Grignard-based anionic ring-opening polymerization of propylene oxide activated by triisobutylaluminum

2,5-Diketopiperazines (DKPs) are the smallest cyclic dipeptides found in nature with various attractive properties. In this study, we have demonstrated the successful modification of proline-based DKPs using anionic ring-opening polymerization (AROP) as a direct approach. Four different proline-based DKPs with various side chains and increasing steric hindrance were used as initiating species for the polymerization of 1,2-epoxybutane or ethoxyethyl glycidyl ether in the presence of t-BuP 4 phosphazene base. The addition of a Lewis acid, tri-isobutyl aluminum, to the reaction mixture strongly decreased the occurrence of side reactions. Impact of the DKP side-chain functionalities on molar mass control and dispersity was successfully evidenced.

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“…MeTHF was chosen as a polymerization solvent instead of THF to avoid the complexation with i-Bu 3 Al. 33…”

Section: Resultsmentioning

confidence: 99%

Modification of proline‐based 2,5‐diketopiperazines by anionic ring‐opening polymerization

Tezgel

Puchelle

et al. 2019

J. Polym. Sci. Part A: Polym. Chem.

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“…This result is in agreement with Carlotti and coworkers who showed that THF is not a suitable solvent for epoxide polymerization in the presence of triisobutylaluminum due to competitive complexation. 27 Later, we used MeTHF as a solvent. Compared to THF, the methyl group of MeTHF decreases its polarity and thus the aforementioned interaction should be reduced.…”

Section: Figure 3 Sec Profiles In Dmf Of Poly(glycidylphthalimide)mentioning

confidence: 99%

Anionic ring‐opening polymerization of N‐glycidylphthalimide: Combination of phosphazene base and activated monomer mechanism

Rassou

Illy

Tezgel

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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Anionic ring‐opening polymerization of glycidyl phthalimide, initiated with alcohol–phosphazene base systems and based on monomer activation with a Lewis acid (iBu3Al), has been studied. No propagation occurred for initiator: iBu3Al ratios less or equal to 1:3. For larger Lewis acid amounts, the first anionic ring‐opening polymerizations of glycidyl phthalimide were observed. Polymers were carefully characterized by NMR, MALDI‐TOF mass spectrometry, and size exclusion chromatography and particular attention was given to the detection of eventual transfer or side‐reactions. However, polymer precipitation and transfer reaction to aluminum derivative were detrimental to monomer conversion, polymerization control, and limited polymer chain molar masses. The influence of reaction temperature and solvent on polymer precipitation and transfer reactions was studied and reaction conditions have been optimized leading to afford end‐capped poly(glycidyl phthalimide) with narrow molar mass distributions. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1091–1099

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“…In the work reported here, self‐assembled macromolecular micelles of the triblock energetic copolymer PLA n ‐ b ‐GAP m ‐ b ‐PS h ( n , m and h denote the number of repeat units in the copolymer chain) were synthesized for obtaining a controllable porous energetic skeleton of nano‐energetic materials. Atom‐transfer radical polymerization (ATRP) of styrene with the energetic macroinitiator GAP‐Br firstly generated the GAP‐ b ‐PS diblock copolymer, which then further participated in the ring‐opening polymerization of d,l ‐lactide to furnish the eventual PLA‐ b ‐GAP‐ b ‐PS triblock copolymer. The block ratio ( f PS,PLA ) could be controlled by adjusting the molecular weight of the PS and PLA chains.…”

Section: Introductionmentioning

confidence: 99%

Amphiphilic block copolymer poly(lactic acid)‐block‐(glycidylazide polymer)‐block‐polystyrene: synthesis and self‐assembly

Dong

Liu

et al. 2017

Polymer International

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The triblock energetic copolymer poly(lactic acid)‐block‐(glycidylazide polymer)‐block‐polystyrene (PLA‐b‐GAP‐b‐PS) was synthesized successfully through atom‐transfer radical polymerization (ATRP) of styrene and ring‐opening polymerization of d,l‐lactide. The energetic macroinitiator GAP‐Br, which was made from reacting equimolar GAP with α‐bromoisobutyryl bromide, firstly triggered the ATRP of styrene with its bromide group, and then the hydroxyl group on the GAP end of the resulting diblock copolymer participated in the polymerization of lactide in the presence of stannous octoate. The triblock copolymer PLA‐b‐GAP‐b‐PS had a narrow distribution of molecular weight. In the copolymer, the PS block was solvophilic in toluene and improved the stability of the structure, the PLA block was solvophobic in toluene and served as the sacrificial component for the preparation of porous materials, and GAP was the basic and energetic material. The three blocks of the copolymer were fundamentally thermodynamically immiscible, which led to the self‐assembly of the block copolymer in solution. Further studies showed that the concentration and solubility of the copolymer and the polarity of the solvent affected the morphology and size of the micelles generated from the self‐assembly of PLA‐b‐GAP‐b‐PS. The micelles generated in organic solvents at 10 mg mL−1 copolymer concentration were spherical but became irregular when water was used as a co‐solvent. The spherical micelles self‐assembled in toluene had three distinct layers, with the diameter of the micelles increasing from 60 to 250 nm as the concentration of the copolymer increased from 5 to 15 mg L−1. © 2017 Society of Chemical Industry

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Grignard-based anionic ring-opening polymerization of propylene oxide activated by triisobutylaluminum

Cited by 14 publications

References 48 publications

Modification of proline‐based 2,5‐diketopiperazines by anionic ring‐opening polymerization

Modification of proline‐based 2,5‐diketopiperazines by anionic ring‐opening polymerization

Anionic ring‐opening polymerization of N‐glycidylphthalimide: Combination of phosphazene base and activated monomer mechanism

Amphiphilic block copolymer poly(lactic acid)‐block‐(glycidylazide polymer)‐block‐polystyrene: synthesis and self‐assembly

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