Kinetic modeling of two-step RAFT process for the production of novel fluorosilicone triblock copolymers

Zhou, Yin‐Ning; Guan, Cheng-Mei; Luo, Zheng‐Hong

doi:10.1016/j.eurpolymj.2010.09.002

Cited by 11 publications

(6 citation statements)

References 18 publications

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“…Silicone containing diblock or triblock copolymers with well-defined structures can be prepared by living anionic polymerization through the sequential addition of monomers, using ROP or ATRP.Another widely utilized method is the chemical coupling of functionally terminated blocks usually prepared by anionic polymerization. Each of these synthetic techniques and the properties of copolymers obtained will be discussed separately in the forthcoming sections.Several other methods which can also be used for the preparation of silicone containing block copolymers include free radical copolymerization using macroinitiators (21,(28)(29)(30), iodine transfer polymerization (24,31) and reversible additionfragmentation chain transfer (RAFT) polymerization (32)(33)(34). Unfortunately, some of these techniques do not provide very good control of the block lengths, may require the use of specific monomers and also may lead to extensive homopolymer contamination (29,30).…”

Section: Silicone Containing Diblock or Triblock Copolymersmentioning

confidence: 99%

Silicone containing copolymers: Synthesis, properties and applications

Yılgör

2014

Progress in Polymer Science

439

322

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A comprehensive survey of the recent developments on the synthesis, properties and applications of silicone containing copolymers is provided. Influence of (−R 2 Si−O−) backbone composition on the physicochemical properties of silicone copolymers, such as thermal transitions, solubility parameter and surface tension is discussed. Preparation and properties of well-defined α,ω-reactive organofunctionally terminated (telechelic) silicone oligomers and their utilization in the preparation of a wide range of block and segmented copolymers through step-growth,anionic, ring-opening and living free-radicalpolymerization techniques are provided. Use of silicone oligomers in the modification of polymeric network structures is also discussed. Special emphasis is given to the discussion of the effect of silicone oligomer and organic segment structure and molecular weight on the morphology and surface and bulk properties of the resultant silicone containing copolymers and networks.

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Section: Silicone Containing Diblock or Triblock Copolymersmentioning

confidence: 99%

Silicone containing copolymers: Synthesis, properties and applications

Yılgör

2014

Progress in Polymer Science

439

322

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“…The results demonstrated that both diffusion‐controlled radical termination and radical addition accelerated the polymerization rate, but the former narrowed and the latter broadened the molar mass distributions of resulting polymers. According to the practicability of the modeling method, Guan and Zhou investigated the effect of initiator concentration, chain transfer agent concentration, and monomer concentration on the RAFT polymerization kinetics . In order to provide a quantitative tool for directly analyzing experiment data, Gao and Zhu made efforts to derive analytical equations to calculate the concentration, chain length, and dispersity of various chain species in RAFT system based on an simplified mechanism .…”

Section: Batch Polymerization Rate and Average Chain Propertiesmentioning

confidence: 99%

State‐of‐the‐Art and Progress in Method of Moments for the Model‐Based Reversible‐Deactivation Radical Polymerization

Zhou

Luo

2016

Macro Reaction Engineering

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polymerization (FRP). However, because of the slow initiation, rapid propagation, and termination involving many different chain lengths, FRP is difficult to control over the polymer architectures and the minimum dispersity of the molar mass distribution is 2. [4,5] What's exciting is that controlled radical polymerization (also termed as reversible-deactivation radical polymerization (RDRP)) was discovered about two decades ago. [6,7] In most of RDRP systems, the initiation or degeneratively exchange is fast, propagation is relatively slow, and termination is suppressed per present chain, referring to the dominance of dormant chains in the final mixture. As a result, polymerization proceeds in a controlled manner, allowing one to prepare various well-defined block copolymers, stars, bottlebrushes, and hybrid materials. [6] Therefore, RDRP has attracted increasing interest from both academic and industrial fields. [8][9][10] Facing the increasing demand on high qualified and tailor-made polymeric materials, despite the technological promise, there are only limited products and investigations based on RDRP techniques at industrial scale. This can be attributed to the limited commercial RDRP agents Reversible-deactivation radical polymerization (RDRP) techniques have received lots of interest for the past 20 years, not only owing to their simple, mild reaction conditions and broad applicability, but also their accessibility to produce polymeric materials with well-defined structures. Modeling is widely applied to optimize the polymerization conditions and processes. In addition, there are numerous literatures on the kinetic and reactor models for RDRP processes, which show the accessibility on polymerization kinetics insight, process optimization, and controlling over chain microstructure with predetermined molecular weight and low dispersity, copolymer composition distribution, and sequence distribution. This review highlights the facility of the method of moments in the modeling field and presents a summary of the present state-of-the-art and future perspectives focusing on the model-based RDRP processes based on the method of moments. Summary on the current status and challenges is discussed briefly.in large quantities at reasonable costs and the extra cost of the polymer purification processes. [10] From the view point of chemical engineering, the productivity and quality of the polymer products, as well as the polymer chain composition and chain topology, are largely influenced by the engineering problems, such as micromixing, residence time distribution of reactor, mass and heat transfers. It normally takes a long time to obtain an optimized operation condition and products only through practices. The ongoing paradigm of polymerization processes begins to shift from process design and operation by experiments and empirical methods to one by the combination of experiments and mathematical models. [11,12] In order to speed up the industrialization of RDRP techniques, the polymerization engineers can take advant...

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“…To fully explore the potential of the RAFT polymerization technique it is therefore crucial to accurately map the impact of the aforementioned process parameters on the RAFT polymerization characteristics. Several research groups have focused on this important research task, both experimentally and via computer simulations . However, the number of kinetic studies considering the simultaneous impact and interaction of all relevant process parameters is limited.…”

Section: Introductionmentioning

confidence: 99%

An Update on the Pivotal Role of Kinetic Modeling for the Mechanistic Understanding and Design of Bulk and Solution RAFT Polymerization

Rybel

Steenberge

Reyniers

et al. 2016

Macro Theory & Simulations

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The importance of the development of kinetic modeling tools to mechanistically understand and design bulk and solution reversible addition fragmentation chain transfer (RAFT) polymerization is highlighted. Both deterministic and stochastic kinetic modeling methods are covered, considering a detailed reaction scheme and accounting for the impact of diffusional limitations on the reaction rates. A novel strategy is introduced to fundamentally calculate the diffusional contributions for the apparent RAFT addition and fragmentation rate coefficients. Next to literature examples, case studies are included to demonstrate that detailed theoretical studies are indispensable to completely map the effect of the polymerization conditions and RAFT agent reactivity on the control over microstructural properties and the overall polymerization time. Guidelines for future kinetic modeling activities are formulated to enhance joined theoretical and experimental research.

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Kinetic modeling of two-step RAFT process for the production of novel fluorosilicone triblock copolymers

Cited by 11 publications

References 18 publications

Silicone containing copolymers: Synthesis, properties and applications

Silicone containing copolymers: Synthesis, properties and applications

State‐of‐the‐Art and Progress in Method of Moments for the Model‐Based Reversible‐Deactivation Radical Polymerization

An Update on the Pivotal Role of Kinetic Modeling for the Mechanistic Understanding and Design of Bulk and Solution RAFT Polymerization

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