Synthesis of Polystyrenes−Poly(alkyl methacrylates) Block Copolymers via Anionic Polymerization Using an Integrated Flow Microreactor System

Abstract

The polystyrene living polymer end, which was produced by butyllithium initiated anionic polymerization of styrene in a flow microreactor system was found to be effectively trapped with 1,1-diphenylethylene. The resulting organolithium species could be used as a macro initiator for anionic polymerization of alkyl methacrylates to obtain styrene−alkyl methacrylate diblock copolymers using an integrated flow microreactor system. A high level of control of molecular weight was achieved at easily accessible temperatures such as +24 to −28 °C by virtue of the fast mixing, fast heat transfer, and residence time control. Triblock copolymers were also synthesized by sequential introduction of styrene and two different alkyl methacrylates in a similar manner.

Synthesis of amphiphilic block copolymers containing ferrocene–boronic acid and their micellization, redox-responsive properties and glucose sensing

“…The introduction of different functional groups into the polymer greatly enhances its practical applications in biodiagnosis, separation media and therapeutics [1][2][3]. The selection of monomers depends on their intended applications.…”

Synthesis of high molecular weight poly(styrene-b-methyl methacrylate) using a plug flow reactor system by anionic polymerization

“…25,[32][33][34] Nagaki et al demonstrated block copolymerizations of styrene and alkyl methacrylate (M n : 3,900-17,000 g·mol -1 , M w /M n : 1.1-1.5) in THF using an integrated flow micro reactor system consisting of syringe pumps and three T-shaped mixing elements. 20 The polystyrene end groups were capped with DPE within 3 s with high capping efficiency (81% at 0 o C) using the flow micro reactor system.…”

“…14 Many studies on anionic polymerizations of styrene, styrene derivatives, and alkyl methacrylate to homopolymers and block copolymers in THF have been performed using flow reactors. [15][16][17][18][19][20][21] In particular, Yoshida & Nagaki et al demonstrated anionic block copolymerization (M n 16,900 g·mol -1 ) of styrene and alkyl methacrylate using a micro flow reactor. 16 For practical applications in the industrial field, such as anti-reflective coating materials and nano-patterning in PSb-PMMA, block copolymers with molecular weights greater than 100×10 3 g·mol -1 are necessary to be produced in large scale.…”

Polymerization Using Flow Microreactor System

“…With the need to suppress such side reactions, anionic polymerization of methacrylates has been more difficult than anionic polymerization of styrenes [11,12]. The flow microreactor system allows anionic polymerization of methacrylates under the conditions that are easily accessible in industrial production (−30°C or above) [13][14][15].…”