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Block copolymer brushes are of great interest due to their rich phase behavior and value-added properties compared to homopolymer brushes. Traditional synthesis involves grafting-to and grafting-from methods. In this work, a recently developed “polymer-single-crystal-assisted-grafting-to” method is applied for the preparation of block copolymer brushes on flat glass surfaces. Triblock copolymer poly(ethylene oxide)-b-poly(L-lactide)-b-poly(3-(triethoxysilyl)propyl methacrylate) (PEO-b-PLLA-b-PTESPMA) was synthesized with PLLA as the brush morphology-directing component and PTESPMA as the anchoring block. PEO-b-PLLA block copolymer brushes are obtained by chemical grafting of the triblock copolymer single crystals onto a glass surface. The tethering point and overall brush pattern are determined by the single crystal morphology. The grafting density is calculated to be ~ 0.36 nm-2 from the atomic force microscopy results and is consistent with the theoretic calculation based on the PLLA crystalline lattice. This work provides a new strategy to synthesize well-defined block copolymer brushes.
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Construction of a corresponding empirical model to bridge thermal properties and synthesis of thermoresponsive poloxamines
The thermoresponsive properties of poloxamine (tetra-branch PEO-PPO block copolymer) hydrogels are related to several variables. Of particular interest to this study were the molecular weight of the polymer, the molar ratio between PEO and PPO blocks, and the concentration of the aqueous solution. Accurately controlling the thermoresponsive behaviors of the polymer is critical to the application of such materials; therefore, the structure–property relationship of tetra-branch PEO-PPO block copolymer was studied by synthesis via anionic ring-opening polymerization (AROP). The structure–property relationships were studied by measuring the thermoresponsive behavior via differential scanning calorimetry (DSC) and developing an empirical model which statistically fit the collected data. This empirical model was then used for designing poloxamines that have critical micellization temperatures (CMT) between room temperature and physiological temperature. The model was validated with three polymers that targeted a CMT of 308 K (35°C). The empirical model showed great success in guiding the synthesis of poloxamines showing a temperature difference of less than 3 K between the predicted and the observed CMTs. This study showed a great potential of using an empirical model to set synthesis parameters to control the properties of the polymer products.
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- Award ID(s):
- 2210686
- PAR ID:
- 10541755
- Publisher / Repository:
- UK Limited, trading as Taylor & Francis Group
- Date Published:
- Journal Name:
- Designed Monomers and Polymers
- Volume:
- 27
- Issue:
- 1
- ISSN:
- 1568-5551
- Page Range / eLocation ID:
- 1 to 9
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
-
Accepted Manuscript
- Journal Article:
- https://doi.org/10.1080/15685551.2024.2313268
