The rheology and gelation of bidisperse 1,4-polybutadiene

Roy, Dilip; Giller, C.B.; Hogan, T. E.; Roland, C. M.

doi:10.1016/j.polymer.2015.11.004

Cited by 11 publications

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“…The polymers with tailored were synthesized in ab atch system without the assistance of an external pump.Aunique aspect of this approach is that was tuneable from 1.11 to 1.50 in any segment in diblock, triblock, and multiblock copolymers and in any form of star and brush polymer without segmental or topological restriction. [13][14][15] Thep olymers need to be prepared in multiple independent runs,a nd the blended polymers often have multimodal molecular weight distribution. [1][2][3][4][5][6] Living radical polymerization (LRP) facilitates the synthesis of polymers with small values,a sw ell as pre-determined molecular weights and sophisticated architectures.…”

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confidence: 99%

“…[1][2][3][4][5][6] Living radical polymerization (LRP) facilitates the synthesis of polymers with small values,a sw ell as pre-determined molecular weights and sophisticated architectures. [13][14][15] Thep olymers need to be prepared in multiple independent runs,a nd the blended polymers often have multimodal molecular weight distribution. Several approaches have been developed to manipulate values.Blending polymers with different molecular weights is often applied.…”

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confidence: 99%

“…Several approaches have been developed to manipulate values.Blending polymers with different molecular weights is often applied. [13][14][15] Thep olymers need to be prepared in multiple independent runs,a nd the blended polymers often have multimodal molecular weight distribution. By optimizing the polymerization conditions such as catalyst loadings, initiators,temperatures,and additional chain-transfer agents, the was modulated at 1.1-2.0 in LRP.…”

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Polymer Dispersity Control by Organocatalyzed Living Radical Polymerization

2019

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Molecular weight distribution of polymers,t ermed dispersity (), is af undamental parameter for determining polymer material properties.T his paper reports an ovel approach for controlling by exploiting at emperatureselective radical generation in organocatalyzed living radical polymerization. The polymers with tailored were synthesized in ab atch system without the assistance of an external pump.Aunique aspect of this approach is that was tuneable from 1.11 to 1.50 in any segment in diblock, triblock, and multiblock copolymers and in any form of star and brush polymer without segmental or topological restriction. This approach is amenable to various monomers and free from metals and thus attractive for applications.T he approach also generated polymer brushes on surfaces with tailored .A n interesting finding was that the polymer brushes exhibited unique interaction with external molecules,d epending on the value.Molecular weight distribution of polymers,t ermed dispersity ( = M w /M n ), is afundamental parameter in determining polymer properties such as processability,viscoelasticity,and self-assembly behaviors,w here M w and M n are the weightand number-average molecular weights,r espectively. [1][2][3][4][5][6] Living radical polymerization (LRP) facilitates the synthesis of polymers with small values,a sw ell as pre-determined molecular weights and sophisticated architectures. [7][8][9][10][11][12] However,p olymers with large values are occasionally desired for improved physical properties such as miscibility and processability,a nd the manipulation of in LRP is an important topic but still challenging. Several approaches have been developed to manipulate values.Blending polymers with different molecular weights is often applied. [13][14][15] Thep olymers need to be prepared in multiple independent runs,a nd the blended polymers often have multimodal molecular weight distribution. By optimizing the polymerization conditions such as catalyst loadings, initiators,temperatures,and additional chain-transfer agents, the was modulated at 1.1-2.0 in LRP. [16][17][18] However,t he attained large usually arose from inefficient control in LRP. Thus,t he obtained polymers hardly undergo further chain extension. Recently,F ors et al. elegantly varied and molecular weight distribution "shapes" by metering the addition of an initiator using af eeding pump in anionic and nitroxide-mediated polymerizations. [19][20][21][22] This approach was applied to homopolymers and the first segment of block copolymers but not to the other segments of block copolymers.B oyer et al. recently metered the addition of the polymeric initiator (macro-initiator) in ap hotocontrolled LRP and successfully obtained block copolymers with tailored in the second segment. [23,24] However, the pumpassisted method is always inapplicable to heterogeneous systems,s uch as polymer brush synthesis from solid substrates,a nd thus limits applications.We have developed an organocatalyzed LRP,t hat is, reversible complexation mediated polymerization (RCMP) t...

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Polymer Dispersity Control by Organocatalyzed Living Radical Polymerization

2019

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“…Several approaches have been developed to manipulate Đ values. Blending polymers with different molecular weights is often applied . The polymers need to be prepared in multiple independent runs, and the blended polymers often have multimodal molecular weight distribution.…”

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confidence: 99%

Polymer Dispersity Control by Organocatalyzed Living Radical Polymerization

2019

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Molecular weight distribution of polymers, termed dispersity (Đ), is a fundamental parameter for determining polymer material properties. This paper reports a novel approach for controlling Đ by exploiting a temperature‐selective radical generation in organocatalyzed living radical polymerization. The polymers with tailored Đ were synthesized in a batch system without the assistance of an external pump. A unique aspect of this approach is that Đ was tuneable from 1.11 to 1.50 in any segment in diblock, triblock, and multiblock copolymers and in any form of star and brush polymer without segmental or topological restriction. This approach is amenable to various monomers and free from metals and thus attractive for applications. The approach also generated polymer brushes on surfaces with tailored Đ. An interesting finding was that the polymer brushes exhibited unique interaction with external molecules, depending on the Đ value.

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“…The Đ value is an important parameter in determining various polymer properties such as miscibility, processability, and self-assembly behaviors. − Therefore, polymers with tailored Đ values are desirable, and several methods have been developed. Blending presynthesized polymers with different molecular weights is widely used. − There has been great attention in the controlled modulation of the Đ value via precise regulation of reactions in living polymerizations. − The combination of flow chemistry and living polymerizations opened a new avenue to modulate the Đ value by regulating the flow rate, external stimuli, and reagent compositions. − The control of the polymerization conditions such as the kinds and amounts of catalysts, initiating species, energy, and additional agents in living polymerizations also enabled the modulation of the Đ value. − Recently, computer-assisted polymer design and automated polymerization methods are emerging for modulating the Đ value. − …”

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One Reagent with Two Functions: Simultaneous Living Radical Polymerization and Chain-End Substitution for Tailoring Polymer Dispersity

2021

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The molecular weight distribution of polymer, termed dispersity (Đ), is a fundamental parameter that determines polymer properties. Sodium azide (NaN 3 ) functions as a catalyst in organocatalyzed living radical polymerization when the reaction medium is nonpolar. In contrast, NaN 3 can act as a nucleophile when the reaction medium is polar. In this paper, we report an efficient approach to dispersity control by exploiting the dual functions of NaN 3 under the varied solvent polarity. Simultaneous polymerization and chainend substitution allowed us to tune the Đ values of various polymethacrylates and poly(butyl acrylate). Notably, the Đ value could be tuned to a wide range approximately from 1.2 to 2.0 for polymethacrylates and to 3.8 for poly(butyl acrylate). This approach afforded polymer brushes on surfaces with tailored Đ values. An interesting finding was that the polymer brushes exhibited a unique interaction with external molecules, depending on the Đ value.

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The rheology and gelation of bidisperse 1,4-polybutadiene

Cited by 11 publications

References 97 publications

Polymer Dispersity Control by Organocatalyzed Living Radical Polymerization

Polymer Dispersity Control by Organocatalyzed Living Radical Polymerization

Polymer Dispersity Control by Organocatalyzed Living Radical Polymerization

One Reagent with Two Functions: Simultaneous Living Radical Polymerization and Chain-End Substitution for Tailoring Polymer Dispersity

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