Monodisperse Styrene-Maleic Anhydride-Isoprene Terpolymer Microspheres with Tunable Crosslinking Density Prepared by Self-Stabilized Precipitation Polymerization

Abstract

Synthesis and industrial production of functional monodisperse microspheres still face enormous challenges like precise size control and process simplification. Herein, a strategy to prepare monodisperse styrene-maleic anhydride-isoprene terpolymer microspheres via self-stabilized precipitation polymerization was reported. The prepared microspheres with different isoprene proportions have uniform particle sizes (623−1156 nm) and narrow size distributions. The structure analysis showed that the copolymerization proceeded in an alternating way between the electron donor (styrene and isoprene) and electron acceptor (maleic anhydride) monomer, and isoprene was incorporated into the polymer chain through 1, 4 addition. The gel fraction of microspheres varies from 0 to 99% along with an increasing isoprene feeding ratio. The Diels−Alder (D−A) reaction between maleic anhydride and isoprene can be effectively inhibited by increasing the amount of initiator or decreasing the polymerization temperature. The resultant uniform microspheres contain reactive anhydride groups and unsaturated C�C bonds derived from isoprene, which can be used to covalently attach functional moieties and have great potential in fields of adsorption and separation, drug delivery, biodetection, and enzyme immobilization.

Facile and High-Yield Synthesis of Monodisperse and Heat-Resistant Polymaleimide Microspheres by Self-Stabilized Precipitation Polymerization

“…What’s more, the separated solvent containing residual monomers can be directly reused to reduce environmental pollution, which makes the 2SP process suitable for large-scale industrial production. A series of styrene/maleic anhydride (St/MAH, SMA) copolymer microspheres , with tunable particle sizes, molecular weights, and copolymer composition have been prepared by the 2SP process. Apart from St, MAH can also copolymerize with other electron-donating monomers such as vinyl acetate, vinyl chloride, and aromatic olefins , and terpolymerize with St/acrylamide and St/isoprene by the 2SP process, leading to the formation of polymer particles with different chemical compositions and molecular structures.…”

Tunable Red Clusteroluminescence Polymers Prepared by a Simple Heating Process

“…PMV is a typical nonconjugated CLgens with solvatochromism . The self-stabilized precipitation polymerization (2SP) method is a common two-phase reaction system to realize the large-scale preparation of PMV or other copolymers of maleic microspheres without the use of stabilizers. − According to our previous work, the polymer chains of PMV are randomly entangled during the 2SP. The entangled polymer chains are therefore unfavorable for the forming of clusters, resulting in low QY of PMV.…”

Synthesis of High-Molecular-Weight Poly(ether-alt-ester) by Selective Double Ring-Opening Polymerization of Spiroorthoesters

“…The synthesis of sequence-controlled polymers, which offers new pathways to a variety of physical, mechanical, and chemical properties in myriad applications, is challenging . Among sequence-controlled polymers, alternating copolymers are generally prepared using comonomer pairs, such as olefins and cyclic anhydrides, , olefins and CO, − aziridines and CO, , aziridines and carbonyl sulfide, , cyclic acetals and cyclic anhydrides, epoxides and CO 2 , − epoxides and CO, − and epoxides and cyclic anhydrides. − However, in most cases, sequence skipping prevents the formation of perfectly alternating copolymers. , Additionally, the scope of comonomer pairs is limited; for example, only a few examples of the alternating copolymerization of epoxides and lactones have been reported, which yield low-molecular-weight polymers. Coates and co-workers reported the alternating copolymerization of dihydrocoumarin with epoxides to form alternating polyesters with molecular weights of 7–19 kDa .…”