Poly(vinylphosphonate)s functionalized polymer microspheres via rare earth metal-mediated group transfer polymerization

Abstract

We demonstrate a facile, yet efficient method for the functionalization of crosslinked polystyrene (PS) microspheres with biocompatible poly(vinylphosphonate)s via the combination of a UV grafting polymerization and a surface-initiated group transfer polymerization. Self-initiated photografting and photopolymerization of ethylene glycol dimethacrylate results in direct photografting of poly(ethylene glycol dimethacrylate) on the PS microspheres with dangling methacrylate functionalities, which are used to immobilize ytterbocene complexes to form the surface-bound rare-earth metal catalyst system. The surfaceinitiated GTP of dialkyl vinylphosphonates from the initiator system leads to the functionalization of PS microspheres with poly(-vinylphosphonate) brushes. Polymerization kinetic investigation indicates that surface-initiated GTP leads to a constant and remarkably rapid weight gain of the microsphere (a microsphere weight increase of 600% within 3 min), owing to the highly living and efficient character of GTP. The surface-initiated GTP occurring inside the microsphere causes an accumulation of the tension between the polymer chains in the microsphere, which eventually induces fracture of the microsphere for longer polymerization time.

Metal‐Catalyzed Group‐Transfer Polymerization: A Versatile Tool for Tailor‐Made Functional (Co)Polymers

“…Analysis of the mass gain as a function of time in combination with monitoring the growth of the beads by SEM revealed a linear increase for polymerization times up to 3 min (Figure , right, a–d). After this point, rupture of the particles occurred, which was attributed to accumulated repulsion between the grafted polymer chains and growth of chains inside the particles (Figure , right, e and f) …”

“…After this point, rupture of the particles occurred, which was attributed to accumulatedr epulsion between the grafted polymer chains andg rowth of chains inside the particles (Figure 10, right, ea nd f). [42] Conclusions Metal-catalyzed GTP has made major contributions to the development of functionalp olymers. Considering catalystd esign, al ot of effort was made to increase the performance in polymerization catalysis.…”

One‐Reactant Photografting of ATRP Initiators for Surface‐Initiated Polymerization

“…Interestingly, and despite the practical simplicity of the technique, studies of SIPGP are relatively few in number, but some recent studies present elegant uses and broaden the application of SIPGP to carbon and inorganic substrates. [8][9][10][11][12][13][14][15][16] Here, we explored whether an initiator-functionalized surface could be generated by SIPGP of a polymerizable initiator monomer, i.e., an acrylate-functionalized initiator molecule, in a simple one-step one-reactant process. Since controlled reversible-deactivation radical polymerizations, such as atom transfer radical polymerization (ATRP), [ 17 ] have potential benefi ts over uncontrolled polymerization techniques for surface coatings, an ATRP initiator monomer was used in this study.…”

“…This method was seemingly independently observed by three research groups in the 1990s and early 2000s: (i) Uchida et al, (ii) Belfort and co‐workers, and (iii) Deng et al SIPGP is powerful as it requires only substrate, monomer, and UV light source, and does not require addition of an extra molecule as a free radical source. Interestingly, and despite the practical simplicity of the technique, studies of SIPGP are relatively few in number, but some recent studies present elegant uses and broaden the application of SIPGP to carbon and inorganic substrates …”

Study on the Self-polymerization and Co-polymerization Properties of Gadolinium Methacrylate

“…Recently rare earth-containing polymer as a kind of functional material has been received more and more attention, because it combines with the unique properties of the rare earth and the special properties of the polymer, such as light weight, excellent mechanical behavior and varied preparation method [5][6].…”