Flash cationic polymerization followed by bis-end-functionalization. A new approach to linear-dendritic hybrid polymers

Tani, Yosuke; Takumi, Masahiro; Moronaga, Satori; Nagaki, Aiichiro; Yoshida, Jun‐ichi

doi:10.1016/j.eurpolymj.2016.02.021

Cited by 13 publications

(4 citation statements)

References 68 publications

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“…The peripheral modification of both the initiating and dendritic terminating ends leads to the formation of dendritic− linear−dendritic (D−L−D) hybrid polymers. 109 3.4.3. Stabilized ArCH 2 + Ions.…”

Section: Stabilized Glycosyl Cationsmentioning

confidence: 99%

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Electrogenerated Cationic Reactive Intermediates: The Pool Method and Further Advances

2017

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Electrochemistry serves as a powerful method for generating reactive intermediates, such as organic cations. In general, there are two ways to use reactive intermediates for chemical reactions: (1) generation in the presence of a reaction partner and (2) generation in the absence of a reaction partner with accumulation in solution as a "pool" followed by reaction with a subsequently added reaction partner. The former approach is more popular because reactive intermediates are usually short-lived transient species, but the latter method is more flexible and versatile. This review focuses on the latter approach and provides a concise overview of the current methods for the generation and accumulation of cationic reactive intermediates as a pool using modern techniques of electrochemistry and their reactions with subsequently added nucleophilic reaction partners.

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Section: Stabilized Glycosyl Cationsmentioning

confidence: 99%

“…For example, the block copolymerization of two vinyl ethers followed by trapping with nucleophiles gave structurally well-defined macromolecules. The peripheral modification of both the initiating and dendritic terminating ends leads to the formation of dendritic–linear–dendritic (D–L–D) hybrid polymers …”

Section: Carbocationsmentioning

confidence: 99%

Electrogenerated Cationic Reactive Intermediates: The Pool Method and Further Advances

2017

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“…35 Ever rising demand for polymers with tailored properties for specific applications makes microfluidics for polymerization a suitable option. Microfluidics for polymerization is widely reported in the literature and effectively applied for almost every type of polymerization reaction, 36,37 such as flash cationic polymerization (Figure 2B), 38 anionic polymerization (Figure 2E), 39 reversible addition−fragmentation chain transfer (RAFT) polymerization (Figure 2A), 40 enzyme-catalyzed polymerization (Figure 2D), 41 etc. The utilization of highthroughput (Figure 2C) 42 and autonomous self-optimizing (Figure 2F) 43 microfluidic platforms is also highlighted in the literature.…”

Section: Microfluidics For Polyolefin Catalysismentioning

confidence: 99%

Perspectives on Polyolefin Catalysis in Microfluidics for High-Throughput Screening: A Minireview

Sharma

Hartman

2022

Energy Fuels

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Polyolefins are the largest produced plastics in the world, wherein continuous stirred tank reactors and fluidized bed reactors are traditionally employed for commercial production. The operating condition, reaction kinetics, and molecular interactions inside the reactor strongly affect the polyolefin properties, which require a stringent process control in conventional procedures. Understanding the catalytic pathway, behavior of polymer particles, and effect of reactor conditions is essential for designing specific polymer properties, namely, the molecular weight, chain length, polydispersity, etc. Microfluidics can play a significant role in designing polymers tailored to the user needs. Smaller channel dimensions help obtain uniform reaction conditions over the length of the microfluidic reactor in a controlled environment. With real-time monitoring techniques in microfluidics, even single-particle growth of polymer can be studied to understand the parameters affecting the polymer properties. High-throughput microfluidics can help catalyst screening in a short duration with less consumption of reagents, generating less waste. When supplemented with efficient machine-learning algorithms, automated high-throughput microfluidics has the potential to rapidly optimize the process and facilitate the development of new knowledge even with a limited data set. When trained on data sets generated using microfluidic experiments that are designed efficiently with working knowledge of the process, machine-learning algorithms can provide the relationship between the multivariable parameters space and polymer properties, which is not possible with the traditional statistical methods and interpolation techniques. The rise in the utilization of microfluidics, with the advancement of machine-learning algorithms, for polyolefin catalysis, highlights the importance of microfluidics for catalyst discovery, parameter optimization, and understanding the reaction pathway for producing polymers with specific properties for specialized applications.

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“…Flow microreactors serve as effective methods for accomplishing controlled/living anionic polymerization. − Poly(styrenes), poly(alkyl methacrylates), poly( tert -butyl acrylate), and poly(perfluoroalkyl methacrylates) can be obtained with very narrow molecular weight distribution under easily accessible conditions. However, the feasibility studies on continuous flow controlled/living anionic polymerizations have not been reported from a viewpoint of industrial production.…”

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confidence: 99%

Feasibility Study on Continuous Flow Controlled/Living Anionic Polymerization Processes

Nagaki

Nakahara

Furusawa

et al. 2016

Org. Process Res. Dev.

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A practical microchemical reaction system for keeping process flow at defined conditions, which is one of the key issues of industrial production, was developed. Controlled/living anionic polymerization was chosen as a test reaction because the molecular weight and molecular weight distribution of polymer products are quite sensitive to the relative flow rate of an initiator solution and that of a monomer solution. The polymerization of styrene in THF/hexane was carried out using a flow microreactor system consisting of two T-shaped micromixers and two microtube reactors using Smoothflow pumps at 0°C. Poly(styrene) with higher molecular weight such as Mn > 10000 could be synthesized using sBuLi (Mn = 14 000, M w /M n = 1.11). n-BuLi could also be used as an initiator. The continuous operation was performed for 3 h without any problems to obtain ca. 1 kg of the polymer, indicating the feasibility of continuous flow processes for controlled/living anionic polymerization on a relatively large scale. F low microreactors 1−3 have received significant research interests both from academia and industry, because they are expected to make revolutionary changes in chemical synthesis and production. The flow microreactor technology improves not only selectivity, safety, and sustainability of reactions, but also speed and efficiency of discovery and optimization of new drugs and functional materials. Moreover, another attractive feature of flow microreactor technology is that the scale-up of a reaction from laboratory synthesis to industrial production can be performed with minimun reoptimiziation of the process. Because of these advantages, the flow microreactor technology is expected to serve as a key technology for chemical and pharmaceutical industries. To accelerate the progress of this field the Micro Chemical Production Study Consortium in Kyoto University (MCPSC-KU) 4 was founded in 2009. The consortium has promoted research and development relevant to the flow microreactor technology and has disseminated industry−academia collaboration facilitating the development of next-generation chemical plants based on the technology. The members of MCPSC-KU identified that keeping process flow at defined conditions during the operation is one of the key issues of the microchemical production in industry.We chose to study controlled/living anionic polymerization as a test reaction because the molecular weight and molecular weight distribution of polymer products are quite sensitive to the relative flow rate of an initiator solution and that of a monomer solution. Also, controlled/living anionic polymerization 5,6 using flow microreactors has received significant interest from industry because it enables the production of structurely well-defined polymers such as end-functionalized polymers, block polymers, gradient polymers, graft polymers, and star polymers under easily accessible conditions because of livingness and high reactivity of the anionic polymer chain ends. 7 In contrast, the batch controlled/living anionic polymeriz...

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Flash cationic polymerization followed by bis-end-functionalization. A new approach to linear-dendritic hybrid polymers

Cited by 13 publications

References 68 publications

Electrogenerated Cationic Reactive Intermediates: The Pool Method and Further Advances

Electrogenerated Cationic Reactive Intermediates: The Pool Method and Further Advances

Perspectives on Polyolefin Catalysis in Microfluidics for High-Throughput Screening: A Minireview

Feasibility Study on Continuous Flow Controlled/Living Anionic Polymerization Processes

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