Hybrid Polymerization of Ring-Opening Metathesis and Cross-Metathesis for Polyolefins with Tunable Architectures

Ren, Ning; Zhu, Xinyuan

doi:10.1021/acs.macromol.8b02135

Cited by 14 publications

(8 citation statements)

References 46 publications

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“…We expected this alkene impurity to be susceptible to cross-metathesis during ROMP, leading to high dispersity polymers with limited control over molecular weight, Figure S2. 52 Thus, we performed a postpolymerization hydrogenation to eliminate this alkene impurity. The MALDI data in Figure 1 show a 2 g/mol increase in molecular weight for each of the peaks identified in the alkene chain end population, blue squares to green circles, which indicates that this chain end modification was successful without changing the molecular weight distribution.…”

mentioning

confidence: 99%

“…We employed established methods to limit this side reaction using 18-crown-6 ether, , but roughly 7 mol % (from NMR) of the chains have this impurity. We expected this alkene impurity to be susceptible to cross-metathesis during ROMP, leading to high dispersity polymers with limited control over molecular weight, Figure S2 . Thus, we performed a postpolymerization hydrogenation to eliminate this alkene impurity.…”

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confidence: 99%

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Synthesis and Micellization of Bottlebrush Poloxamers

et al. 2022

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Bottlebrush polymers are characterized by an expansive parameter space, including graft length and spacing along the backbone, and these features impact various structural and physical properties such as molecular diffusion and bulk viscosity. In this work, we report a synthetic strategy for making grafted block polymers with poly(propylene oxide) and poly(ethylene oxide) side chains, bottlebrush analogues of poloxamers. Combined anionic and sequential ring-opening metathesis polymerization yielded low dispersity polymers, at full conversion of the macromonomers, with control over graft length, graft end-groups, and overall molecular weight. A set of bottlebrush poloxamers (BBPs), with identical graft lengths and composition, was synthesized over a range of molecular weights. Dynamic light scattering and transmission electron microscopy were used to characterize micelle formation in aqueous buffer. The critical micelle concentration scales exponentially with overall molecular weight for both linear and bottlebrush poloxamers; however, the bottlebrush architecture shifts micelle formation to a much higher concentration at a comparable molecular weight. Consequently, BBPs can exist in solution as unimers at significantly higher molecular weights and concentrations than the linear analogues.

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Synthesis and Micellization of Bottlebrush Poloxamers

et al. 2022

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“…115 This method has been widely studied since Hillmyer et al first report in 2011. Various studies have utilised this allyl functionalised monomer, 94,114,116,117,125,[127][128][129][130][131][132] and it is also effective for Schrock-type catalysts. Grubbs-type ruthenium catalysts yield polymers with trans-double bonds, while Schrock-type catalysts produce polymers with cis-double bonds.…”

Section: Cyclooctenesmentioning

confidence: 99%

Design of biomaterials through direct ring-opening metathesis polymerisation of functionalised cyclic alkenes

Kobayashi

Tanaka

2023

Mol. Syst. Des. Eng.

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“…As a result, the viscosity will increase at a slower rate when a vinyl pendant group is present. 23 Furthermore, the slow introduction of crossmetathesis reactions permits the formation of branch points in the polymer chain potentially leading to lower overall viscosity as well. Hence, this phenomenon can be leveraged to permit a window of time when the material can be dispensed by a printer prior to gelation.…”

Section: Introductionmentioning

confidence: 99%

Low-Loss Dielectric Ink for Printed Radio Frequency and Microwave Devices

Piro

Areias

Luce

et al. 2023

ACS Appl. Mater. Interfaces

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Direct write printing is restricted by the lack of dielectric materials that can be printed with high resolution and offer dissipation factors at radio frequency (RF) within the range of commercial RF laminates. Herein, we outline the development of dielectric materials with dielectric loss below 0.006 in X and Ku frequency bands (8.2−18 GHz), the range required for radio frequency and microwave applications. The described materials were designed for printability and processability, specifically a prolonged viscosity below 1000 cps and a robust cure procedure, which requires minimal heat treatment. In the first stage of this work, nonpolar ring-opening metathesis polymerization (ROMP) is demonstrated at room temperature in an open-air environment with a low-viscosity monomer, 5-vinyl-2-norbornene, using the second-generation Grubbs catalyst (G-II). Differential scanning calorimetry (DSC) was used to study how the catalyst activity is increased with heating at various stages in the reaction, which is then used as a strategy to cure the material after printing. The resulting cured poly(5-vinyl-2-norbornene) material is then characterized for dielectric and mechanical performance before and after a secondary heat treatment, which mimics processing procedures to incorporate subsequent printed conductor layers for multilayer applications. After the secondary heat treatment, the material exhibits a 55.0% reduction in the coefficient of thermal expansion (CTE), an increase in glass-transition temperature (T g ) from 32.4 to 46.1 °C, and an increased 25 °C storage modulus from 428 to 1031 MPa while demonstrating a minimal change in dielectric loss. Lastly, samples of the developed dielectric material are printed with silver overtop to demonstrate how the material can be effectively incorporated into fully printed, multilayer RF applications.

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Hybrid Polymerization of Ring-Opening Metathesis and Cross-Metathesis for Polyolefins with Tunable Architectures

Cited by 14 publications

References 46 publications

Synthesis and Micellization of Bottlebrush Poloxamers

Synthesis and Micellization of Bottlebrush Poloxamers

Design of biomaterials through direct ring-opening metathesis polymerisation of functionalised cyclic alkenes

Low-Loss Dielectric Ink for Printed Radio Frequency and Microwave Devices

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