Physical Sciences and Mathematics Commons^™

Synthesis Of Block Copolymer Additives For Examining Phase Morphology And Improving Mechanical Properties Of Thermoplastics Elastomers., Bishal Upadhyay

Masters Theses

Polystyrene-block-poly(1,4-butaidene)-block-polystyrene (PS-PB-PS) triblock copolymers are one of the most widely studied thermoplastic elastomers (TPEs) due to their ease of synthesis, non-polar nature, and commercial applicability. Like many block copolymers, incompatibility between PS and PB causes these TPEs to undergo microphase segregation. Many studies have examined the mechanical properties of blends of TPEs and PS homopolymer additives. However, there have been few studies focused on understanding the morphology and mechanical properties of blends of TPEs and copolymer additives with different architectures. Herein, I describe the synthesis of linear and graft copolymer additives based on the random copolymers poly(methyl methacrylate-random-cyclohexyl methacrylate) (PrC). …

Fabrication And Characterization Of Dna Templated Electronic Nanomaterials And Their Directed Placement By Self-Assembly Of Block Copolymers, Dulashani Ruwanthika Ranasinghe Weerakkodige

Theses and Dissertations

Bottom-up self-assembly has the potential to fabricate nanostructures with advanced electrical features. DNA templates have been used to enable such self-assembling methods due to their versatility and compatibility with various nanomaterials. This dissertation describes research to advance several different steps of biotemplated nanofabrication, from DNA assembly to characterization. I assembled different nanomaterials including surfactant-coated Au nanorods, DNA-linked Au nanorods and Pd nanoparticles on DNA nanotubes ~10 micrometer long, and on ~400 nm long bar-shaped DNA origami templates. I optimized seeding by changing the surfactant and magnesium ion concentrations in the seeding solution. After successful seeding, I performed electroless plating on …

Huisgen 1,3-Dipolar Azide-Alkyne Cycloaddition “Click” Reaction In Polymer Synthesis And Curing, Jie Wu

Dissertations

This dissertation’s key focus is on utilizing Huisgen 1,3-dipolar azide-alkyne cycloaddition (AAC) reaction in copolymer synthesis and modification, including thermoplastic block copolymer and commercially available two-component polyurethane system. It can be divided into two major projects, introduced as follows.

The first project involves the development of a modular synthetic approach toward polyisobutylene (PIB)-based triphasic pentablock thermoplastic elastomer with enhanced moisture permeability. This terpolymer consists of a poly(styrene-b-isobutylene-b-styrene) (SIBS) core and appended hydrophilic polymer blocks (HBs). The SIBS core was synthesized via living cationic polymerization (LCP) of isobutylene followed by sequential addition of styrene. AAC was utilized …

Determining Particle Size Of Polymeric Micelles In Thermothickening Aqueous Solutions, Jessica Diane Bruer

MSU Graduate Theses

Many active pharmaceutical ingredients (APIs) are poorly soluble and cause inadequate drug absorption. Soluplus^®, a polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft copolymer, is a commercial excipient (BASF Corp) that enhances the solubility and bioavailability of many APIs. The mechanism of enhancement is related to the ability to form polymeric micelles in solution. These micelles store insoluble APIs in their hydrophobic interior and transport them to targeted sites in the body. An important characteristic of solubility enhancers is the particle size exhibited in solution before and after loading with APIs. This is most commonly determined by dynamic light scattering (DLS) …

Synthesis And Study Of The Micellization Behavior Of A Dual Temperature- And Ph-Responsive Paa-B-Pnipam Block Copolymer, Ehsan Zarshenas Moghadam

Master's Theses and Doctoral Dissertations

Amphiphilic diblock copolymers are composed of hydrophilic and hydrophobic regions. When they are exposed to water, the hydrophobic blocks aggregate to form a hydrophobic core surrounded by hydrophilic regions outside to give a core-shell micelle. These micelles have many potential applications, such as a drug delivery system, surfactants, or nanoreactor. Many studies have been done to optimize the performance of these copolymers. In this thesis work, nine dual temperature- and pH-responsive poly(acrylic acid-block-N-isopropylacrylamide) (PAA-b-PNIPAM) diblock copolymers with different relative chain lengths of the hydrophobic and hydrophilic blocks were synthesized by reversible addition fragmentation chain transfer polymerization. The preliminary results showed …

Hybrid Micellar Network Hydrogels Of Thermosensitive Hydrophilic Triblock Copolymers And Thermosensitive Hairy Nanoparticles, Bin Hu

Doctoral Dissertations

Hybrid micellar network hydrogels, composed of thermosensitive hydrophilic triblock copolymers and thermosensitive polymer brush-grafted nanoparticles (hairy NPs), exhibit intriguing rheological properties. This dissertation work studies thermosensitive hybrid hydrogels with NPs positioned either inside or outside the core of block copolymer micelles.

Chapter 1 is an introduction. Chapter 2 examines the effect of NP’s location on properties of hybrid hydrogels of a thermosensitive ABA triblock copolymer and hairy NPs. Two batches of thermoresponsive polymer brush-grafted silica NPs and an ABA triblock copolymer with thermosensitive outer blocks were prepared. When the lower critical solution temperature (LCST) of hairy NPs was similar to …

Synthetic Approach Towards P3eht-B-Pss Conjugated And Ionic Block Copolymer, Zhaoyuan Liu

LSU Master's Theses

This work is focused on the design, synthesis and characterization of block copolymers (BCPs) containing both conjugated and polyelectrolyte blocks. This type of rod-coil BCP is considered to have microphase separation which is different compared to coil-coil BCPs. The conjugated block used for studies is regioregular poly(3-alkylthiophene) (P3AT), which can be synthesized by Grignard metathesis (GRIM) polymerization. The polyelectrolyte block used is polystyrene sulfonate with well-defined structure, which can be synthesized by atom transfer radical polymerization (ATRP). Chapter II is focused on evaluation of synthetic routes for P3EHT-b-PSS, including using bifunctional initiator to synthesize both blocks, and separately synthesizing end-functionalized …

Novel Thermoplastic Elastomers Based On Benzofulvene: Synthesis And Mechanical Properties, Weiyu Wang

Doctoral Dissertations

Thermoplastic elastomers (TPEs) are of great importance both academically and technologically. Currently TPEs are the predominated form of styrene-diene copolymers. However, these styrenic TPEs have serious limitations in applications, especially at higher temperature, because of their low upper service temperature (UST). The work described in this dissertation aimed to developing thermoplastic elastomers with a higher UST and lower cost.

In order to develop TPEs with a higher UST, we employed benzofulvene, an anionically polymerizable monomer in hydrocarbon solvent at room temperature, as the glassy block and copolymerized it with isoprene to prepare polybenzofulvene-polyisoprene-polybenzofulvene (FIF) triblock copolymers. Among all triblock copolymers …

Nanoscale Surface Patterning And Applications: Using Top-Down Patterning Methods To Aid Bottom-Up Fabrication, Anthony Craig Pearson

Theses and Dissertations

Bottom-up self-assembly can be used to create structures with sub-20 nm feature sizes or materials with advanced electrical properties. Here I demonstrate processes to enable such self-assembling systems including block copolymers and DNA origami, to be integrated into nanoelectronic devices. Additionally, I present a method which utilizes the high stability and electrical conductivity of graphene, which is a material formed using a bottom-up growth process, to create archival data storage devices. Specifically, I show a technique using block copolymer micelle lithography to fabricate arrays of 5 nm gold nanoparticles, which are chemically modified with a single-stranded DNA molecule and used …

Synthesis Of Self-Immolative Monomers And Their Applications In Polymeric Materials, Matthew A. Dewit

Electronic Thesis and Dissertation Repository

Self-immolative spacers are a unique class of molecules employed in a variety of applications, particularly in the biomedical field. Most commonly, they are molecules containing two reactive termini with a capping group at one terminus and a substrate of interest at the other. Upon removal of the capping group, the spacer undergoes an intramolecular reaction that results in its removal from the molecule and liberation of the substrate. These spacers have been extensively studied in monomeric form within prodrugs, as well as to form dendrimers that have been used for applications such as signal amplification, molecular logic gates and amplified …