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
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- 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
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- 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
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- 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
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- 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
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- General Chemical & Material Sciences (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
本发明涉及一种含有螺吡喃的多重响应性的树枝状聚合物的制备方法。用树枝状聚酯和己内酯通过开环聚合制备树枝状聚己内酯，把得到的树枝状聚己内酯和二溴异丁酰溴以及三乙胺反应得到树枝状大分子引发剂，用大分子引发剂和甲基丙烯酸叔丁酯通过原子转移自由基聚合得到HPs‑Star‑PCL‑b‑PtbMA,将得到的产物经过水解得到HPs‑Star‑PCL‑b‑PMAA,把羟基螺吡喃和HPs‑Star‑PCL‑b‑PMAA通过酯化反应的到HPs‑Star‑PCL‑b‑PMAA‑SP。通过自组装形成胶束，本发明制备的胶束具有PH响应性和光响应性。通过紫外可见光照射或者酸碱性进行可逆调节，在生物细胞成像，光电器件，分子逻辑开关，药物控制释放等领域具有广泛应用。
The present invention relates to a preparation method of a multi-responsive dendrimer containing spiropyran. Use dendritic polyester and caprolactone to prepare dendritic polycaprolactone by ring-opening polymerization, react the obtained dendritic polycaprolactone with dibromoisobutyryl bromide and triethylamine to obtain a dendritic macromolecular initiator, and use Macroinitiator and tert-butyl methacrylate obtain HPs-Star-PCL- b -PtbMA through atom transfer radical polymerization, the product obtained is obtained through hydrolysis to obtain HPs-Star-PCL- b -PMAA, the hydroxyspiropyran and HPs‑Star‑PCL‑ b ‑PMAA by esterification to HPs‑Star‑PCL‑ b ‑PMAA‑SP. Through self-assembly to form micelles, the micelles prepared by the present invention have pH responsiveness and light responsiveness. It can be reversibly regulated by UV-visible light irradiation or acid and alkalinity, and has a wide range of applications in biological cell imaging, optoelectronic devices, molecular logic switches, drug controlled release and other fields.
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.
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