CN108424482B - Spiropyran-containing multi-responsiveness dendritic polymer and preparation method thereof - Google Patents
Spiropyran-containing multi-responsiveness dendritic polymer and preparation method thereof Download PDFInfo
- Publication number
- CN108424482B CN108424482B CN201810160635.6A CN201810160635A CN108424482B CN 108424482 B CN108424482 B CN 108424482B CN 201810160635 A CN201810160635 A CN 201810160635A CN 108424482 B CN108424482 B CN 108424482B
- Authority
- CN
- China
- Prior art keywords
- solvent
- dendritic
- pcl
- star
- hps
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000412 dendrimer Substances 0.000 title claims abstract description 17
- 229920000736 dendritic polymer Polymers 0.000 title claims abstract description 17
- 230000004043 responsiveness Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 22
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 21
- 229920000728 polyester Polymers 0.000 claims abstract description 12
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 10
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 9
- GGXRSUUOWQBVFB-UHFFFAOYSA-N 2,3-dibromo-2-methylpropanoyl bromide Chemical compound BrCC(Br)(C)C(Br)=O GGXRSUUOWQBVFB-UHFFFAOYSA-N 0.000 claims abstract description 8
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- 239000002904 solvent Substances 0.000 claims description 40
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 229960001701 chloroform Drugs 0.000 claims description 17
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- FLHJIAFUWHPJRT-UHFFFAOYSA-N 2,3,3-trimethylindole Chemical compound C1=CC=C2C(C)(C)C(C)=NC2=C1 FLHJIAFUWHPJRT-UHFFFAOYSA-N 0.000 claims description 8
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 claims description 8
- IHFRMUGEILMHNU-UHFFFAOYSA-N 2-hydroxy-5-nitrobenzaldehyde Chemical compound OC1=CC=C([N+]([O-])=O)C=C1C=O IHFRMUGEILMHNU-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 7
- 101710141544 Allatotropin-related peptide Proteins 0.000 claims description 7
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 7
- 239000007832 Na2SO4 Substances 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 7
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000693 micelle Substances 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 5
- 238000013270 controlled release Methods 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000003384 imaging method Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Abstract
The invention relates to a preparation method of a spiropyran-containing dendritic polymer with multiple responsiveness. Preparing dendritic polycaprolactone by ring-opening polymerization of dendritic polyester and caprolactone, reacting the obtained dendritic polycaprolactone with dibromo isobutyryl bromide and triethylamine to obtain dendritic macroinitiator, and carrying out atom transfer radical polymerization of the macroinitiator and tert-butyl methacrylate to obtain HPs-Star-PCL-bPtbMA, hydrolyzing the obtained product to obtain HPs-Star-PCL-bPMAA, hydroxy-spiropyran HPs-Star-PCL-bPMAA to HPs-Star-PCL-Acone by esterificationb-PMAA-SP. The micelle prepared by the invention has pH responsiveness and light responsiveness by self-assembly to form the micelle. The reversible regulation is carried out by ultraviolet and visible light irradiation or acid-base, and the method has wide application in the fields of biological cell imaging, photoelectric devices, molecular logic switches, drug controlled release and the like.
Description
Technical Field
The invention belongs to the fields of high molecular materials, nano materials and biomedicine, and particularly relates to a spiropyran-containing multi-responsiveness dendritic polymer and a preparation method thereof.
Background
The photochromic compound is a compound A which generates a compound B through isomerization reaction under the irradiation of light with a certain wavelength, and the compound B can be converted and recovered to A under the irradiation of light with another wavelength or under the action of heat.
The spiropyran compounds are important photochromic compounds, and become a hot point of research in the current photochromic field due to the characteristics of excellent photochromic property, thermal stability, fatigue resistance, capability of serving as a good organic light storage material and the like. When ultraviolet light irradiation or PH is reduced, hydrophobic spiropyrans may be converted into hydrophilic partial phthalocyanines, which may gradually revert back to spiropyrans when visible light irradiation or PH is increased. Therefore, after the spiropyran amphiphilic polymer is assembled into the vesicle or the micelle, the vesicle or the micelle can be fused or disintegrated under the stimulation of ultraviolet light and visible light or the change of acid-base conditions.
The dendritic polyester has the characteristics of high set symmetry, accurate molecular structure, a large number of functional groups, a large number of cavities in molecules, controllability of molecular chain growth and the like in the structure, so that the dendritic polyester has wide application prospects in the fields of industry and agriculture, national defense, materials science, medicine, life science, environmental protection and the like. For example, it can be used as high-efficiency catalyst, information storage material, medicine slow-release carrier, liquid crystal material, separation membrane, photosensitive material and sewage treatment material.
Polycaprolactone (PCL) is a hydrophobic polymer with good drug permeability and biocompatibility, and an amphiphilic dendritic polymer taking PCL as a hydrophobic block can form a stable micelle taking PCL as a core and a hydrophilic polymer as a shell in an aqueous solution.
Tert-butyl methacrylate (tBMA) is a monomer with high reactivity and strong hydrophobicity, and has wide application in the preparation of functionalized microspheres and copolymers.
Ring-opening polymerization grafting polycaprolactone by using dendritic polymer, then bromination to generate dendritic macromolecular initiator, and atom transfer radical polymerization to generate HPs-Star-PCL-b-PtbMA. Hydrolyzing the obtained product and grafting hydroxy spiropyran by esterification reaction to obtain HPs-Star-PCL-b-PMAA-SP。
Disclosure of Invention
The invention aims to provide a preparation method of a spiropyran-containing dendritic polymer with multiple responsiveness.
The invention aims to introduce spiropyrans and dendritic polyesters with multiple responsibilities into polymers. The preparation of the light-responsive and PH-responsive dendrimer with multiple responsiveness is realized. The preparation method comprises the steps of preparing N-hydroxyethyl-3 ', 3 ' -dimethyl (2H-5-nitro-benzo spiropyran-2, 2 ' -indole) by using commercial 2,3, 3-trimethyl indole, 2-bromoethanol and 5-nitro salicylaldehyde, synthesizing a macroinitiator by using commercial dendritic polyester and caprolactone, connecting tert-butyl methacrylate by using the macroinitiator through an atom transfer radical polymerization method, obtaining HPs-Star-PCL-b-PMAA through hydrolysis, and finally connecting HPs-Star-PCL-b-PMA and hydroxy spiropyran to obtain the spiropyran-containing dendritic polymer with multiple responsibilities.
The invention provides a preparation method of a spiropyran-containing multi-responsiveness dendritic polymer, which comprises the following specific steps:
(1) mixing 2,3, 3-trimethylindole and 2-bromoethanol (the molar ratio is 1: 1.5) in a solvent A, refluxing and stirring for 1-24 hours to obtain a mixture; then standing the mixture at room temperature for 1-12 h, filtering to obtain a solid, washing the crude product with a solvent B, dissolving the solid in an NaOH aqueous solution, extracting with chloroform for three times, combining organic phases, drying with anhydrous Na2SO4, evaporating the solvent, dissolving the residual product and 5-nitro salicylaldehyde in a solvent C, reacting at 40-120 ℃ for 2-8 h, pouring the reaction solution into 100-400 mL of distilled water while the reaction solution is hot, filtering, and drying to obtain the hydroxy spiropyran;
(2) reacting dendritic polyester and caprolactone (the molar ratio is 1: 25) at 40-180 ℃ for 1-4 h in a vacuum environment, and cooling to room temperature; adding a toluene solution of stannous octoate, reacting for 12-24 h under a vacuum condition, and cooling to room temperature; adding a solvent D for dissolution, and then precipitating by using a precipitator E to obtain dendritic polycaprolactone;
(3) dissolving star-shaped polycaprolactone by using a solvent F, adding triethylamine and dibromo isobutyryl bromide (the molar ratio is 1: 1.1: 1.1), and reacting at normal temperature for 30 hours to obtain a dendritic macromolecular initiator;
(4) the obtained dendritic macromolecule initiator, CuBr and methacrylate (the molar ratio is 1: 1: 40) are subjected to ATRP in a solvent G for reaction for 10-24 h to obtain HPs-Star-PCL-b-PtbMA；
(5) Dissolving HPs-Star-PCL-ketone obtained in the step (4) by using a solvent HbAdding trifluoroacetic acid into PtbMA, reacting for 2-8 h (molar ratio 1: 1) to obtain HPs-Star-PCL-b-PMAA；
(6) HPs-Star-PCL-bAnd (2) adding DCC and DMAP (molar ratio of 1: 1.1: 0.1) into PMAA and the hydroxy spiropyran obtained in the step (1) to react in a solvent I for 3-12 h to obtain a final product.
In the invention, the solvent A in the step (1) is one or more of methanol, ethanol or ethyl acetate, the solvent B is one or more of tetrahydrofuran, DMF or acetone, and the solvent C is one or more of dichloromethane, trichloromethane or acetone.
In the invention, the solvent D in the step (2) is one or more of dichloromethane, chloroform or tetrahydrofuran, and the precipitant E is one or more of methanol, diethyl ether or n-hexane.
In the invention, the solvent F according to the step (3) is one or more of dichloromethane, tetrahydrofuran or DMF.
In the invention, the solvent G in the step (4) is one or more of toluene, xylene or DMF.
In the invention, the solvent H in the step (5) is one or more of dichloromethane, trichloromethane or toluene.
In the invention, the solvent I in the step (6) is one or more of tetrahydrofuran, DMF or toluene.
The invention has the beneficial effects that: the raw materials have wide sources, the used raw materials such as tert-butyl methacrylate, a solvent, a catalyst and the like can be industrially produced, and the synthetic method is simple and easy to implement. A spiropyran-containing multi-responsive dendrimer is synthesized. The copolymer can self-assemble into stable nano-micelles in water. The copolymer has both light responsiveness and pH responsiveness, and thus has wide application in biological cell imaging, photoelectric device, molecular logic switch, medicine controlled release and other fields.
Drawings
FIG. 1 is a schematic diagram of the structure of a spiropyran-containing multi-responsive dendrimer prepared in example 1.
Detailed Description
Example 1
6g of 2,3, 3-trimethylindole and 7g of 2-bromoethanol are mixed in methanol and stirred under reflux for 4 h. Standing the mixture at room temperature for 3 hr, filtering to obtain solid, washing the crude product with acetone, dissolving the solid in NaOH aqueous solution, extracting with chloroform for three times, mixing the organic phases, and adding anhydrous Na2SO4Drying, evaporating the solvent, dissolving the residual product and 4g of 5-nitro salicylaldehyde in dichloromethane, reacting at 40 ℃ for 2h, pouring the hot reaction liquid into 100 mL of distilled water, filtering, and drying to obtain the spiropyran SP.
0.5g of the dendritic polyester and 10g of caprolactone are reacted at 40 ℃ for 1h under vacuum and cooled to room temperature. 1ml of stannous octoate solution in toluene is added to react for 12h under vacuum condition, and the mixture is cooled to room temperature. Adding dichloromethane to dissolve, and precipitating with methanol to obtain dendritic polycaprolactone. Dissolving 7g of dendritic polycaprolactone by using dichloromethane, adding 2ml of triethylamine and 2ml of dibromo isobutyryl bromide, and reacting at normal temperature for 30 hours to obtain the dendritic macromolecular initiator. The obtained dendrimer initiator 200mg CuBr and 4ml methacrylate were ATRP reacted in toluene for 10 hours to obtain HPs-Star-PCL-b-PtbMA. HPs-Star-PCL-b-PtbMA was dissolved in chloroform, and 2ml of trifluoroacetic acid was added to react for 2 hours to obtain HPs-Star-PCL-b-PMAA. 2g HPs-Star-PCL-b-PMAA and 0.5g hydroxy spiropyran were added to 0.5g DCC,05g DMAP was reacted in DMF for 3h to obtain the final product.
Example 2
8g of 2,3, 3-trimethylindole and 6g of 2-bromoethanol are mixed in methanol under reflux and stirred for 5 h. And then standing the mixture at room temperature for 4h, filtering to obtain a solid, washing a crude product by tetrahydrofuran, dissolving the solid in an aqueous solution of NaOH, extracting the solid for three times by using chloroform, combining organic phases, drying by using anhydrous Na2SO4, evaporating the solvent, dissolving the residual product and 5g of 5-nitro salicylaldehyde in dichloromethane, reacting at 60 ℃ for 2h while the reaction solution is hot, pouring the reaction solution into 150 mL of distilled water, filtering, and drying to obtain the spiropyran SP.
0.2g of the dendritic polyester and 11g of caprolactone are reacted under vacuum at 180 ℃ for 4h and cooled to room temperature. 1.1 ml of stannous octoate solution in toluene is added to react for 12h under vacuum condition, and then cooled to room temperature. Adding trichloromethane for dissolving, and then precipitating with diethyl ether to obtain the dendritic polycaprolactone. Dissolving 6g of dendritic polycaprolactone by using dichloromethane, adding 2ml of triethylamine and 1ml of dibromo isobutyryl bromide, and reacting at normal temperature for 20 hours to obtain the dendritic macromolecular initiator. The obtained dendrimer initiator 250mg CuBr and 4ml methacrylate were ATRP reacted in toluene for 14h to obtain HPs-Star-PCL-b-PtbMA. HPs-Star-PCL-ion dissolved by chloroformbPtbMA, 2.5 ml trifluoroacetic acid was added and reacted for 2h to obtain HPs-Star-PCL-b-PMAA. 2g HPs-Star-PCL-b-PMAA and 0.5g hydroxy spiropyran are added into 0.5g DCC,05g DMAP is reacted in toluene for 4h to obtain the final product.
Example 3
8g of 2,3, 3-trimethylindole and 6g of 2-bromoethanol are mixed in ethanol and stirred under reflux for 6 h. And then standing the mixture at room temperature for 2h, filtering to obtain a solid, washing the crude product with acetone, dissolving the solid in an aqueous solution of NaOH, extracting with chloroform for three times, combining organic phases, drying with anhydrous Na2SO4, evaporating the solvent, dissolving the residual product and 5g of 5-nitro salicylaldehyde in tetrahydrofuran, reacting at 60 ℃ for 2h, pouring the reaction solution into 250 mL of distilled water while the reaction solution is hot, filtering, and drying to obtain the spiropyran SP.
0.6g of the dendritic polyester and 11g of caprolactone are reacted at 100 ℃ for 4h under vacuum and cooled to room temperature. 1.1 ml of stannous octoate solution in toluene is added to react for 12h under vacuum condition, and then cooled to room temperature. Adding tetrahydrofuran to dissolve, and then precipitating by using normal hexane to obtain the dendritic polycaprolactone. Dissolving 5g of dendritic polycaprolactone by using dichloromethane, adding 2ml of triethylamine and 1ml of dibromo isobutyryl bromide, and reacting at normal temperature for 22 hours to obtain the dendritic macromolecular initiator. The obtained dendrimer initiator 230mg CuBr and 4ml methacrylate were ATRP reacted in xylene for 13h to obtain HPs-Star-PCL-b-PtbMA. HPs-Star-PCL-b-PtbMA was dissolved in toluene, and 1.5ml of trifluoroacetic acid was added to react for 6 hours to obtain HPs-Star-PCL-b-PMAA. 2g HPs-Star-PCL-b-PMAA and 0.3g hydroxy spiropyran are added into 0.4g DCC,05g DMAP is reacted in toluene for 7h to obtain the final product.
Example 4
5.6g of 2,3, 3-trimethylindole and 6.7g of 2-bromoethanol are mixed in ethyl acetate and stirred under reflux for 5 h. Then the mixture is kept stand for 4h at room temperature, solid is obtained by filtration, the solid is taken out after the crude product is washed by DMF and is dissolved in NaOH aqueous solution, chloroform is used for extraction for three times, organic phases are combined, anhydrous Na2SO4 is dried, and after the solvent is evaporated, the product and 5 are remained. 5g of 5-nitro salicylaldehyde is dissolved in dichloromethane, reacted at 110 ℃ for 2h, and the reaction liquid is poured into 170 mL of distilled water while the reaction liquid is hot, filtered and dried to obtain the spiropyran SP.
3g of dendritic polyester and 11g of caprolactone were reacted at 112 ℃ for 4.5h under vacuum and cooled to room temperature. 1.3 ml of stannous octoate solution in toluene is added to react for 12h under vacuum condition, and then cooled to room temperature. Adding trichloromethane for dissolving, and then precipitating with methanol to obtain the dendritic polycaprolactone. Dissolving 6g of dendritic polycaprolactone by using dichloromethane, adding 2ml of triethylamine and 1ml of dibromo isobutyryl bromide, and reacting at normal temperature for 18h to obtain the dendritic macromolecular initiator. The resulting dendrimer initiator, 200mg CuBr, and 3.4ml of methacrylate were reacted in toluene by ATRP for 11.5h to give HPs-Star-PCL-b-PtbMA. HPs-Star-PCL-b-PtbMA was dissolved in dichloromethane, and 2.5 ml of trifluoroacetic acid was added to react for 2h to obtain HPs-Star-PCL-b-PMAA. 2g HPs-Star-PCL-b-PMAA and 0.5g hydroxy spiropyran were added to 0.5g DCC,05g DMAP in DMF and reacted for 2.5h to give the final product.
Example 5
8g of 2,3, 3-trimethylindole and 6 are added. 5g of 2-bromoethanol is mixed in ethanol, refluxed and stirred for 5 hours. And then standing the mixture at room temperature for 4h, filtering to obtain a solid, washing the crude product with DMF, dissolving the solid in NaOH aqueous solution, extracting with chloroform for three times, combining organic phases, drying with anhydrous Na2SO4, evaporating the solvent, dissolving the residual product and 4g of 5-nitro salicylaldehyde in dichloromethane, reacting at 65 ℃ for 3h, pouring the reaction solution into 220 mL of distilled water while the reaction solution is hot, filtering, and drying to obtain the spiropyran SP.
0.4g of the dendritic polyester and 10.5g of caprolactone are reacted at 140 ℃ for 4.5h under vacuum and cooled to room temperature. 1.1 ml of stannous octoate solution in toluene is added to react for 5h under vacuum condition, and then cooled to room temperature. Adding dichloromethane to dissolve, and precipitating with diethyl ether to obtain the dendritic polycaprolactone. Dissolving 4.5g of dendritic polycaprolactone by using tetrahydrofuran, adding 1ml of triethylamine and 1.5ml of dibromo isobutyryl bromide, and reacting at normal temperature for 10 hours to obtain the dendritic macromolecular initiator. 250mg of CuBr and 3.5ml of methacrylate are subjected to ATRP reaction in xylene for 14h to obtain HPs-Star-PCL-b-PtbMA. HPs-Star-PCL-b-PtbMA was dissolved in chloroform, and 1.5ml of trifluoroacetic acid was added to react for 2 hours to give HPs-Star-PCL-b-PMAA. 2g HPs-Star-PCL-b-PMAA and 0.5g hydroxy spiropyran are added into 0.5g DCC,05g DMAP is reacted in tetrahydrofuran for 4h to obtain the final product.
Claims (1)
1. A preparation method of a spiropyran-containing multi-responsiveness dendritic polymer is characterized by comprising the following specific steps:
(1) mixing 2,3, 3-trimethylindole and 2-bromoethanol in a solvent A, refluxing and stirring for 1-24 hours to obtain a mixture; then standing the mixture at room temperature for 1-12 h, filtering to obtain a solid, washing the crude product with a solvent B, dissolving the solid in an NaOH aqueous solution, extracting with chloroform for three times, combining organic phases, and adding anhydrous Na2SO4Drying, evaporating the solvent, dissolving the residual product and 5-nitro salicylaldehyde in the solvent C, reacting at 40-120 ℃ for 2-8 h, pouring the hot reaction liquid into 100-400 mL of distilled water, filtering, and drying to obtain the final productA hydroxy spiropyran;
(2) reacting dendritic polyester and caprolactone at 40-180 ℃ for 1-4 h in a vacuum environment, and cooling to room temperature; adding a toluene solution of stannous octoate, reacting for 12-24 h under a vacuum condition, and cooling to room temperature; adding a solvent D for dissolution, and then precipitating by using a precipitator E to obtain dendritic polycaprolactone;
(3) dissolving dendritic polycaprolactone by using a solvent F, adding triethylamine and dibromo isobutyryl bromide, and reacting at normal temperature for 30 hours to obtain a dendritic macromolecular initiator;
(4) carrying out ATRP reaction on the obtained dendritic macromolecular initiator, CuBr and tert-butyl methacrylate in a solvent G to obtain HPs-Star-PCL-b-PtBMA;
(5) dissolving HPs-Star-PCL-b-PtBMA obtained in the step (4) with a solvent H, and adding trifluoroacetic acid to obtain HPs-Star-PCL-b-PMAA;
(6) adding the HPs-Star-PCL-b-PMAA obtained in the step (5) and the hydroxy spiropyran obtained in the step (1) into DCC and DMAP to react in a solvent I for 3-12 h to obtain a final product;
wherein: the solvent A is one or more of methanol, ethanol or ethyl acetate, the solvent B is one or more of tetrahydrofuran, DMF or acetone, the solvent C is one or more of dichloromethane, trichloromethane or acetone, the solvent D is one or more of dichloromethane, trichloromethane or tetrahydrofuran, the precipitating agent E is one or more of methanol, diethyl ether or n-hexane, the solvent F is one or more of dichloromethane, tetrahydrofuran or DMF, the solvent G is one or more of toluene, xylene or DMF, the solvent H is one or more of dichloromethane, trichloromethane or toluene, and the solvent I is one or more of tetrahydrofuran, DMF or toluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810160635.6A CN108424482B (en) | 2018-02-27 | 2018-02-27 | Spiropyran-containing multi-responsiveness dendritic polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810160635.6A CN108424482B (en) | 2018-02-27 | 2018-02-27 | Spiropyran-containing multi-responsiveness dendritic polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108424482A CN108424482A (en) | 2018-08-21 |
| CN108424482B true CN108424482B (en) | 2020-06-02 |
Family
ID=63157260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810160635.6A Expired - Fee Related CN108424482B (en) | 2018-02-27 | 2018-02-27 | Spiropyran-containing multi-responsiveness dendritic polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108424482B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456460B (en) * | 2018-11-01 | 2020-12-18 | 武汉纺织大学 | Force-sensitive color-changing self-repairing intelligent polyester elastomer and preparation method thereof |
| CN112126322A (en) * | 2020-08-27 | 2020-12-25 | 苏州宏琦材料科技有限公司 | Preparation method of responsive structural color optical variable anti-counterfeiting coating |
| CN113072689B (en) * | 2021-03-26 | 2022-12-23 | 郑州师范学院 | Method for preparing degradable polymer based on light control of spiropyran and application |
| CN113897247B (en) * | 2021-10-13 | 2023-11-21 | 曲阜师范大学 | Preparation of biodiesel by photo-magnetic dual-response emulsion method |
| CN114014868A (en) * | 2021-12-02 | 2022-02-08 | 江苏华昌织物有限公司 | Preparation method of spiropyran compound for light conversion agent |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311862A (en) * | 1998-07-30 | 2001-09-05 | 美国拜尔公司 | Photochromic ophthalmic lens |
| CN1738842A (en) * | 2003-03-20 | 2006-02-22 | 株式会社德山 | Polymerization curable composition |
| CN101311244A (en) * | 2007-05-21 | 2008-11-26 | 中国科学院化学研究所 | Photo-acid polymer-doped spirooxazine or spiropyran reversible photochromic film, preparation method and use thereof |
| CN101704921A (en) * | 2008-06-27 | 2010-05-12 | 上海金发科技发展有限公司 | Method for synthesizing spiropyran polymers |
| CN103597006A (en) * | 2011-06-03 | 2014-02-19 | 薇薇美德实验室欧洲有限公司 | Photochromic polymers |
| CN105542066A (en) * | 2016-01-05 | 2016-05-04 | 中南大学 | Preparation method for spiropyran-based random copolymer P(SPMA-co-MAA) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090047517A1 (en) * | 2007-06-27 | 2009-02-19 | Francesco Caruso | Multilayer polymer films |
-
2018
- 2018-02-27 CN CN201810160635.6A patent/CN108424482B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311862A (en) * | 1998-07-30 | 2001-09-05 | 美国拜尔公司 | Photochromic ophthalmic lens |
| CN1738842A (en) * | 2003-03-20 | 2006-02-22 | 株式会社德山 | Polymerization curable composition |
| CN101311244A (en) * | 2007-05-21 | 2008-11-26 | 中国科学院化学研究所 | Photo-acid polymer-doped spirooxazine or spiropyran reversible photochromic film, preparation method and use thereof |
| CN101704921A (en) * | 2008-06-27 | 2010-05-12 | 上海金发科技发展有限公司 | Method for synthesizing spiropyran polymers |
| CN103597006A (en) * | 2011-06-03 | 2014-02-19 | 薇薇美德实验室欧洲有限公司 | Photochromic polymers |
| CN105542066A (en) * | 2016-01-05 | 2016-05-04 | 中南大学 | Preparation method for spiropyran-based random copolymer P(SPMA-co-MAA) |
Non-Patent Citations (4)
| Title |
|---|
| Environmental effects on mechanochemical activation of spiropyran in linear PMMA;Beiermann, Brett A，等;《Journal of Material Chemistry》;20110531;第21卷(第23期);第8443-8447页 * |
| Interaction between dispersed photochromic compound and polymer matrix;Jeng-ShyongLi;《EUROPEAN POLYMER JOURNAL 》;20030831;第39卷(第8期);第1693-1700页 * |
| Reversible Fluorescence Switching of Spiropyran-Conjugated Biodegradable Nanoparticles for Super-Resolution Fluorescence Imaging;Zhu Ming Qiang,等;《Macromolecules》;20140311;第47卷(第5期);第1543-1552页 * |
| 含螺吡喃嵌段聚合物的合成及其光敏性能研究;张磊，等;《2013年全国高分子学术论文报告会论文摘要集》;20131012;第17页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108424482A (en) | 2018-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108424482B (en) | Spiropyran-containing multi-responsiveness dendritic polymer and preparation method thereof | |
| Zhang et al. | Efficient fabrication of photosensitive polymeric nano-objects via an ingenious formulation of RAFT dispersion polymerization and their application for drug delivery | |
| Sehlinger et al. | Passerini and Ugi multicomponent reactions in polymer science | |
| CN103524751B (en) | A kind of preparation method of double-sensitivity cyclodextrin supermolecule aggregate | |
| Blasco et al. | Light induced molecular release from vesicles based on amphiphilic linear-dendritic block copolymers | |
| Yuan et al. | Light-and pH-dually responsive dendrimer-star copolymer containing spiropyran groups: synthesis, self-assembly and controlled drug release | |
| WO1985000372A1 (en) | Biodegradable polypeptide and utilization thereof for the progressive release of drugs | |
| CN101935373B (en) | Preparation method of multi-sensitivity photosensitive polyamphoteric electrolyte micelle | |
| Cui et al. | Photo-responsive polymers: properties, synthesis and applications | |
| CN113773539B (en) | Preparation method of pseudopolyrotaxane film and pseudopolyrotaxane film prepared by preparation method | |
| Xiong et al. | Photoresponsive polymers | |
| CN110664751A (en) | PH responsive polymer nano micelle and preparation and application thereof | |
| Zhang et al. | Schizophrenic poly (ε-caprolactone) s: synthesis, self-assembly and fluorescent decoration | |
| CN108641092B (en) | Preparation method of supramolecular polymer composite micelle based on hydrogen bond | |
| Qiu et al. | Recyclable DMAP-Functionalized polymeric nanoreactors for highly efficient acylation of alcohols in aqueous systems | |
| He et al. | Sodium Bis (acyl) phosphane oxide (SBAPO): An efficient photoinitiator for blue light initiated aqueous RAFT dispersion polymerization | |
| Chamsaz et al. | Photoresponsive polyesters by incorporation of alkoxyphenacyl or coumarin chromophores along the backbone | |
| CN103467746B (en) | A kind of amphipathic nature polyalcohol and preparation method thereof | |
| CN111662406B (en) | Intelligent response type branched copolymer containing metastable state photoacid and preparation method thereof | |
| CN101239966B (en) | Method for preparing annular aliphatic carbonic ester containing cinnamoyloxy group and polymers thereof | |
| CN109384869B (en) | Fluorine-containing azobenzene amphiphilic polymer, visible light response polymer nanotube and preparation method thereof | |
| JP2665522B2 (en) | New alpha-oxyacid polymer | |
| Zhang et al. | Synthesis and characterization of star-shaped block copolymer sPCL-b-PEG-GA | |
| CA2859134A1 (en) | Substituted phenacyl molecules and photoresponsive polymers | |
| Liu et al. | Self‐assembled, fluorescent polymeric micelles of a graft copolymer containing carbazole for thermo‐controlled drug delivery in vitro |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200602 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |