Fluorescent block-grafted copolymer with temperature sensitivity and preparation method and application thereof

A technology of graft copolymer and graft polymer, which is applied in the field of fluorescent block graft copolymer and its preparation, can solve the problems of regulation performance, uneven particle size distribution of spheres, and large steric hindrance of the inner core, etc., and achieve reaction Mild conditions, high conversion rate, and improved fluorescence response sensitivity

Inactive Publication Date: 2013-05-22
GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] Patent 200610166475.3 discloses a method for synthesizing temperature-sensitive fluorescent nanomaterials. The microspheres with dual responsiveness synthesized by this method are limited to block-type polymers, and the particle size distribution of the spheres is uneven, and the core-shell structure is not obvious; Patent application 201210160087.X discloses the preparation of an environmental pH-responsive polyurethane fluorescent light-emitting medical material, which mainly introduces fluorescent small molecules into the polyurethane main chain to prepare pH-responsive materials, but the material synthesis method belongs to a one-pot method , its performance cannot be adjusted by controlling its structure, which has limitations; patent 201010131134.9 discloses a preparation method of a fluorescent polymer with a hydrophilic shell and a hydrophobic core, but the polymer cannot be well controlled due to the limitation of the synthesis method The degree of polymerization of the inner core, and the inner core itself has a large steric hindrance, which leads to low efficiency of the next addition reaction and affects the performance of the final product; patent 200910183637.8 discloses a comb polymer containing carbazole side chains and its preparation method , but the polymer has not researched or developed other intelligent properties other than fluorescent properties
[0005] To sum up, at present, most of the research and discussion on temperature-sensitive fluorescent materials and their applications at home and abroad stay at the single structure or single performance level of simple binary copolymerization, and seldom involve the multiple functionalization of such materials. , especially the synthesis of block-grafted dual-responsive materials with special configurations is rarely reported

Method used

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  • Fluorescent block-grafted copolymer with temperature sensitivity and preparation method and application thereof
  • Fluorescent block-grafted copolymer with temperature sensitivity and preparation method and application thereof
  • Fluorescent block-grafted copolymer with temperature sensitivity and preparation method and application thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0051] Embodiment 1: PCEMA-b-(PGMA-g-PNIPAM) and its preparation

[0052] (1) Preparation of PCEMA-b-PGMA: 6.32g of fluorescent functional group monomer carbazole ethyl methacrylate (CEMA), 4.92g of glycidyl methacrylate (GMA), 0.111g of initiator 2-bromoisobutyl Ethyl acetate, 0.081g cuprous bromide, 0.025g cuprous bromide and 14mL anisole were added to a 50mL single-port reaction bottle and the bottle mouth was sealed. 0.216g catalyst PMDETA and continue through three cycles once, put it in an oil bath at 65°C for 4 hours, freeze it with liquid nitrogen and dilute it with dichloromethane, then stir and oxidize it for 1 hour, remove the catalyst through neutral alumina, concentrate at room temperature for 30 minutes and then precipitate In 150mL of n-hexane, filter and evaporate the solvent, take the residue and dissolve it with 7mL of tetrahydrofuran and precipitate it with 200mL of n-hexane and circulate it twice, then take the precipitate and dry it under vacuum at room te...

Embodiment 2

[0067] Embodiment 2: PCEMA-b-(PGMA-g-PDNIPAM) and its preparation

[0068] (1) Preparation of PCEMA-b-PGMA: same as step (1) of Example 1;

[0069] (2) Preparation of PDNIPAM: 7.46g of temperature-sensitive monomer N,N-diisopropylacrylamide, 0.28g of chain transfer agent S-dodecyl-S'-(α-methyl-α "-propargyl isopropionate) trisulfide, 0.014g initiator AIBN and 14mL dioxane were added to a 25mL single-necked flask filled with argon and sealed well, after three cycles of gas blowing-freezing-thawing , placed in an oil bath at 75°C for 7 hours, then stopped the reaction in an ice-water bath, distilled under reduced pressure at 45°C to remove most of the dioxane and precipitated in 200mL of cold ether, took the precipitate, dried it at 25°C and dissolved it in 4mL Precipitate in 200mL cold diethyl ether (repeat this operation 3 times), take the precipitate, and dry it in vacuum at room temperature to obtain 5.43g of PDNIPAM;

[0070] The structural formula of PDNIPAM is as follow...

Embodiment 3

[0079] Embodiment 3: PCEMA-b-(PGMA-g-PmPEGMA) and its preparation

[0080] (1) Preparation of PCEMA-b-PGMA: 7.02g of fluorescent functional group monomer carbazole ethyl methacrylate (CEMA), 6.85g of glycidyl methacrylate (GMA), 0.166g of initiator 2-bromoisobutyl Acetate methyl ester, 0.145g cuprous bromide, 0.02g cuprous bromide and 20mL anisole were added to a 50mL single-port reaction bottle, and the bottle mouth was sealed. 0.086g catalyst PMDETA and continue through three cycles once, placed in an oil bath at 70 ° C for 7 hours. Freeze in liquid nitrogen and dilute with dichloromethane, stir and oxidize for 1 h, remove the catalyst through neutral alumina, concentrate at room temperature for 30 min, and precipitate in 200 mL of n-hexane, dissolve the precipitate in 4 mL of tetrahydrofuran and precipitate in 200 mL of n-hexane (repeat the operation 3 times) Finally, take the precipitate and dry it under vacuum at room temperature to obtain 8.42g of fluorescent copolymer;...

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Abstract

The invention discloses a fluorescent block-grafted copolymer with temperature sensitivity and a preparation method and application thereof. According to the fluorescent block-grafted copolymer and the preparation method and application of the fluorescent-block-grafted copolymer, an acrylate monomer containing a fluorophore is copolymerized with methacrylic glyceride through atom transfer radical polymerization to introduce an azide group to an epoxy group on the side chain, and then, a polymer with temperature response is grafted to the copolymer through clicking chemical reaction so as to form the block-grafted copolymer; and the reaction conditions are mild, and the conversion rate is high. The fluorescent block-grafted copolymer and the preparation method and application of the fluorescent block-grafted copolymer have the advantages that the polymer with temperature response is initiatively polymerized with the side chain of the copolymer with a fluorescence effect through grafting, so that the macromolecular polymer not only has fluorescent characteristics, but also the temperature response, side chain length and hydrophilicity strength of the macromolecular polymer can be controlled through adjusting the length of hydrophilic side chains and grafting efficiency, and the controllable adjustment is realized; and the structure of the copolymer is provided with hydrophilic chain segments, so that not only can kernel fluorescent chromophores be protected, but also the chromophores can be gathered together, thereby improving fluorescence response sensitivity.

Description

technical field [0001] The invention belongs to the technical field of polymer materials, and in particular relates to a temperature-sensitive fluorescent block graft copolymer and its preparation method and application. Background technique [0002] With the continuous deepening of research on intelligent polymer materials and the continuous improvement of market demand, the research and development of intelligent polymer materials with dual or even multiple responsiveness has become an important development direction in this field. For temperature-responsive polymers, when the temperature is lower than the critical micelle dissolution temperature, the molecular chain is in a free stretch state, and when the temperature is higher than the critical micelle dissolution temperature, the molecular chain is due to the hydrogen bond between the solvent and the solvent. Or the intermolecular hydrogen bonds are broken to cause shrinkage and aggregation behavior. This kind of polym...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G81/02C08F220/32C08F220/34C08F8/30C08F120/54C08F120/28C08F220/18C08F120/34C09K11/06A61K47/34
Inventor 庞浩蒋冰艳廖兵张磊郑景新刘海露
Owner GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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