CN108299590B - β -ketoester functionalized polymer nano material and photochemical synthesis method thereof - Google Patents
β -ketoester functionalized polymer nano material and photochemical synthesis method thereof Download PDFInfo
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- CN108299590B CN108299590B CN201810245576.2A CN201810245576A CN108299590B CN 108299590 B CN108299590 B CN 108299590B CN 201810245576 A CN201810245576 A CN 201810245576A CN 108299590 B CN108299590 B CN 108299590B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 77
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 72
- 238000001308 synthesis method Methods 0.000 title claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 53
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 44
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 230000000977 initiatory effect Effects 0.000 claims abstract description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000012674 dispersion polymerization Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 19
- 239000012987 RAFT agent Substances 0.000 claims description 15
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 6
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 6
- 229920001002 functional polymer Polymers 0.000 claims description 5
- ANRPYDCTHDLWGE-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;3-oxobutanoic acid Chemical group CC(=O)CC(O)=O.CC(=C)C(=O)OCCO ANRPYDCTHDLWGE-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 3
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 3
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-UHFFFAOYSA-N 0.000 claims description 3
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 3
- FXIVKZGDYRLHKF-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)(=O)C1=CC=CC=C1 FXIVKZGDYRLHKF-UHFFFAOYSA-N 0.000 claims description 3
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 claims description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- HUESYMTZYJBOFW-UHFFFAOYSA-M sodium phenyl-(2,4,6-trimethylbenzoyl)oxyphosphinate Chemical compound CC1=C(C(=O)OP([O-])(=O)C2=CC=CC=C2)C(=CC(=C1)C)C.[Na+] HUESYMTZYJBOFW-UHFFFAOYSA-M 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 51
- 238000006243 chemical reaction Methods 0.000 description 22
- 230000005540 biological transmission Effects 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 17
- 239000002202 Polyethylene glycol Substances 0.000 description 17
- 229920001223 polyethylene glycol Polymers 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
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- 239000000047 product Substances 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 7
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
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- UDPGUMQDCGORJQ-UHFFFAOYSA-N (2-chloroethyl)phosphonic acid Chemical compound OP(O)(=O)CCCl UDPGUMQDCGORJQ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical group CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- TVZRAEYQIKYCPH-UHFFFAOYSA-N 3-(trimethylsilyl)propane-1-sulfonic acid Chemical compound C[Si](C)(C)CCCS(O)(=O)=O TVZRAEYQIKYCPH-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- FLDUEDUWKAFINQ-UHFFFAOYSA-M sodium;1-trimethylsilylpropane-1-sulfonate Chemical compound [Na+].CCC([Si](C)(C)C)S([O-])(=O)=O FLDUEDUWKAFINQ-UHFFFAOYSA-M 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- 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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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—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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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a β -ketoester functionalized polymer nano material and a photochemical synthesis method thereof, wherein the photochemical synthesis method comprises the following steps of mixing β -ketoester functional group monomer, methacrylate monomer, photoinitiator, macromolecular RAFT reagent and solvent, and carrying out dispersion polymerization under the irradiation of an initiation light source to obtain a β -ketoester functionalized polymer nano material.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an β -ketoester functionalized polymer nano material and a photochemical synthesis method thereof.
Background
The polymer nano material with the shapes of sphere, fiber, vesicle and the like has good application prospect in the aspects of catalysis, nano reactors, enzymatic reaction, biological medicine, diagnostic imaging and the like due to the advantages of small size, multifunction and the like (Chemical Society Reviews, 2012, 41 (41): 5969-5985). Block polymer nanomaterials are mainly prepared by a self-assembly method from polymer solutions, but this method is complicated to operate and has a low polymer solids content (< 1%), which largely limits their industrial applicability (Journal of the American Chemical Society, 2005, 127 (51): 17982-. In recent years, the development of polymerization-induced self-assembly provides a new idea for synthesizing polymer nano materials in large scale. The amphiphilic block polymer is formed by aggregation of weak intermolecular forces such as hydrogen bonds, hydrophobic forces and the like, is easily influenced by solvents, pH, surfactants and temperature to generate morphology change and even disassembly, and the instability limits the application of the block polymer nano material. Therefore, in order to improve the stability of the block polymer nanomaterial, it is generally necessary to crosslink it. However, related studies have demonstrated that the addition of a certain amount of cross-linking agent in polymerization-induced self-assembly can limit the formation of higher order features (e.g., fibrils, vesicles, etc.). The effective method is to use functional monomers as polymerization monomers to obtain full-functional block polymer nano materials, and further react and modify the block polymer nano materials to obtain the cross-linked block polymer nano materials.
The preparation of the functional polymer by using visible light as an initiating means is a research hotspot of the current polymer discipline, has the advantages of low reaction temperature, high initiating efficiency, low energy consumption, space-time light control property, friendly biological materials and the like, provides a new means for preparing intelligent polymers, however, a method for synthesizing β -ketoester functional polymer nano materials by polymerization-induced self-assembly initiated by visible light is not reported.
In summary, the existing preparation method of the β -ketoester functionalized polymer nanomaterial has the technical defects of complex operation and easy appearance change or even disassembly due to the influence of solvents, pH, surfactants and temperature.
Disclosure of Invention
In view of the above, the invention provides an β -ketoester functionalized polymer nanomaterial and a photochemical synthesis method thereof, which can effectively solve the technical problem of complex operation of the existing preparation method of β -ketoester functionalized polymer nanomaterial.
The invention provides a photochemical synthesis method of β -ketoester functionalized polymer nano-material, which comprises the following steps:
mixing a polymerization monomer, a photoinitiator and a macromolecular RAFT reagent with a solvent, and carrying out dispersion polymerization under the irradiation of an initiation light source to obtain β -ketoester functional polymer nano material, wherein the polymerization monomer comprises β -ketoester functional monomer and methacrylate monomer, and the macromolecular RAFT reagent has a structure shown in formula I;
wherein R is an alkyl group having 2 to 14 carbon atoms, and n is an integer of 20 to 200.
Specifically, the macromolecular RAFT reagent has a structure shown in a formula I, and the synthesis method of the structure shown in the formula I comprises the following steps: and (3) carrying out esterification reaction on polyethylene glycol monomethyl ether (mPEG) and a carboxyl-containing RAFT reagent (CRPA) to obtain the macromolecular RAFT reagent. The structural formula of the macromolecular RAFT reagent is shown as formula I:
wherein R in the formula I is an alkyl group containing 2-14 carbon atoms, and n is a natural number of 20-200; preferably, the R group is ethyl, propyl or dodecyl; preferably, the molar ratio of the polyethylene glycol monomethyl ether to the carboxyl-containing RAFT reagent is 1: 1.2-1.5.
Preferably, the molecular weight of the polyethylene glycol monomethyl ether is 2000-5000.
Wherein the structural formula of the carboxyl-containing RAFT reagent is shown as formula II:
wherein R in the formula II is an alkyl group containing 2-14 carbon atoms; more preferably, the R group is ethyl (correspondingly, the carboxyl group-containing RAFT agent is abbreviated CEPA) or dodecyl (correspondingly, the carboxyl group-containing RAFT agent is abbreviated CDPA).
Specifically, the structure of CEPA is as shown in formula II:
Specifically, the structure of CDPA is as formula ii:
More specifically, as a preferred possible embodiment, the method of synthesis of the macromolecular RAFT agent is as follows:
mixing polyethylene glycol monomethyl ether, CDPA and anhydrous dichloromethane, and stirring uniformly. And (3) placing the mixture in an ice-water bath, dropwise adding a dichloromethane solution dissolved with Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) when the temperature is reduced to 0 ℃, preserving the temperature for 1h, and reacting at room temperature for 48 h. After the reaction, insoluble matter was removed by filtration, and the filter cake was washed with dichloromethane. The solvent was distilled off under reduced pressure and precipitated with a mixture of ethyl acetate and n-hexane (v: v ═ 1: 1) to give a crude product as a yellow solid. Then purified by silica gel column chromatography with dichloromethane and methanol as mobile phase (v: v ═ 20: 1). And removing the rest solvent, and then drying in vacuum to finally obtain the macromolecular RAFT reagent.
More preferably, the molar ratio of the polyethylene glycol monomethyl ether to the CDPA is 1: 1.2-1: 1.5.
More preferably, the molecular weight of the polyethylene glycol monomethyl ether is 2000-5000.
Specifically, the photochemical synthesis method comprises the step of mixing β -ketone ester functional group monomer, methacrylate monomer, photoinitiator and macromolecule RAFT reagent with an ethanol/water mixed solution in a nitrogen atmosphere, preferably, the solvent is the ethanol and water mixed solution, and preferably, the mass ratio of ethanol to water is 80/20.
Preferably, the β -keto functional monomer is ethylene glycol acetoacetate methacrylate.
Preferably, the methacrylate-based monomer is one or more of methyl methacrylate, ethyl methacrylate, isobornyl methacrylate, butyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, isobutyl methacrylate, isodecyl methacrylate, isooctyl methacrylate, and 2-hydroxypropyl methacrylate.
Preferably, the photoinitiator is one of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, sodium (2,4, 6-trimethylbenzoyl) phenylphosphonate or ethyl (2,4, 6-trimethylbenzoyl) phenylphosphonate.
Preferably, the wavelength of the initiation light source is 405-465 nm, and the light intensity is 0.3-50 mW/cm2。
Preferably, the weight percentage of the polymerized monomer in the β -ketoester functionalized polymer nano material is 10-30 wt%.
Preferably, the molar ratio of the polymerized monomer to the macro RAFT agent is (30-500) to 1.
Preferably, the molar ratio of the acetoacetic acid glycol methacrylate to the methacrylate monomer is 1: 1.
Preferably, the molar ratio of the macromolecular RAFT reagent to the photoinitiator is (1-5) to 1
Preferably, the reaction temperature of the dispersion polymerization reaction is 40 to 70 ℃.
Preferably, the reaction time is 1-4 h.
The invention also provides an β -ketoester functionalized polymer nano material, which is the β -ketoester functionalized polymer nano material prepared by the photochemical synthesis method of the β -ketoester functionalized polymer nano material.
The invention aims at the defects of the prior art, and mainly aims to provide a photochemical synthesis method of β -ketoester functionalized polymer nano-material with simple operation and high stability, wherein the method directly uses a monomer with a functional group to carry out polymerization reaction, and provides a new design idea for designing stable functionalized polymer nano-material, wherein, the invention discovers that acetoacetic acid ethylene glycol methacrylate (AAEM) is a monomer containing β -ketoester functional group, β -ketoester functional group can react with amino, β -ketoester can be complexed with metal ions such as silver ions, and then metal particles are generated under the action of a reducing agent, so the AAEM is a monomer with very high application value.
The technical scheme includes that β -keto ester functional monomer, methacrylate monomer, photoinitiator and macromolecular RAFT reagent are mixed with a solvent, and are subjected to dispersion polymerization reaction under irradiation of an initiation light source to obtain the β -keto ester functionalized polymer nanomaterial, wherein the macromolecular RAFT reagent is used as a stabilizer and a hydrophilic solvent chain segment to perform RAFT light dispersion polymerization, and the stable β -keto ester functionalized polymer nanomaterial is synthesized.
The method has the advantages that visible light is utilized to initiate RAFT dispersion polymerization, polyethylene glycol monomethyl ether (mPEG) is used as a structure of a macromolecular RAFT reagent, AAEM containing β -ketone functional groups and methacrylate monomers are used as polymerization monomers, and photoinitiation polymerization is conducted in a solvent to induce self-assembly to synthesize the β -ketoester functional polymer nano material, the whole macromolecular RAFT reagent is a stabilizer and a solvophilic chain segment, the macromolecular RAFT reagent is high in stability and has solvophilic property, after a general polymer is formed, the macromolecule RAFT reagent and the polymer can not form a copolymer after being added with the monomer.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a Transmission Electron Microscope (TEM) image of β -ketoester functionalized polymer nanomaterial prepared in example 2 provided by the invention;
FIG. 2 is a Gel Permeation Chromatography (GPC) graph of β -ketoester functionalized polymer nanomaterial prepared in example 2 provided by the present invention;
FIG. 3 is a Transmission Electron Microscope (TEM) image of β -ketoester functionalized polymer nanomaterial prepared in example 3 provided by the present invention;
FIG. 4 is a Transmission Electron Microscope (TEM) image of β -ketoester functionalized polymer nanomaterial prepared in example 4 provided by the present invention;
FIG. 5 is a Transmission Electron Microscope (TEM) image of β -ketoester functionalized polymer nanomaterial prepared in example 5 provided by the present invention;
FIG. 6 is a Transmission Electron Microscope (TEM) image of β -ketoester functionalized polymer nanomaterial prepared in example 6 provided by the present invention;
FIG. 7 is a Transmission Electron Microscope (TEM) image of β -ketoester functionalized polymer nanomaterial prepared in example 7 according to the present invention;
FIG. 8 is a Transmission Electron Microscope (TEM) image of β -ketoester functionalized polymer nanomaterial prepared in example 8 provided by the present invention;
FIG. 9 is a Transmission Electron Microscope (TEM) image of β -ketoester functionalized polymer nanomaterial prepared in example 9 provided by the present invention;
FIG. 10 is a Transmission Electron Microscope (TEM) image of β -ketoester functionalized polymer nanomaterial prepared in example 10 provided by the present invention;
FIG. 11 is a Transmission Electron Microscope (TEM) image of β -ketoester functionalized polymer nanomaterial prepared in example 11 provided by the present invention;
FIG. 12 shows the photochemical synthesis of β -ketoester functionalized polymer nanomaterial1H NMR spectrum.
Detailed Description
The invention provides an β -ketoester functionalized polymer nano material and a photochemical synthesis method thereof, which can effectively solve the technical problem of complex operation of the existing preparation method of β -ketoester functionalized polymer nano material.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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 invention provides a photochemical synthesis method of β -ketoester functionalized polymer nano-material, which comprises the following steps:
mixing a polymerized monomer, β -ketone functional group monomer, methacrylate monomer, photoinitiator and macromolecular RAFT reagent with a solvent, and carrying out dispersion polymerization under the irradiation of an initiation light source to obtain the β -ketone ester functionalized polymer nanomaterial, wherein the polymerized monomer comprises β -ketone functional group monomer and methacrylate monomer, and the macromolecular RAFT reagent has a structure shown in formula I;
wherein R is an alkyl group having 2 to 14 carbon atoms, and n is an integer of 20 to 200.
Specifically, the synthesis of the macromolecular RAFT agent is as follows: and (3) carrying out esterification reaction on polyethylene glycol monomethyl ether (mPEG) and a carboxyl-containing RAFT reagent (CRPA) to obtain the macromolecular RAFT reagent. The structural formula of the macromolecular RAFT reagent is shown as formula I:
wherein R in the formula I is an alkyl group containing 2-14 carbon atoms, and n is a natural number of 20-200; preferably, the R group is ethyl, propyl or dodecyl; preferably, the molar ratio of the polyethylene glycol monomethyl ether to the carboxyl-containing RAFT reagent is 1: 1.2-1.5.
Preferably, the molecular weight of the polyethylene glycol monomethyl ether is 2000-5000.
Wherein the structural formula of the carboxyl-containing RAFT reagent is shown as formula II:
wherein R in the formula II is an alkyl group containing 2-14 carbon atoms; more preferably, the R group is ethyl (correspondingly, the carboxyl group containing RAFT agent is abbreviated CEPA) or dodecyl (correspondingly, the carboxyl group containing RAFT agent is abbreviated CDPA).
Specifically, the structure of CEPA is as shown in formula II:
Specifically, the structure of CDPA is as formula ii:
More specifically, as a preferred embodiment, the method of synthesis of the macromolecular RAFT agent is as follows:
mixing polyethylene glycol monomethyl ether, CDPA and anhydrous dichloromethane, and stirring uniformly. And (3) placing the mixture in an ice-water bath, dropwise adding a dichloromethane solution dissolved with Dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) when the temperature is reduced to 0 ℃, preserving the temperature for 1h, and reacting at room temperature for 48 h. After the reaction, insoluble matter was removed by filtration, and the filter cake was washed with dichloromethane. The solvent was distilled off under reduced pressure and precipitated with a mixture of ethyl acetate and n-hexane (v: v ═ 1: 1) to give a crude product as a yellow solid. Then purified by silica gel column chromatography with dichloromethane and methanol as mobile phase (v: v ═ 20: 1). And removing the rest solvent, and then drying in vacuum to finally obtain the macromolecular RAFT reagent.
More preferably, the molar ratio of the polyethylene glycol monomethyl ether to the CDPA is 1: 1.2-1: 1.5.
More preferably, the molecular weight of the polyethylene glycol monomethyl ether is 2000-5000.
Specifically, the photochemical synthesis method comprises the step of mixing β -ketone ester functional group monomer, methacrylate monomer, photoinitiator and macromolecule RAFT reagent with an ethanol/water mixed solution in a nitrogen atmosphere, preferably, the solvent is the ethanol and water mixed solution, and preferably, the mass ratio of ethanol to water is 80/20.
Preferably, the β -keto functional monomer is ethylene glycol acetoacetate methacrylate.
Preferably, the methacrylate-based monomer is one or more of methyl methacrylate, ethyl methacrylate, isobornyl methacrylate, butyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, isobutyl methacrylate, isodecyl methacrylate, isooctyl methacrylate, and 2-hydroxypropyl methacrylate.
Preferably, the photoinitiator is one or more of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, sodium (2,4, 6-trimethylbenzoyl) phenylphosphonate or ethyl (2,4, 6-trimethylbenzoyl) phenylphosphonate.
Preferably, the wavelength of the initiation light source is 405-465 nm, and the light intensity is 0.3-50 mW/cm2。
Preferably, the weight percentage of the polymerized monomer in the β -ketoester functionalized polymer nano material is 10-30 wt%.
Preferably, the molar ratio of the polymerized monomers to the macro RAFT agent is (30-500) to 1.
Preferably, the molar ratio of the acetoacetic acid glycol methacrylate to the methacrylate monomer is 1: 1.
Preferably, the molar ratio of the macro RAFT agent to the photoinitiator is (1-5) to 1.
Preferably, the reaction temperature of the dispersion polymerization reaction is 40 to 70 ℃.
Preferably, the reaction time of the dispersion polymerization reaction is 1 to 4 hours.
Specifically, the β -ketoester functionalized polymer nanomaterial provided by the invention can also perform a crosslinking reaction with a crosslinking agent, so that the β -ketoester functionalized polymer nanomaterial has more stable performance, and the technical problem that the β -ketoester functionalized polymer nanomaterial is easily influenced by a solvent, pH, a surfactant and temperature to cause appearance change and even disassembly is solved.
The raw materials of the following examples are all commercially available or self-made.
Example 1
The example discloses a synthetic route of a macromolecular RAFT reagent, which includes:
the structure of the synthesized macromolecule RAFT reagent is shown as a formula I, and the preparation method of the formula I specifically comprises the following steps: the modified polyethylene glycol monomethyl ether (mPEG) is obtained by carrying out esterification reaction on a carboxyl-containing RAFT reagent, wherein the structural formula of the carboxyl-containing RAFT reagent is as shown in a formula (2):
R is an alkyl group having 2 to 14 carbon atoms.
The invention provides a specific preparation route of a macromolecular RAFT reagent, which comprises the following specific steps:
to a 150mL round bottom flask was added polyethylene glycol monomethyl ether mPEG with a molecular weight of 200045(20g, 10mmol), CDPA (6.06g, 15mmol) and dry dichloromethane (50mL) were stirred well and placed in an ice-water bath. A solution (20mL) of DCC (3.09g, 15mmol) and DMAP (0.18g, 1.5mmol) in dichloromethane was added dropwise at 0 deg.C, and the reaction was continued at 0 deg.C for 1 h. After 48 hours of reaction at room temperature, the reaction mixture was filtered to remove insoluble matter, distilled under reduced pressure, and precipitated with a mixture of ethyl glacial ether and n-hexane (v: v ═ 1: 1) to give a crude product as a yellow solid. The column was then further purified by chromatography on silica gel with dichloromethane and methanol as mobile phase (v: v ═ 20: 1). Removing solvent, vacuum drying to obtain final product labeled mPEG45-a macromolecular RAFT agent of CDPA wherein R is an alkane group containing 12 carbon atoms and n ═ 45.
Example 2
The invention provides a first photochemical synthesis method of β -ketoester functionalized polymer nano-material, which comprises the following steps:
acetoacetic acid ethylene glycol methacrylate (AAEM, 0.96g, 4.5mmol), isobornyl methacrylate (IBOMA, 1g, 4.5mmol), mPEG of example 1 were weighed45-CDPA (mPEG45CDPA, 0.14g, 0.06mmol), photoinitiator phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide (0.0084g, 0.02mmol) was placed in a 25mL round bottom flask, and ethanol/water mixed solvent (6.28g/1.57g, 80: 20, w/w) was added and stirred well until the reagents were completely dissolved. And continuously introducing nitrogen for 20min in a dark condition, and sealing. The round bottom flask was then placed in a 40 ℃ water bath for 10min at constant temperature using an initiating light source (465nm, light intensity 4 mW/cm) at 40 DEG2) And (5) performing light reaction for 4 hours. The Transmission Electron Microscope (TEM) image and the Gel Permeation Chromatography (GPC) image of the obtained product are shown in the attached figures 1 and 2, the material prepared in example 2 is shown as a vesicle morphology with a cavity in the middle, the GPC image shows that the number average molecular weight (Mn) of the polymer is 24347g/mol, the molecular weight distribution index (PDI: Mw/Mn) is 1.30, the peak shape of the GPC image is symmetrical and the distribution is narrow, which indicates that the poly-mer is shown in the GPC imageThe synthesis reaction is controllable.
Referring to FIG. 12, the β -ketoester functionalized polymer nanomaterial of the present invention is prepared by mixing a polymerizable monomer, a photoinitiator, a macro-RAFT agent, and a solvent, and sampling before and after polymerization1H NMR characterization, FIG. 12 is1H NMR spectrum with DSS (sodium trimethylsilyl propanesulfonate)1According to the H NMR standard, the conversion rate of the monomer is calculated to be more than 90% by comparing the peak area of the double bond on the monomer, and as can be seen from figure 12, the peak area of the polymerized monomer is obviously reduced after photochemical synthesis, and a signal peak of the polymer appears, so that the β -ketoester functionalized polymer nano material is formed after the raw material of the monomer is subjected to photochemical synthesis, the content of the free monomer is reduced, and the conversion rate of the monomer reaches 90% by calculation, so that the conversion rate of the monomer is higher.
Example 3
The invention provides a second photochemical synthesis method of β -keto ester functionalized polymer nano-material, which comprises the following specific steps of replacing phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide in example 2 with diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide as a photoinitiator, keeping the molar quantity unchanged, ensuring the light reaction time to be 2h, ensuring the types and the amounts of the other reagents and the implementation process to be the same as those in example 2, and showing the Transmission Electron Microscope (TEM) picture of the obtained product as shown in figure 3, wherein figure 3 illustrates that the material prepared in example 3 shows the shape of vesicles.
Example 4
The invention provides a third photochemical synthesis method of β -ketoester functionalized polymer nano-materials, which comprises the following specific steps of adding polyethylene glycol monomethyl ether mPEG with the molecular weight of 5000 into a 150mL round-bottom flask113(20g, 10mmol), CDPA (6.06g, 15mmol) and dry dichloromethane (50mL) were stirred well and placed in an ice-water bath. A solution (20mL) of DCC (3.09g, 15mmol) and DMAP (0.18g, 1.5mmol) in dichloromethane was added dropwise at 0 deg.C, and the reaction was continued at 0 deg.C for 1 h. After 48 hours of reaction at room temperature, the reaction mixture was filtered to remove insoluble matter, distilled under reduced pressure, and precipitated with a mixture of ethyl glacial ether and n-hexane (v: v ═ 1: 1) to give a yellow colored precipitateThe crude product was solid. The column was then further purified by chromatography on silica gel with dichloromethane and methanol as mobile phase (v: v ═ 20: 1). Removing solvent, vacuum drying to obtain final product labeled mPEG113-CDPA, wherein R is an alkane group having 12 carbon atoms and n is an integer of 113. mPEG113CDPA instead of mPEG in example 245CDPA and the molar quantities are unchanged, the remaining reagents and amounts and the procedure are the same as in example 2. A Transmission Electron Microscope (TEM) photograph of the resulting product is shown in FIG. 4. As shown in fig. 4, fig. 4 illustrates that the material prepared in example 4 exhibits a spherical morphology.
Example 5
The present invention provides a fourth photochemical synthesis method of β -ketoester functionalized polymer nanomaterial, which comprises the following steps of replacing isobornyl methacrylate (IBOMA) in example 2 with Methyl Methacrylate (MMA), keeping the same molar weight, and keeping the types and amounts of the other reagents and the implementation procedures as in example 2. the Transmission Electron Microscope (TEM) photograph of the obtained product is shown in FIG. 5. As shown in FIG. 5, FIG. 5 shows that the material prepared in example 5 shows vesicle morphology.
Example 6
The invention provides a fifth photochemical synthesis method of β -ketoester functionalized polymer nano-material, which comprises the following steps that the reaction temperature is 70 ℃ instead of 40 ℃ in example 2, the types and the amounts of other reagents and the implementation process are the same as those in example 2, a Transmission Electron Microscope (TEM) picture of the obtained product is shown in figure 6, and figure 6 shows that the material prepared in example 6 shows the shape of a vesicle.
Example 7
The invention provides a sixth photochemical synthesis method of β -ketoester functionalized polymer nano-materials, which comprises the following specific steps of adding polyethylene glycol monomethyl ether mPEG with molecular weight of 8850 into a 150mL round-bottom flask200(20g, 10mmol), CDPA (6.06g, 15mmol) and dry dichloromethane (50mL) were stirred well and placed in an ice-water bath. A solution of DCC (3.09g, 15mmol) and DMAP (0.18g, 1.5mmol) in dichloromethane (20mL) was added dropwise at 0 deg.C and continuedThe reaction was carried out at 0 ℃ for 1 h. After 48 hours of reaction at room temperature, the reaction mixture was filtered to remove insoluble matter, distilled under reduced pressure, and precipitated with a mixture of ethyl glacial ether and n-hexane (v: v ═ 1: 1) to give a crude product as a yellow solid. The column was then further purified by chromatography on silica gel with dichloromethane and methanol as mobile phase (v: v ═ 20: 1). Removing solvent, vacuum drying to obtain final product labeled mPEG200-macromolecular RAFT agent of CDPA, wherein R is an alkanyl radical containing 12 carbon atoms, n is an integer of 200, mPEG200CDPA instead of mPEG in example 245-CDPA, and mPEG200CDPA was used (0.088g, 0.01mmol) and the remaining reagents and amounts and procedures were the same as in example 2. A Transmission Electron Microscope (TEM) photograph of the resultant product is shown in fig. 7, and the result of fig. 7 shows that the material prepared in example 7 exhibits a spherical morphology.
Example 8
The invention provides a seventh photochemical synthesis method of β -ketoester functionalized polymer nano-material, which comprises the following steps of weighing acetoacetic acid ethylene glycol methacrylate (AAEM, 0.96g, 4.5mmol), isobornyl methacrylate (IBOMA, 1g, 4.5mmol) and mPEG of example 145-CDPA (mPEG45CDPA, 0.35g, 0.06mmol), photoinitiator phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide (0.021g, 0.02mmol) was placed in a 25mL round bottom flask, and ethanol/water mixed solvent (6.28g/1.57g, 80: 20, w/w) was added and stirred well until the reagents were completely dissolved. And continuously introducing nitrogen for 20min in a dark condition, and sealing. The round bottom flask was then placed in a 40 ℃ water bath for 10min at constant temperature using an initiating light source (465nm, light intensity 4 mW/cm) at 40 DEG2) The light reaction is carried out for 4 hours, and the types and the use amounts of the rest reagents and the implementation process are the same as those of the example 2. A Transmission Electron Microscope (TEM) photograph of the resultant product is shown in FIG. 8, and FIG. 8 illustrates that the material prepared in example 8 exhibits a fibrous appearance.
Example 9
The invention provides an eighth photochemical synthesis method of β -ketoester functionalized polymer nano-material, which comprises the following specific steps of using an initiating light source (405nm, light intensity of 0.3 mW/cm)2) Instead of the initiation light source in example 2 (465nm,light intensity of 4mW/cm2) The remaining reagent types and amounts and the procedure were the same as in example 2. A Transmission Electron Microscope (TEM) photograph of the resultant product is shown in fig. 9, and the result of fig. 9 shows that the material prepared in example 9 exhibits a vesicular appearance.
Example 10
The invention provides a ninth photochemical synthesis method of β -ketoester functionalized polymer nano-materials, which comprises the following specific steps that the light intensity of an initiating light source is 40mW/cm2Instead of 0.3mW/cm as in example nine2The light reaction time is 1h, and the types, the amounts and the implementation processes of other reagents are the same as those of the example 2. A Transmission Electron Microscope (TEM) photograph of the resultant product is shown in fig. 10, and the result of fig. 10 shows that the material prepared in example 10 exhibits a vesicular appearance.
Example 11
The invention provides a synthesis method of β -ketoester functionalized polymer nano-material with good stability, which comprises the following specific steps of taking 0.5g of β -ketoester functionalized polymer nano-material obtained in example 2 out, adding ethanol/water mixed solution (1.2g/0.3g, 80: 20, w/w), stirring uniformly, adding 0.02 g of cross-linking agent ethylenediamine, reacting for 24h to obtain β -ketoester functionalized polymer nano-material with good stability after cross-linking, and dissolving the obtained product in good solvent tetrahydrofuran, namely a Transmission Electron Microscope (TEM) photograph as shown in figure 11, wherein the result of figure 11 shows that the material prepared in example 11 still shows a vesicle appearance in tetrahydrofuran, which shows that the stability is good.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A photochemical synthesis method of β -ketoester functionalized polymer nano-material is characterized by comprising the following steps:
mixing a polymerization monomer, a photoinitiator and a macromolecular RAFT reagent with a solvent, and carrying out dispersion polymerization under the irradiation of an initiation light source to obtain β -ketoester functional polymer nano material, wherein the polymerization monomer comprises β -ketoester functional monomer and methacrylate monomer, and the macromolecular RAFT reagent has a structure shown in formula I;
formula I;
wherein R is an alkyl group containing 2-14 carbon atoms, n = an integer of 20-200, and the β -ketone functional group monomer is acetoacetic acid ethylene glycol methacrylate.
2. The method of β -ketoester functionalized polymer nanomaterial, according to claim 1, wherein the methacrylate-based monomer is one or more of methyl methacrylate, ethyl methacrylate, isobornyl methacrylate, butyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, isobutyl methacrylate, isodecyl methacrylate, isooctyl methacrylate, and 2-hydroxypropyl methacrylate.
3. The photochemical synthesis method of β -keto-ester-functionalized polymer nanomaterial, according to claim 1, wherein the photoinitiator is one of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, sodium (2,4, 6-trimethylbenzoyl) phenylphosphonate, or ethyl (2,4, 6-trimethylbenzoyl) phenylphosphonate.
4. The method for photochemical synthesis of β -ketoester functionalized polymer nanomaterial according to claim 1, wherein the wavelength of the initiation light source is 405-465 nm, and the intensity of the initiation light source is 0.3-50 mW/cm2。
5. The photochemical synthesis method of β -ketoester functionalized polymer nanomaterial according to claim 1, wherein the polymerized monomer accounts for 10-30 wt% of the β -ketoester functionalized polymer nanomaterial.
6. The photochemical synthesis method of β -ketoester functionalized polymer nanomaterial according to claim 1, wherein the molar ratio of the polymerized monomer to the macromolecular RAFT agent is (30-500): 1.
7. The photochemical synthesis method of β -ketoester functionalized polymer nanomaterial according to claim 2, wherein the molar ratio of the acetoacetic acid glycol methacrylate to the methacrylate monomer is 1: 1.
8. The method for the photochemical synthesis of β -ketoester functionalized polymer nanomaterial according to claim 1, wherein the molar ratio of the macromolecular RAFT agent to the photoinitiator is (1-5): 1.
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| "Dispersion RAFT polymerization of 4-vinylpyridine in toluene mediated with the macro-RAFT agent of polystyrene dithiobenzoate: Effect of the macro-RAFT agent chain length and growth of the block copolymer nano-objects";Meihan Dan,etc.;《Journal of Polymer Science Part A Polymer Chemistry》;20130105;第51卷(第7期);第1573-1584页 * |
| "水相光引发聚合诱导自组装制备CO2响应性聚合物囊泡";张雪超等;《影像科学与光化学》;20171130;第35卷(第6期);第833-842页 * |
| "酮基表面功能PMMA微球的制备与研究";彭毅成等;《2015第十六届中国辐射固化年会暨中国感光学会2015年学术年会论文报告集》;20150921;第186-195页 * |
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