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A kind of linear comb fluorescent polylactic acid and its preparation method

A polylactic acid and linear technology, applied in the field of linear comb-shaped fluorescent polylactic acid and its preparation, can solve the problems of harsh reaction conditions, low biological activity, limited application, poor controllability, etc., and achieve simple functionalization methods and mild synthesis reaction conditions High efficiency, improved polymer properties and effects of fluorescence developing efficiency

Active Publication Date: 2021-09-24
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] At present, the low reactivity and biological activity of the most commonly used polylactic acid (PLA) material itself limits its further application in biological response, tracking, and regulation of degradation and release. Therefore, functional modification and chemical Modification has become one of the most important research directions in the field of biomedical materials
Commonly used functional modification methods include monomer modification and post-functionalization of the main chain. The process is relatively complicated, the reaction conditions are harsh, and the controllability is poor. Therefore, the functional modification of the initiator and the end modification become crucial. important

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0014] Preparation of hydroxylated linear liquid polybutadiene: using classic ionic polymerization method, using cyclohexane as solvent, n-butyllithium as initiator and silicon tetrachloride as coupling agent to prepare linear liquid polybutadiene, The number average molecular weight of polybutadiene before coupling is 1600g / mol, and the number average molecular weight of linear liquid polybutadiene after coupling is 6515g / mol (using gel permeation chromatography GPC test), molecular weight distribution index (referred to as PDI , the same below) is 1.11. Add 3.6g of the above-mentioned linear liquid polybutadiene into a 250mL reactor and dissolve it in 150mL of toluene, turn on the stirring and temperature, add 1.25g of 98% formic acid when the temperature rises to 40°C, and add 3.02g of it dropwise within 30min The hydrogen peroxide of 30% is washed to neutrality with deionized water after reacting for 2h, and the solvent is removed by rotary evaporation to obtain a transpar...

Embodiment 2

[0018] Preparation of linear comb polylactic acid: normal temperature and pressure, under the protection of inert gas argon, 3 g of L-lactide, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) 0.016g (calculated according to the molar ratio of TBD and monomer is 1:200), 0.98g of the hydroxylated linear liquid polybutadiene initiator synthesized in Example 1 was added in 10mL of dichloromethane, and reacted for 1h at 25°C After adding benzoic acid to terminate the reaction, the linear comb-like polylactide is obtained after treatment. Product M n 14×10 4 g / mol, PDI is 1.39; the hydroxyl initiation efficiency is 48.7%, and the number of arms is 22.

Embodiment 3

[0020] Preparation of linear comb polylactic acid: under normal temperature and pressure, under the protection of inert gas argon, 5 g of racemic lactide, nitrogen methyl-1,5,7-triazabicyclo[4.4.0]decane- 5-ene 0.025g (wherein the molar concentration of racemic lactide monomer is calculated as 1:200), the hydroxylated linear liquid polyisoprene initiator 1g synthesized in Example 1 is added in 10mL toluene, in- After reacting at 20°C for 10 h, benzoic acid was added to terminate the reaction, and linear comb polylactide was obtained after treatment. Product M n 2.1×10 4 g / mol, PDI is 1.28; hydroxyl initiation efficiency is 91%, and the number of arms is 12.

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Abstract

A linear comb-like fluorescent polylactic acid and its preparation method belong to the technical field of polymer materials, and its structure is: the main chain is a linear macromolecular initiator residue, the side chain is polylactic acid, and the end of the side chain is a fluorescent functional group; The number average molecular weight of the linear comb fluorescent polylactic acid is 1×10 4 -50×10 4 g / mol, the number average molecular weight per arm is 0.1×10 4 -2×10 4 g / mol; the linear macromolecular initiator is a linear hydroxylated polymer, the number of hydroxyl groups of the linear macromolecular initiator is 8‑60, and the number average molecular weight is 0.1×10 4 -2×10 4 g / mol; the fluorescent functional group is a small fluorescent molecule containing a carboxyl group, and the capping rate of the small fluorescent molecule is 10%‑100%. First, a linear hydroxylated polymer initiator was synthesized by an active anion reaction, and an organic base was used as a catalyst to catalyze the ring-opening polymerization of lactide to synthesize a kind of linear comb-like polylactic acid and a fluorescent functional group for grafting reaction to prepare a linear comb highly branched fluorescent polylactic acid. The functionalization method is simple, the synthesis reaction conditions are mild, and the linear comb-like highly branched structure effectively improves the performance of the polymer and the fluorescence developing efficiency.

Description

technical field [0001] The invention belongs to the technical field of polymer materials, and relates to a class of linear comb-shaped fluorescent polylactic acid and a preparation method thereof. Background technique [0002] Aliphatic polyester is renewable, biodegradable, biocompatible and absorbable, and is an environmentally friendly green polymer material, which has a wide range of applications in the field of biomedicine, especially as a controlled release of drugs. drug delivery carrier. Due to the complexity and diversity of polymer structures, polymer materials can be endowed with more superior properties by changing the structure and composition of polymers to expand their application range. The development trend of polymer structure is from linear structure to branched structure. Most of the currently synthesized biodegradable aliphatic polyesters have linear, linear, dendritic and hyperbranched structures, and most of them have disadvantages such as low molecu...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G63/91C08G63/06C09K11/06
CPCC08G63/06C08G63/912C09K11/06C09K2211/14C09K2211/145
Inventor 冷雪菲李杨边宇飞魏志勇王艳色
Owner DALIAN UNIV OF TECH
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