CN112028900A - Synthesis of star polymer and monomolecular micelle by light-operated in-situ bromine-iodine conversion RDRP method - Google Patents
Synthesis of star polymer and monomolecular micelle by light-operated in-situ bromine-iodine conversion RDRP method Download PDFInfo
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- CN112028900A CN112028900A CN202010947955.3A CN202010947955A CN112028900A CN 112028900 A CN112028900 A CN 112028900A CN 202010947955 A CN202010947955 A CN 202010947955A CN 112028900 A CN112028900 A CN 112028900A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 13
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- 238000003786 synthesis reaction Methods 0.000 title claims description 9
- 230000015572 biosynthetic process Effects 0.000 title claims description 8
- 101710118046 RNA-directed RNA polymerase Proteins 0.000 title abstract 2
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- 239000003999 initiator Substances 0.000 claims abstract description 18
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 17
- 150000004033 porphyrin derivatives Chemical class 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 30
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 16
- 229910052740 iodine Inorganic materials 0.000 claims description 16
- 239000011630 iodine Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 12
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- 239000003960 organic solvent Substances 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
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- 239000002245 particle Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
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- 230000009471 action Effects 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 22
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 21
- 239000004926 polymethyl methacrylate Substances 0.000 description 21
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- 238000012360 testing method Methods 0.000 description 18
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000003708 ampul Substances 0.000 description 8
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- 238000009826 distribution Methods 0.000 description 7
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- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- 230000002776 aggregation Effects 0.000 description 4
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
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- 238000001291 vacuum drying Methods 0.000 description 3
- WAKFRZBXTKUFIW-UHFFFAOYSA-N 2-bromo-2-phenylacetic acid Chemical compound OC(=O)C(Br)C1=CC=CC=C1 WAKFRZBXTKUFIW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 150000001351 alkyl iodides Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- VFHDWGAEEDVVPD-UHFFFAOYSA-N chembl507897 Chemical compound C1=CC(O)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(O)=CC=1)=C1C=CC(=N1)C(C=1C=CC(O)=CC=1)=C1C=CC(N1)=C1C=2C=CC(O)=CC=2)=C2N=C1C=C2 VFHDWGAEEDVVPD-UHFFFAOYSA-N 0.000 description 1
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- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- XGDZEDRBLVIUMX-UHFFFAOYSA-N methyl 2-(4-hydroxyphenyl)acetate Chemical compound COC(=O)CC1=CC=C(O)C=C1 XGDZEDRBLVIUMX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
- C08F299/028—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight photopolymerisable compositions
Abstract
The invention relates to a light-operated in-situ bromine-iodine conversion RDRP method for synthesizing star polymers and monomolecular micelles. The invention designs and synthesizes porphyrin derivatives which are used as star initiator precursors to initiate hydrophobic and hydrophilic methacrylate monomers, and the amphiphilic four-arm star block copolymer is prepared by light-controlled in-situ bromine-iodine conversion reversible-inactivation free radical polymerization.
Description
Technical Field
The invention relates to the technical field of star polymer preparation, in particular to a light-operated in-situ bromine-iodine conversion RDRP method for synthesizing a star polymer and a monomolecular micelle.
Background
In recent years, polymer micelle nanomaterials have received much attention. Compared with small molecular compounds, the polymer micelle has the advantages of easy structure regulation, long blood circulation time and the like. In general, the higher the molecular weight of the linear polymer, the higher the stability of the formed micelle, but the micelle particle size also increases. The excessive size makes the micelle difficult to penetrate the physiological barrier and easy to be captured by the immune system, which greatly limits its application. Unimolecular micelles (UIM) are expected to solve this problem, and some topological polymers can form not only multi-molecular associated micelles at high concentrations but also unimolecular micelles at low concentrations. The micelle formed by single molecule is only 10-20 nm, which is easy to avoid the capture of immune system and go deep into the pathological tissue. On the other hand, once the linear polymer micelle is injected into a body, the concentration is sharply reduced due to the blood dilution effect, and the micelle structure is very easy to collapse to lose the efficacy; however, the hydrophilic/hydrophobic structure of the monomolecular micelle is stabilized by a covalent bond and is not destroyed by the change of factors such as concentration, temperature and the like, so that the monomolecular micelle has unique advantages in the biomedical field.
There are three main types of polymers that can form monomolecular micelles: star polymers, dendrimers, and hyperbranched polymers. Compared with star polymers, the synthesis method of the dendritic polymer and the hyperbranched polymer has the defects of long time consumption, high cost, low efficiency, complex steps and the like, so that the development potential of the dendritic polymer and the hyperbranched polymer in the large-scale industrialization direction is insufficient. On the contrary, the synthesis of star polymers is relatively simple and is expected to become the main research direction of monomolecular micelles. Star polymers have a unique three-dimensional snowflake-like structure comprising a core and a plurality of polymer "arms". There are two main strategies for synthesizing star polymers: "arm before nucleus" and "arm before nucleus". Firstly, designing a multifunctional macromolecule or micromolecule as a core by a 'core-first-arm-second' strategy, and initiating monomer polymerization to grow an arm; the "arm-first-core" strategy is to first synthesize the polymer arms and then assemble them to the core in a chemically cross-linked manner. The "arm-first-nucleus" strategy generally has the following disadvantages: the number of polymer arms is difficult to control accurately and is not easily characterized. Whereas in the "core-first-arm-second" the number of arms is relatively easier to determine, the emphasis is on how to control the length of each arm to be relatively uniform, which depends primarily on the choice of polymerization method. There are currently many polymerization methods applied to the synthesis of star polymers, such as ring-opening polymerization (ROP), anionic polymerization, reversible addition-fragmentation chain transfer (RAFT) polymerization, Atom Transfer Radical Polymerization (ATRP), and iodine-mediated reversible-inactivated radical polymerization (RDRP). ROP applies only to cyclic monomers; the anionic polymerization conditions are very severe; RAFT polymerisation requires the use of RAFT reagents which are expensive and not easily synthesised; the residue of transition metals in ATRP greatly limits its applications; the alkyl iodide reagents used in iododine-mediated RDRP are structurally unstable and difficult to store. Therefore, it is of great importance to find a low-toxicity, efficient, environment-friendly and simple polymerization method suitable for synthesizing star polymers.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a light-operated in-situ bromine-iodine conversion RDRP method for synthesizing a star polymer and a monomolecular micelle.
The invention discloses a porphyrin derivative, the structural formula of the porphyrin derivative is shown as formula (1) or formula (2):
the porphyrin derivative takes porphyrin as a core and contains four C-Br bonds.
The second object of the present invention is to disclose the use of the above porphyrin derivatives as initiators for polymerization reactions for the synthesis of star polymers.
Further, the polymerization reaction is light-controlled in-situ bromine-iodine conversion reversible-inactivation free radical polymerization (BIT-RDRP).
Further, the polymerization reaction is carried out in the presence of a metal salt of iodine and under the irradiation of visible light having a wavelength of 400 to 660 nm.
The third purpose of the invention is to provide a method for synthesizing an amphiphilic star block copolymer, which is synthesized by adopting a light-operated in-situ bromine-iodine conversion RDRP reaction and comprises the following steps:
(1) under the irradiation of visible light with the protective atmosphere and the wavelength of 400-660 nm, carrying out light-controlled in-situ bromine-iodine conversion reversible-inactivation free radical polymerization reaction on a hydrophobic methacrylate monomer in an organic solvent under the action of a star initiator precursor, a metal salt of iodine and organic amine, wherein the reaction temperature is room temperature (20-30 ℃), and obtaining a hydrophobic star homopolymer after the reaction is completed; wherein the star-shaped initiator precursor comprises a porphyrin derivative shown in a formula (1) or a formula (2);
(2) under the action of metal salt of iodine and organic amine, continuously reacting a hydrophobic star homopolymer with a hydrophilic methacrylate monomer in an organic solvent under the irradiation of protective atmosphere and visible light with the wavelength of 400-660 nm to obtain an amphiphilic star block copolymer of the formula (3) after the reaction is completed; wherein the structural formula of formula (3) is as follows:
when the initiator is of formula (1), R is
When the initiator is of the formula (2), R is
In R, x represents a group attachment site;
wherein R is1Selected from benzyl or C1-C6 alkyl; r2Selected from methoxypolyethylene glycol or dimethylamino;
m＝90～170；n＝30～110。
preferably, in the step (1), the star-shaped initiator precursor is a porphyrin derivative represented by the formula (2),is named as THPP-Br4。
Preferably, R1Selected from methyl, n-butyl or benzyl.
Preferably, R2Selected from methoxypolyethylene glycols.
Further, in step (1), the hydrophobic methacrylate-based monomer includes Methyl Methacrylate (MMA), ethyl methacrylate, Butyl Methacrylate (BMA) or benzyl methacrylate (BnMA), preferably MMA.
Further, in the step (1), the mole ratio of the hydrophobic methacrylate monomer, the star-shaped initiator precursor, the metal salt of iodine and the organic amine is 100-400: 1: 8-12: 1-3. Preferably, the mole ratio of the hydrophobic methacrylate monomer, the star-shaped initiator precursor, the metal salt of iodine and the organic amine is 200-400: 1:12: 2.
Further, in steps (1) and (2), the organic amine is Triethylamine (TEA), Tributylamine (TBA), Tetramethylethylenediamine (TMEDA), or pentamethyldiethylenetriamine. Preferably, the organic amine is Triethylamine (TEA).
Further, in the step (1), the metal salt of iodine is potassium iodide (KI) or sodium iodide (NaI). Preferably, the metal salt of iodine is sodium iodide (NaI).
Further, in the step (1), the organic solvent is N, N '-Dimethylformamide (DMF), N' -dimethylacetamide, or dimethylsulfoxide. Preferably DMF.
Further, in the step (2), the hydrophilic methacrylate-based monomer includes polyethylene glycol methacrylate (PEGMA) or dimethylaminoethyl methacrylate.
Further, the hydrophilic methacrylate monomer has an average molecular weight of 300 to 950g/mol, preferably 500 g/mol.
Further, in the step (2), the organic solvent is methanol or ethanol. Ethanol is preferred.
Further, in the step (2), the molar ratio of the hydrophilic methacrylate monomer to the hydrophobic star-shaped homopolymer to the metal salt of iodine to the organic amine is 100-400: 1: 8-12: 1-3. Preferably, the mole ratio of the hydrophilic methacrylate monomer to the hydrophobic star homopolymer to the metal salt of iodine to the organic amine is 100-200: 1:12: 2.
Further, in the steps (1) and (2), the volume ratio of the monomer to the organic solvent is 1: 0.5-2. Preferably, the volume ratio of monomer to solvent is 1: 2.
Further, in the steps (1) and (2), the protective atmosphere is an argon atmosphere.
Preferably, in steps (1) and (2), the reaction temperature is 25 ℃.
Further, in the steps (1) and (2), the visible light with the wavelength of 400-660 nm is the light emitted by an LED lamp light source. Preferably, the light source has a wavelength of 460nm and a power of 0.015W/cm2The blue LED lamp of (1).
Preferably, the polymerization reaction time of the step (1) is 8 to 14 hours.
Preferably, the polymerization reaction time of the step (2) is 20 to 24 hours.
Preferably, the hydrophobic methacrylate monomer is methyl methacrylate, the hydrophilic methacrylate monomer is polyethylene glycol methacrylate with the average molecular weight of 500g/mol, and the structural formula of the obtained amphiphilic star-shaped block copolymer is as follows:
when the initiator is of formula (1), R is
When the initiator is of the formula (2), R is
In R, x represents a group attachment site;
m＝90～170；n＝30～110。
the light-controlled in-situ bromine-iodine conversion reversible-deactivation free radical polymerization (BIT-RDRP) method adopts the porphyrin derivative as an initiator precursor, and reacts with metal salt of iodine in a polymerization system to generate an alkyl iodide reagent (R-I) in situ.
The fourth object of the present invention is to provide a method for synthesizing a star polymer monomolecular micelle, comprising the steps of:
the amphiphilic star block copolymer prepared by the method is dissolved in an organic solvent, and then the obtained organic solution of the amphiphilic star block copolymer is self-assembled in water to form the star polymer monomolecular micelle, wherein the concentration of the organic solution of the amphiphilic star block copolymer is less than 0.564 mg/mL.
Further, the obtained amphiphilic star block copolymer organic solution was stirred at room temperature for 24 hours, and then the solution was transferred to a dialysis bag and dialyzed at room temperature for 48 hours to obtain a star polymer monomolecular micelle solution.
The invention also claims the star polymer monomolecular micelle prepared by the method, and the particle size of the star polymer monomolecular micelle is 8-21 nm.
By the scheme, the invention at least has the following advantages:
the invention establishes a high-efficiency, clean and convenient strategy for synthesizing the amphiphilic star block copolymer by the light-operated BIT-RDRP method at room temperature without using any expensive reagent or toxic and harmful transition metal. The invention uses cheap and easily obtained raw materials, and uses clean and environment-friendly visible light as energy; ln of monomers in polymerization ([ M ]]0/[M]) The molecular weight of the polymer linearly increases along with the increase of the conversion rate, and the polymer conforms to the activity characteristic of general reversible-deactivation polymerization; the obtained amphiphilic star-shaped block copolymer has a relatively uniform and regular four-arm structure, and can form monomolecular micelles with small particle sizes in water.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 shows THPP-Br4Is/are as follows1H NMR test results;
FIG. 2 is a graph of the polymerization kinetics during PMMA preparation;
FIG. 3 is a GPC outflow curve of PMMA and PMMA-b-PPEGMA;
FIG. 4 is a drawing of PMMA-b-PPEGMA1H NMR test results;
FIG. 5 is the DLS test results of PMMA-b-PPEGMA star polymer monomolecular micelles;
FIG. 6 shows the results of Critical Aggregation Concentration (CAC) measurements of PMMA-b-PPEGMA star polymer monomolecular micelles;
FIG. 7 shows TEM test results of PMMA-b-PPEGMA star polymer monomolecular micelles.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the following examples of the present invention, Methyl Methacrylate (MMA) and polyethylene glycol methacrylate (PEGMA) were passed through a neutral alumina column and used. Pyrrole, 4-hydroxybenzaldehyde, 2-bromo-2-phenylacetic acid, propionic acid and N, N' -Dicyclohexylcarbodiimide (DCC), 4-dimethylaminopyridine (4-DMAP), sodium iodide (NaI), Triethylamine (TEA) and pyrene (99) were obtained from Macklin (Shanghai), tetrahydrofuran (THF analytical reagent), N, N-dimethylformamide (DMF analytical reagent) and others were all commercially available and used as they were.
In the invention, the following test methods are adopted:
1. number average molecular weight (M) of the Polymern，GPC) And molecular weight distribution (M)w/Mn) Measured by TOSOH HLC-8320 Gel Permeation Chromatography (GPC), equipped with a TOSOH differential refractometer detector, one guard column (4.6X 20mm, TSKgel guard column SuperMP-N) and two test columns (4.6X 150mm, TSKgel SuperMultip)oreHZ-N), the molecular weight range measurable is from 5X 102To 5X 105g/mol. THF was used as the mobile phase for the test at 40 ℃ and a flow rate of 0.35 mL/min. Samples were tested by TOSOH autosampler aspiration and linear PMMA purchased from TOSOH was selected as a standard when analyzing the data. The samples tested for GPC were prepared as follows: mu.L of the polymer mixture was taken, lyophilized to remove the solvent, the polymer was dissolved in THF, passed through a small column of neutral alumina and a syringe equipped with a 0.45 μm filter head, and the pure polymer solution was finally injected into the test flask.
2. The NMR spectra of the small molecular compounds and the polymer were obtained by Bruker 300MHz NMR spectrometer with deuterated reagent CDCl3As a solvent, Tetramethylsilane (TMS) was used as an internal standard.
3. The hydrodynamic diameter of the micelles was determined by dynamic light scattering (DLS, nanobook 90Plus) and the micelles were dispersed in water at a test temperature of 25 ℃.
4. The morphology of the micelles was obtained by FEI TecnaiG22 Transmission Electron Microscope (TEM) with an acceleration voltage of 120 kV. 20 mul of micelle solution with the concentration of 0.1mg/mL is transferred and dropped on a 200-mesh copper net, and the micelle solution is prepared after standing for 30 seconds.
Example 1THPP-Br4Synthesis of (2)
(1) A250 mL three-necked flask was charged with 3.66g (30.0mmol) of 4-hydroxybenzaldehyde and 80mL of propionic acid, and heated to 140 ℃. 2.10g (31.3mmol) of pyrrole were added slowly over 2 hours and reflux was continued for 4 hours. After cooling to room temperature, 50ml of ethanol was added and the mixture was allowed to stand at 4 ℃ for 12 hours. And (4) carrying out suction filtration, collecting a filter cake, and washing the filter cake by using propionic acid and chloroform in sequence. The filter cake was dissolved in ethanol and the insoluble residue was removed. Finally, the ethanol was removed by rotary evaporation to give 3.07g of a purple solid (5, 10, 15, 20-tetrakis (4-hydroxyphenyl) -porphyrin, THPP, yield: 47.7%).
(2) 6.80g (31.6mmol) of 2-bromo-2-phenylacetic acid, 7.60g of DCC (36.8mmol) and 100mL of methylene chloride were placed in a 250mL single-neck flask, and stirred at room temperature for 1 hour. A flask was charged with 1.00g (1.5mmol) of THPP and 0.45g of 4-DMAP (3.7mmol), and stirred at room temperature for 72 hours. DrawerThe filtrate was collected by filtration and excess dichloromethane was removed by rotary evaporation to give a black viscous solid. And (4) performing column chromatography by taking dichloromethane as an eluent, and collecting a first purple band to obtain a crude product. Then carrying out column chromatography by taking petroleum ether/ethyl acetate (4:1) as eluent to finally obtain THPP-Br4(0.78g, yield: 36.2%). The reaction route is as follows:
FIG. 1 shows THPP-Br4Is/are as follows1H NMR test results, analysis results are as follows:
1H-NMR(300MHz，CDCl3，TMS，，ppm)：5.76(s，4H)，7.48-7.53(m，20H)，7.78-7.81(m，8H)，8.19-8.21(d，8H)，8.83(s，8H)。
in addition, a porphyrin derivative represented by the formula (1) can be synthesized in a similar manner except that 4-hydroxybenzaldehyde in the step (1) is replaced by methyl 4-hydroxybenzeneacetate, and the compound represented by the formula (1) is obtained after refluxing with pyrrole and propionic acid, cooling and purifying.
EXAMPLE 2 Synthesis of Star homopolymer PMMA
Polymerizing in an ampoule bottle under argon atmosphere to obtain blue light-emitting diode (LED) lamp strip (lambda)max＝460nm，0.015W/cm2). In a molar ratio of [ MMA]0/[THPP-Br4]0/[NaI]0/[TEA]0The polymerization procedure was as follows: THPP-Br prepared in example 14(10.5mg, 0.00716mmol), NaI (12.6mg, 0.084mmol), MMA (0.30mL, 2.83mmol), TEA (2.0. mu.L, 0.0145mmol), DMF (0.60mL) and a clean magneton were added to a dry 2mL ampoule. The cycle of freeze evacuation-thaw inflation was repeated three times to substantially eliminate dissolved oxygen in the vial and to provide an argon atmosphere before the ampoule was flame sealed. And (3) placing the ampere bottle into a stirring device provided with a blue LED lamp strip, and removing heat brought by LED irradiation in a cooling mode by using an electric fan to keep the polymerization reaction at room temperature. After a period of time, the ampoule was transferred to dark and light-protected to terminate the polymerization. With 5mL of tetrahydroThe sample was diluted with furan and the diluted solution was slowly dropped into 100mL of petroleum ether. Standing for 8 hours, filtering to remove filtrate, and vacuum drying for 6 hours to obtain light purple powdery solid PMMA. The monomer conversion at different polymerization times was calculated by weighing method1H NMR and GPC the molecular weight of the samples was measured and the molecular weight distribution of the samples was measured by GPC as shown in table 1.
TABLE 1 test results of polymerization at different polymerization times
From the results of Table 1, the polymerization kinetics of FIG. 2 were obtained. FIG. 2(a) shows ln ([ M ] of monomer in polymerization reaction]0/[M]) The molecular weight of the polymer increases linearly with the increase of the conversion rate, which is in accordance with the "living" characteristic of general reversible-deactivation polymerization, and the molecular weight distribution of the polymer is always maintained in a narrow range, as shown in fig. 2(b), which is a GPC outflow curve of the polymer in which the reaction time corresponding to the curve from right to left is sequentially extended, and the results thereof show that the polymer exhibits a single-peak distribution at different conversion rates.
EXAMPLE 3 Synthesis of Star-shaped Block copolymer PMMA-b-PPEGMA
Polymerizing in an ampoule bottle under argon atmosphere to obtain blue light-emitting diode (LED) lamp strip (lambda)max＝460nm，0.015W/cm2). Sufficient NaI was added in this example to ensure that all PMMA ends were iodine capped. PMMA of different molecular weights were prepared according to the method of example 2, using PMMA of different molecular weights as macroinitiator, respectively, in a molar ratio of [ PEGMA]0/[PMMA]0/[NaI]0/[TEA]0The star block copolymer PMMA-b-PPEGMA was synthesized with a raw material ratio of 200/1/12/2. Taking PMMA with a molecular weight of 13000g/mol as an example, the polymerization steps are as follows: mixing PMMA (42.5mg, 0.00327mmol), NaI (5.9mg, 0.00649mmol), PEGMA500(0.30mL，0.654mmol)，TEA(0.9μL，0.00649mmol)，C2H5OH (0.60mL) and a cleanMagnetons were added to a dry 2mL ampoule. The cycle of freeze evacuation-thaw inflation was repeated three times to substantially eliminate dissolved oxygen in the vial and to provide an argon atmosphere before the ampoule was flame sealed. And (3) placing the ampere bottle into a stirring device provided with a blue LED lamp strip, and removing heat brought by LED irradiation in a cooling mode by using an electric fan to keep the polymerization reaction at room temperature. After a period of time, the ampoule was transferred to dark and light-protected to terminate the polymerization. The sample was diluted with 5mL of tetrahydrofuran, and the diluted solution was slowly dropped into 100mL of petroleum ether. Standing for 8 hours, filtering to remove filtrate, and vacuum drying for 6 hours to obtain purple viscous solid PMMA-b-PPEGMA. By passing1H NMR and GPC measure the molecular weight of the sample, and the molecular weight distribution of the sample is measured by GPC. Table 2 shows some test results of different molecular weights of PMMA, different molar ratios of polymerization process, where M isn,GPC(g/mol)、Mn,NMR(g/mol)、Mw/MnAll refer to the test results of the product PMMA-b-PPEGMA.
TABLE 2 test results of polymerization for different molecular weights of PMMA and different molar ratios
FIG. 3 is the GPC outflow curve (curve b) for PMMA (curve a) and PMMA-b-PPEGMA of run number 11. FIG. 4 is a drawing of PMMA-b-PPEGMA1H NMR test results.
Example 4 validation of four-arm regularity of Star Polymer
PMMA and PMMA-b-PPEGMA of different molecular weights were prepared according to the methods of examples 2 and 3, respectively, and the regularity thereof was verified by decomposing the four arms of the star polymer in such a manner that the star polymer was hydrolyzed under an alkaline condition.
(1) Verification of four-arm regularity of star homopolymer PMMA
25mg of star homopolymer PMMA was dissolved in 2mL of THF, then 0.2mL of water and 10mg of NaOH were added. Stirring was carried out at 30 ℃ for 24 hours. The sample was diluted with 2mL of THF, and the diluted solution was slowly dropped into 40mL of petroleum ether. Standing for 8 hr, filtering to remove filtrate, and vacuum dryingAfter 6 hours, a linear homopolymer PMMA was obtained. By passing1H NMR measures the molecular weight of the sample, and the molecular weight distribution of the sample is measured by GPC.
(2) Verification of four-arm regularity degree of star block copolymer PMMA-b-PPEGMA
25mg of the star homopolymer PMMA-b-PPEGMA was dissolved in 2mL of THF, then 0.2mL of water and 10mg of NaOH were added. Stirring was carried out at 30 ℃ for 24 hours. The sample was diluted with 2mL of THF, and the diluted solution was slowly dropped into 40mL of petroleum ether. Standing for 8 hours, filtering to remove filtrate, and vacuum drying for 6 hours to obtain the linear copolymer PMMA-b-PPEGMA.
By passing1H NMR measures the molecular weight of the sample, and the molecular weight distribution of the sample is measured by GPC. Table 3 shows the results of verifying the degree of regularity of the four arms of PMMA and PMMA-b-PPEGMA with different molecular weights. As can be seen from Table 3, the ratio of the molecular weight before hydrolysis of the star polymer to the molecular weight after hydrolysis is close to 4, thus demonstrating that the PMMA and the star polymer PMMA-b-PPEGMA obtained by the present invention have relatively regular structures and relatively uniform lengths of four arms.
TABLE 3 results of some tests of PMMA and PMMA-b-PPEGMA of different molecular weights
Example 5 preparation of Star Polymer monomolecular micelle
Preparing the star polymer monomolecular micelle solution by adopting a cosolvent dialysis method. A certain mass of the radial block copolymer PMMA-b-PPEGMA (M) prepared in the experimental group of example 3, No. 11 was weighed outn，NMR＝44600g/mol，Mw/Mn1.15) was dissolved in 5mL of DMF to prepare solutions with concentrations varying from 4.0mg/mL to 0.01mg/mL, and stirred at room temperature for 12 hours. The solution was transferred to a dialysis bag with a molecular weight cut-off of 3500g/mol and dialyzed thoroughly against deionized water for 48 hours to remove DMF, giving a micellar solution. And (3) measuring the critical aggregation concentration of the micelle solution by a pyrene fluorescence method, measuring the particle size of the monomolecular micelle by DLS (digital Living System), and observing the morphology of the monomolecular micelle by TEM (transmission electron microscope).
FIG. 5 is the DLS test results for micellar solutions at concentrations of 4.0mg/mL, 0.10mg/mL, 0.01 mg/mL; FIG. 6 shows the results of Critical Aggregation Concentration (CAC) measurements of PMMA-b-PPEGMA star polymer monomolecular micelles; FIG. 7 shows TEM test results of PMMA-b-PPEGMA star polymer monomolecular micelles; FIG. 5 shows that the polymer micelle solution has both multi-molecular association micelles and single-molecular micelles at a high concentration (4.0mg/mL) and only single-molecular micelles at a low concentration (0.10mg/mL, 0.01mg/mL), and the micelle diameter does not decrease with decreasing concentration. FIG. 6 shows that the critical aggregation concentration of the micelle is 0.564mg/mL, which is consistent with the test results of FIG. 5. Meaning that when the micelle concentration is greater than this value, there will be multimolecular associated micelles present, and when the micelle concentration is less than this value, only monomolecular micelles are present in the solution. The morphology of the monomolecular micelles can be observed in fig. 7, and the monomolecular micelles with uniform particle size and smaller diameter can be seen.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A porphyrin derivative is characterized in that the structural formula of the porphyrin derivative is shown as a formula (1) or a formula (2):
2. use of the porphyrin derivative of claim 1 as an initiator for polymerization reactions for the synthesis of star polymers.
3. Use according to claim 2, wherein the polymerization is a photo-controlled in situ bromine-iodine transition reversible-deactivating free radical polymerization.
4. A method of synthesizing an amphiphilic star block copolymer, comprising the steps of:
(1) under the irradiation of visible light with the protective atmosphere and the wavelength of 400-660 nm, carrying out light-controlled in-situ bromine-iodine conversion reversible-inactivation free radical polymerization reaction on a hydrophobic methacrylate monomer in an organic solvent under the action of a star initiator precursor, a metal salt of iodine and organic amine, wherein the reaction temperature is room temperature (20-30 ℃), and obtaining a hydrophobic star homopolymer after the reaction is completed; wherein the star initiator precursor comprises the porphyrin derivative of claim 1;
(2) under the action of metal salt of iodine and organic amine, the hydrophobic star-shaped homopolymer and the hydrophilic methacrylate monomer continue to react in an organic solvent under the irradiation of protective atmosphere and visible light with the wavelength of 400-660 nm, and the amphiphilic star-shaped block copolymer of the formula (3) is obtained after the reaction is completed; wherein the structural formula of formula (3) is as follows:
when the initiator is of formula (1), R is
When the initiator is of the formula (2), R is
Wherein R is1Selected from benzyl or C1-C6 alkyl; r2Selected from methoxypolyethylene glycol or dimethylamino;
m＝90～170；n＝30～110。
5. the method of claim 4, wherein: in the step (1), the hydrophobic methacrylate monomer includes methyl methacrylate, ethyl methacrylate, butyl methacrylate or benzyl methacrylate.
6. The method of claim 4, wherein: in the step (1), the mole ratio of the hydrophobic methacrylate monomer, the star-shaped initiator precursor, the metal salt of iodine and the organic amine is 100-400: 1: 8-12: 1-3.
7. The method of claim 4, wherein: in the step (2), the hydrophilic methacrylate monomer includes polyethylene glycol methacrylate or dimethylaminoethyl methacrylate.
8. The method of claim 4, wherein: in the step (2), the mole ratio of the hydrophilic methacrylate monomer, the hydrophobic star homopolymer, the iodine metal salt and the organic amine is 100-400: 1: 8-12: 1-3.
9. A method for synthesizing a star polymer monomolecular micelle is characterized by comprising the following steps:
dissolving the amphiphilic star block copolymer prepared by the method of any one of claims 4 to 8 in an organic solvent, and then self-assembling the obtained organic solution of the amphiphilic star block copolymer in water to form the star polymer monomolecular micelles, wherein the concentration of the organic solution of the amphiphilic star block copolymer is below 0.564 mg/mL.
10. The star polymer monomolecular micelle prepared by the method of claim 9, wherein the particle size thereof is 8 to 21 nm.
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