CN110305271B - Method for synthesizing block polymer in one pot by ultraviolet light induction - Google Patents
Method for synthesizing block polymer in one pot by ultraviolet light induction Download PDFInfo
- Publication number
- CN110305271B CN110305271B CN201910644654.0A CN201910644654A CN110305271B CN 110305271 B CN110305271 B CN 110305271B CN 201910644654 A CN201910644654 A CN 201910644654A CN 110305271 B CN110305271 B CN 110305271B
- Authority
- CN
- China
- Prior art keywords
- monomer
- ultraviolet light
- polymer
- block polymer
- pot
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 17
- 230000006698 induction Effects 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 cyclic ester Chemical class 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical group O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 14
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- YFDSDPIBEUFTMI-UHFFFAOYSA-N tribromoethanol Chemical compound OCC(Br)(Br)Br YFDSDPIBEUFTMI-UHFFFAOYSA-N 0.000 claims description 7
- 229950004616 tribromoethanol Drugs 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 238000001955 polymer synthesis method Methods 0.000 claims description 2
- 125000005409 triarylsulfonium group Chemical group 0.000 claims 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000003999 initiator Substances 0.000 abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 11
- 238000001035 drying Methods 0.000 abstract description 6
- 239000011261 inert gas Substances 0.000 abstract description 6
- 238000003760 magnetic stirring Methods 0.000 abstract description 6
- 229920001400 block copolymer Polymers 0.000 abstract description 5
- 230000001376 precipitating effect Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 239000012620 biological material Substances 0.000 abstract description 2
- 238000003889 chemical engineering Methods 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
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 10
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 9
- 230000000977 initiatory effect Effects 0.000 description 7
- 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
- 229940124530 sulfonamide Drugs 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 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 description 1
- UYHNDEQBDLNIJY-UHFFFAOYSA-N 2,2-diaminoethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(N)N UYHNDEQBDLNIJY-UHFFFAOYSA-N 0.000 description 1
- MHXMVFDLNGKBSR-UHFFFAOYSA-N 2-hydroxyethyl 2-bromo-2-methylpropanoate Chemical compound CC(C)(Br)C(=O)OCCO MHXMVFDLNGKBSR-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical group C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 238000010550 living polymerization reaction Methods 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
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 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
- 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
-
- 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
- C08F4/00—Polymerisation catalysts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Graft Or Block Polymers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a method for synthesizing a block polymer in one pot by ultraviolet light induction, which comprises the following steps: dissolving a catalyst, an initiator and an acrylate monomer (or a cyclic ester monomer) in a solvent, placing the solvent in an inert gas environment for reaction, polymerizing under the condition of room-temperature ultraviolet irradiation under magnetic stirring, adding the cyclic ester monomer (or the acrylate monomer) after a certain time, continuing to perform ultraviolet irradiation under magnetic stirring, finally dissolving the polymer with tetrahydrofuran, precipitating in methanol, separating and drying to obtain the polymer. The polymerization process is simple, intermediate separation and purification are not needed, the block copolymers with different performance of two blocks are obtained by continuous feeding in a one-pot method, a metal catalyst is not used, and the obtained polymers have no metal residue and have great application potential in the fields of fine chemical engineering, intelligent drug loading and biological materials.
Description
Technical Field
The invention belongs to the technical field of polymerization, and particularly relates to an ultraviolet light-induced one-pot synthesis method of a block polymer.
Background
The functional block copolymer is a linear copolymer formed by the alternate polymerization of chain segments with different chemical structures, and can combine the excellent properties of all the blocks to obtain a polymer material with more excellent performance. The combination of two polymerization methods, atom transfer radical polymerization and ring-opening polymerization, in living radical polymerization, to prepare two-block copolymers of polystyrene, polyacrylic acid (methyl methacrylate, glycidyl methacrylate, etc.) and biodegradable polyester (polylactic acid, polycaprolactone, polypentanolide, etc.) has become a hot point of research. The two active polymerization methods are respectively suitable for monomers with different structure types, so that the structural advantages of the two types of monomers can be combined to obtain the functional block copolymer with different two-block performances. But in the two polymerization processes, the polymerization is performed again after separation and purification and terminal functionalization synthesis of the macromolecular initiator after one-time polymerization, on one hand, in the process, the active group at the terminal is not easy to graft, the functionalization rate is low, and thus the initiation activity of the initiation site is low; on the other hand, the intermediate separation and purification steps waste time and resources, and the transition metal complex catalyst used in the atom transfer radical polymerization is not consumed in the polymerization process and is difficult to purify, and the metal residues can limit the application of the polymer.
Disclosure of Invention
In view of the above, the present invention provides an ultraviolet light-induced one-pot block polymer synthesis method, which uses an organic small molecule as a catalyst (capable of catalyzing atom transfer radical polymerization and ring-opening polymerization), and combines a dual-site initiator (one end initiates ring-opening polymerization and the other end initiates atom transfer radical polymerization) to obtain a block polymer with high monomer conversion rate (over 60%), a molecular weight meeting a theoretical value, and a narrow molecular weight distribution (< 1.5).
In order to achieve the technical purpose, the invention provides an ultraviolet light-induced one-pot synthesis method of a block polymer. Different from the traditional polymerization mode, the method provided by the invention mainly utilizes a multifunctional catalyst of triaryl ammonium hexafluorophosphate capable of catalyzing atom transfer radical polymerization and ring opening polymerization and a multifunctional initiator simultaneously having a ring opening polymerization initiating group and an atom transfer radical polymerization initiating group to induce acrylate monomers and cyclic ester monomers to respectively react in a one-pot method under the induction of ultraviolet light, thereby obtaining the block polymer. In summary, the method comprises the steps of:
polymerizing a multifunctional catalyst, a multifunctional initiator and two monomers (a first monomer and a second monomer) under the induction of ultraviolet light, and fully reacting to obtain a block polymer;
or polymerizing a system containing a multifunctional catalyst, a multifunctional initiator and a first monomer under the induction of ultraviolet light for a certain time; then adding a second monomer, continuing to polymerize under the induction of ultraviolet light, and fully reacting to obtain a block polymer;
when the first monomer is an acrylate monomer, the second monomer is a cyclic ester monomer; when the first monomer is a cyclic ester monomer, the second monomer is an acrylate monomer.
The invention is realized by the following technical scheme:
an ultraviolet light-induced one-pot synthesis method of a block polymer comprises the following steps: dissolving a catalyst, an initiator, an acrylate monomer and a cyclic ester monomer in a solvent, placing the solvent in an inert gas environment for reaction, polymerizing under the condition of magnetic stirring and ultraviolet light irradiation at room temperature, finally dissolving a polymer by tetrahydrofuran, precipitating in methanol, separating and drying to obtain the polymer.
Or dissolving the catalyst, the initiator and the acrylate monomer (or the cyclic ester monomer) in a solvent, placing the solvent in an inert gas environment for reaction, polymerizing under the condition of magnetic stirring and ultraviolet irradiation at room temperature, adding the cyclic ester monomer (or the acrylate monomer) after a certain time, continuing to perform ultraviolet irradiation under magnetic stirring, finally dissolving the polymer by tetrahydrofuran, precipitating in methanol, separating and drying to obtain the polymer.
Further, the molar ratio of the acrylate monomer to the cyclic ester monomer to the initiator to the catalyst is 50-100:50-100:1: 0.5-1.5.
Further, the catalyst is selected from organic small molecule triaryl ammonium hexafluorophosphate (TSPF 6) with the CAS number of 109037-77-6.
Further, the initiator is selected from tribromoethanol, ethylene glycol bromoisobutyrate and the like, wherein one end of the initiator is provided with a hydroxyl group (capable of initiating ring-opening polymerization), and the other end of the initiator is provided with bromine (capable of initiating atom transfer radical polymerization).
Based on the above principle, those skilled in the art can select the types of the acrylate monomers and the cyclic ester monomers according to actual needs. The two types of monomers are respectively made to belong to two different reaction types of atom transfer radical polymerization and ring opening polymerization, so that the atom transfer radical polymerization and the ring opening polymerization are not influenced mutually.
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 cyclic ester monomer is selected from L-lactide, valerolactone, caprolactone, tetrahydrofuran, trimethylene carbonate and the like.
Further, the solvent is selected from propylene carbonate, tetrahydrofuran, NN-dimethylformamide, NN-dimethylacetamide, toluene, dichloromethane, trichloromethane or dimethyl sulfoxide.
The method can be used for synthesizing the polyester (lactic acid) -b-polyacrylate block copolymer.
The invention has the beneficial effects that:
1) the catalyst is cheap and easy to obtain, has low toxicity (no odor and no color), has high solubility, can catalyze atom transfer radical polymerization and ring opening polymerization, has no metal residue in the obtained block polymer, 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 reaction condition is mild (room temperature), the experimental process is simple to operate, the separation and purification steps between two kinds of polymerization are omitted by one-pot operation, and the time and resources are saved.
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.
The non-metal organic catalyst described in this example was triaryl sulfonamide hexafluorophosphate salt and its homologs (CAS: 109037-77-6 and CAS: 75482-18-7).
Example 1
[ a method for synthesizing a block polymer in one pot by ultraviolet light induction, which comprises the following steps (the using amount of each component is calculated by mol):
adding methyl methacrylate, tribromoethanol and triaryl sulfonamide hexafluorophosphate (100: 1: 0.5) 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 polymerization of methyl methacrylate, sampling after 4 hours to obtain a molecular weight of 6800, adding valerolactone (100), continuing to polymerize for 6 hours, opening the reaction tube, dissolving the polymer by tetrahydrofuran, precipitating in methanol, separating and drying to obtain a polymer, weighing to obtain a conversion rate of 58%, wherein the theoretical molecular weight of the polymer is 9400. The molecular weight of the polymer was 15000 and its molecular weight distribution was 1.40 as determined by gel permeation chromatography.
Example 2
An ultraviolet light-induced one-pot synthesis method of a block polymer comprises the following steps (the using amount of each component is calculated by mol):
valerolactone, tribromoethanol and triaryl sulfonamide hexafluorophosphate (50: 1: 0.5) are added into a reaction tube (50% of propylene carbonate), magnetons are added, inert gas (nitrogen or argon) is introduced for 3 minutes, the piston of the reaction tube is closed, the reaction tube is stirred by magnetic force at room temperature and is irradiated by ultraviolet light to initiate polymerization, the molecular weight is 4000 after 2.5 hours, methyl methacrylate and triaryl sulfonamide hexafluorophosphate (100: 1.5) are added, the polymer is dissolved by tetrahydrofuran after 6 hours, the polymer is precipitated in methanol, and the polymer is obtained after separation and drying, and the conversion rate is 57% after weighing, and the theoretical molecular weight is 8500. The molecular weight of the polymer was 7000 by gel permeation chromatography, and the molecular weight distribution was 1.35.
Example 3
An ultraviolet light-induced one-pot synthesis method of a block polymer comprises the following steps (the using amount of each component is calculated by mol):
adding methyl methacrylate, valerolactone, tribromoethanol and triaryl sulfonamide hexafluorophosphate (50: 50:1: 1) 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 at room temperature by magnetic stirring and ultraviolet irradiation for 6 hours, opening the reaction tube, dissolving a polymer by tetrahydrofuran, precipitating in methanol, separating and drying to obtain the polymer, and weighing to obtain the polymer with the conversion rate of 52% and the theoretical molecular weight of 5200. The molecular weight of the polymer was 5800 as determined by gel permeation chromatography, and the molecular weight distribution was 1.30.
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)
1. An ultraviolet light-induced one-pot synthesis method of a block polymer is characterized by comprising the following steps:
polymerizing a system containing triaryl sulfonium hexafluorophosphate, tribromoethanol, a first monomer and a second monomer under the induction of ultraviolet light, and fully reacting to obtain a block polymer; or polymerizing a system containing triaryl sulfonium hexafluorophosphate, tribromoethanol and a first monomer under the induction of ultraviolet light for a certain time, then adding a second monomer, continuing to polymerize under the induction of ultraviolet light, and fully reacting to obtain a block polymer;
when the first monomer is methyl methacrylate, the second monomer is valerolactone; when the first monomer is valerolactone, the second monomer is methyl methacrylate.
2. The UV-induced one-pot synthesis method of block polymer as claimed in claim 1, wherein the molar ratio of methyl methacrylate, valerolactone, tribromoethanol and triarylsulfonium hexafluorophosphate is (50-100):1: (0.5-1.5).
3. The method for one-pot synthesis of block polymers by ultraviolet light induction according to claim 1, wherein the reaction system of ultraviolet light induction further comprises a proper amount of solvent, wherein the solvent is one or more of propylene carbonate, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, toluene, dichloromethane, trichloromethane or dimethyl sulfoxide.
4. The UV-induced one-pot block polymer synthesis method according to claim 1, wherein the block polymer is formed, and then dissolved in tetrahydrofuran, precipitated in methanol, and separated and dried.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910644654.0A CN110305271B (en) | 2019-07-17 | 2019-07-17 | Method for synthesizing block polymer in one pot by ultraviolet light induction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910644654.0A CN110305271B (en) | 2019-07-17 | 2019-07-17 | Method for synthesizing block polymer in one pot by ultraviolet light induction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110305271A CN110305271A (en) | 2019-10-08 |
| CN110305271B true CN110305271B (en) | 2021-03-19 |
Family
ID=68081203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910644654.0A Active CN110305271B (en) | 2019-07-17 | 2019-07-17 | Method for synthesizing block polymer in one pot by ultraviolet light induction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110305271B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909322B (en) * | 2020-07-29 | 2022-03-11 | 苏州大学 | Synthesis of graft copolymer by combining near infrared light induced iodine regulation RDRP and ultraviolet light induced ring-opening polymerization one-pot method |
-
2019
- 2019-07-17 CN CN201910644654.0A patent/CN110305271B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| Ian A. Barker and Andrew P. Dove.《Triarylsulfonium hexafluorophosphate salts as photoactivated acidic catalysts for ring-opening polymerisation》.《ChemComm》.2012, * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110305271A (en) | 2019-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Eberhardt et al. | RAFT polymerization of pentafluorophenyl methacrylate: preparation of reactive linear diblock copolymers | |
| Jankova et al. | Star polymers by ATRP of styrene and acrylates employing multifunctional initiators | |
| Matyjaszewski et al. | Graft copolymers of polyethylene by atom transfer radical polymerization | |
| US20100121024A1 (en) | Method for producing a copolymer of at least one cyclic monomer | |
| Young et al. | Bulk depolymerization of poly (methyl methacrylate) via chain-end initiation for catalyst-free reversion to monomer | |
| CN111072825B (en) | Carbon nitride catalyzed atom transfer radical polymerization method | |
| CN110305271B (en) | Method for synthesizing block polymer in one pot by ultraviolet light induction | |
| Zhao et al. | Living radical polymerization of acrylates and acrylamides mediated by a versatile cobalt porphyrin complex | |
| CN106947067A (en) | A kind of preparation method of polyester | |
| Schmidt‐Naake et al. | Living free radical donor‐acceptor copolymerization of styrene and N‐cyclohexylmaleimide and the synthesis of poly [styrene‐co‐(N‐cyclohexylmaleimide)]/polystyrene block copolymers | |
| Bai et al. | Controlled Polymerization Under 60Co γ‐Irradiation in the Presence of Dithiobenzoic Acid | |
| Zhou et al. | Enzyme mimetic-catalyzed ATRP and its application in block copolymer synthesis combined with enzymatic ring-opening polymerization | |
| Liu et al. | Synthesis of high-molecular-weight poly (ε-caprolactone) via heterogeneous zinc-cobalt (III) double metal cyanide complex | |
| Danko et al. | Functional polyesters with pendant double bonds prepared by coordination–insertion and cationic ring-opening copolymerizations of ε-caprolactone with renewable Tulipalin A | |
| Yang et al. | Organocatalytic cationic degenerate chain transfer polymerization of vinyl ethers with excellent temporal control | |
| CN110003371B (en) | Ultraviolet light induced atom transfer free radical polymerization method | |
| Bexis et al. | Synthesis of degradable poly (ε-caprolactone)-based graft copolymers via a “grafting-from” approach | |
| Hu et al. | Living cationic ring-opening polymerization of 2-oxazolines initiated by rare-earth metal triflates | |
| CN105801827B (en) | Poly(epsilon-caprolacton) containing functional chlorine atoms and organocatalysis preparation method and application thereof | |
| WO2018197885A1 (en) | Branched polymers | |
| Ata et al. | Copper catalyzed ring opening copolymerization of a vinyl cyclopropane and methyl methacrylate | |
| Ihara et al. | Living polymerizations of alkyl acrylates by the unique catalytic action of rare earth metal complexes | |
| Hernández et al. | Thermoplastic elastomers from vegetable oils via reversible addition-fragmentation chain transfer polymerization | |
| Liu et al. | Fully chemical recyclable poly (γ-butyrolactone)-based copolymers with tunable structures and properties | |
| Endo et al. | A Novel Crosslinking-Decrosslinking System of Polymers Having Spiro Orthoester Moieties in the Side Chains. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |