Ring gradient copolymers as amphiphiles in their ternary blends with two linear homopolymers

Sun, Dachuan; Cho, Junhan

doi:10.1016/j.polymer.2015.04.023

Cited by 12 publications

(6 citation statements)

References 55 publications

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“…The distribution functions satisfied the modified diffusion equation for the Gaussian chains subjected to hypothetical external potentials

, or

, which transferred the effect of

on chain conformations to the partition functions. The conventional SCFT method [ 22 , 23 , 24 ] was employed to derive q and

. The free-energy density

for the incompressible copolymer melt was given as:

where

had its usual meaning of thermal energy.…”

Section: Model and Methodsmentioning

confidence: 99%

Influences of the Periodicity in Molecular Architecture on the Phase Diagrams and Microphase Transitions of the Janus Double-Brush Copolymer with a Loose Graft

Sun

Yang

2022

Polymers

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The backbone of the Janus double-brush copolymer may break during long-term service, but whether this breakage affects the self-assembled phase state and microphase transitions of the material is still unknown. For the Janus double-brush copolymers with a periodicity in molecular architecture ranging from 1 to 10, the influences of the architectural periodicity on their phase diagrams and order–disorder transitions (ODT) were investigated by the self-consistent mean field theory (SCFT). In total, nine microphases with long-range order were found. By comparing the phase diagrams between copolymers of different periodicity, a decrease in periodicity or breakage along the copolymer backbone had nearly no influence on the phase diagrams unless the periodicity was too short to be smaller than 3. For copolymers with neutral backbones, a decrease in periodicity or breakage along the copolymer backbone reduced the critical segregation strengths of the whole copolymer at ODT. The equations for the critical segregation strengths at ODT, the architectural periodicity, and the volume fraction of the backbone were established for the Janus double-brush copolymers. The theoretical calculations were consistent with the previous theoretical, experimental, and simulation results.

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“…The distribution functions satisfied the modified diffusion equation for the Gaussian chains subjected to hypothetical external potentials

, or

, which transferred the effect of

on chain conformations to the partition functions. The conventional SCFT method [ 22 , 23 , 24 ] was employed to derive q and

. The free-energy density

for the incompressible copolymer melt was given as:

where

had its usual meaning of thermal energy.…”

Section: Model and Methodsmentioning

confidence: 99%

Influences of the Periodicity in Molecular Architecture on the Phase Diagrams and Microphase Transitions of the Janus Double-Brush Copolymer with a Loose Graft

Sun

Yang

2022

Polymers

Self Cite

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“…22,23 Due to this behavior, amphiphilic copolymers can be found in several biomedical applications including tissue engineering, drug delivery, carriers for gene therapy, and cell encapsulation. [29][30][31][32][33][34] In general, gradient and block copolymers allow many applications, such as stabilizers for emulsions, 35 compatibilizers of immiscible polymer blends, [36][37][38] thermoplastic elastomers, 39,40 damping materials, 41,42 and multi-shape memory materials. 43 An experimental bottleneck for copolymer precision synthesis is the complete characterization of the monomer sequences per chain with only access to average segment lengths and overall comonomer amounts in specific cases.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Multi-angle evaluation of kinetic Monte-Carlo simulations as tool to evaluate the distributed monomer composition in gradient copolymer synthesis

Conka,

Marien,

Van Steenberge

et al. 2023

React. Chem. Eng.

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“…A very attractive aspect of gradient copolymers is that their properties can be optimized by finetuning the copolymer structure. One of the most common application is as compatibilizers for immiscible polymer blends [49,60,61,[87][88][89]. Multiple reports have experimentally shown the impact of the incorporation of gradient copolymers on mixing in otherwise immiscible homopolymer blends.…”

Section: An Overview Of the Applications Of Gradient Copolymersmentioning

confidence: 99%

“…Gradient copolymers are also expected to possess unique thermal properties, particularly a broad glass transition temperature (Tg) in situations where the corresponding homopolymers have very different glass temperatures [48,50,75,81,86]. Gradient copolymers with their unique chain structures, have applications in many fields, such as compatibilizers of immiscible polymer blends [49,60,61,[87][88][89], stabilizers of emulsions or dispersions [90], thermoplastic elastomers [91,92],…”

Section: Introduction To Gradient Copolymersmentioning

confidence: 99%

Understanding and controlling the structure of thin polymer films used in photolithography

Alam¹

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Line edge roughness (LER) is one of the major impediments to the semiconductor industry achieving the desired device performance and satisfying the goals set by International Technology Roadmap for Semiconductor (ITRS). LER is defined as any sort of unwanted roughness in semiconductor features, and among many other factors, structural heterogeneity of the photoresist materials is one of the sources of LER in photolithographic devices. This gives the motivation to study a new class of copolymer named 'gradient copolymer', which is unique in terms of the copolymer chain structure. The copolymer composition of gradient copolymers changes from one end of the chain to the other gradually, while the copolymer composition is on average constant along the chains for conventional statistical copolymers. In contrast, block copolymers show an abrupt switch in the polymer composition. In this study, statistical, block and gradient copolymers have been synthesized for two different monomer pairs (styreneacrylonitrile and hydroxystyrene t-butyl acrylate) using reversible addition-fragmentation chain transfer (RAFT) and conventional radical polymerization (CvRP) method, and their surface properties extensively studied.The kinetics of copolymerization of styrene (St) and acrylonitrile (AN) by RAFT method was studied in detail. Reactivity ratios of St and AN were determined for nine different feed compositions for RAFT, and the effect of solvent on reactivity ratios was discussed based on the bootstrap model. Batch polymerization of styrene (St) and acrylonitrile (AN) yielded statistical and spontaneous gradient copolymers depending on the monomer feed ratio, and the chain structures were confirmed from the change in the copolymer composition. St-and AN-centered triad distributions were determined using quantitative 13 C NMR. Using the continuous feeding approach, forced gradient St-AN copolymers were prepared, and St-block-AN copolymers synthesized by the chain extension method. Statistical, gradient and block copolymers have also been synthesized for the acetoxystyrenet-butyl acrylate monomer system. The statistical and gradient structures were confirmed from the change in the composition since this pair does not provide any well resolved peaks for different triad sequences in 13 C NMR. Hydroxystyrenet-butyl acrylate (HOST-tBA) copolymers were prepared by selective hydrolysis of 4-acetoxystyrenet-butyl acrylate (AOST-tBA) copolymers.The properties of the both copolymer systems were found to be strongly dependent on the copolymer structure. A unique broad glass transition was observed for the gradient copolymers, which is different from behaviour of the statistical and block copolymers. Surface properties of St-AN statistical, gradient and block copolymer thin films were found to be very different due to the

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Ring gradient copolymers as amphiphiles in their ternary blends with two linear homopolymers

Cited by 12 publications

References 55 publications

Influences of the Periodicity in Molecular Architecture on the Phase Diagrams and Microphase Transitions of the Janus Double-Brush Copolymer with a Loose Graft

Influences of the Periodicity in Molecular Architecture on the Phase Diagrams and Microphase Transitions of the Janus Double-Brush Copolymer with a Loose Graft

Multi-angle evaluation of kinetic Monte-Carlo simulations as tool to evaluate the distributed monomer composition in gradient copolymer synthesis

Understanding and controlling the structure of thin polymer films used in photolithography

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