comprises the following steps:
adding benzyl methacrylate, ethyl 2-bromoisobutyrate and triaryl sulfonamide hexafluorophosphate (8000: 80: 80) into a reaction tube (50% of tetrahydrofuran), adding magnetons, introducing inert gas (nitrogen or argon) for 3 minutes, closing the piston of the reaction tube, irradiating with ultraviolet light under magnetic stirring at room temperature to initiate polymerization, opening the reaction tube after 3 hours, dissolving the polymer with tetrahydrofuran, precipitating in n-hexane, separating and drying to obtain the polymer, and weighing to obtain the conversion rate of 90% and the theoretical molecular weight of 16000. The molecular weight of the polymer was 14000 and the molecular weight distribution was 1.40 as determined by gel permeation chromatography.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
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| CN111072825B (en) * | 2020-01-10 | 2021-06-01 | 西北大学 | A carbon nitride-catalyzed atom transfer radical polymerization method |
| CN115894773B (en) * | 2022-12-07 | 2024-05-14 | 郑州德派医疗器械有限公司 | Photo-curing 3D printing resin for dentistry and preparation method thereof |
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| CN105601777A (en) * | 2016-03-22 | 2016-05-25 | 苏州大学 | Visible-radiation-based water-soluble monomer atom transfer radical polymerization (ATRP) method |
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| CN105601777A (en) * | 2016-03-22 | 2016-05-25 | 苏州大学 | Visible-radiation-based water-soluble monomer atom transfer radical polymerization (ATRP) method |
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