Phosphonated homopolymers and copolymers via ring opening metathesis polymerization: T _g tuning, flame resistance, and photolithography

Abstract

Phosphonated and epoxy‐containing norbornene based monomers were prepared by Diels–Alder reaction. They were then combined with three other commercial cyclic unsaturated monomers to synthesize phosphonated homopolymers and copolymers via ring opening metathesis polymerization (ROMP) using second‐generation Grubbs catalyst. Glass transitions of these polymers were tunable in a broad range from −14 to 91 °C by varying the flexibility of comonomer. Interestingly, copolymerization with cyclopentene inhibited the crystallization of polycyclopentene, and instead, led to a copolymer with two Tgs. Paradoxically, results from thermogravimetric analysis (TGA) were not consistent with the followed flame‐retarding experiment, implying that the early weight loss from phosphonated moieties did not deleteriously affect the flame‐resistant property which actually depended more on the percentage of char residual after thermal degradation. In application studies, the norbornene derivative phosphonated polymer was tested for the first time as flame retarding material, and showed significant self‐extinguishing ability. In a second study, photolithography was also successfully performed via thiol‐ene “click” chemistry, which allowed the phosphonated polymer a promising negative photoresist. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1396‐1408

Post-polymerization modification reactions of poly(glycidyl methacrylate)s

“…[30][31][32][33][34] The synthesis of the backbone itself is not discussed and the reader is referred to a number of important publications in this regard. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Other polymer backbones that carry a side-chain epoxide functionality are important as is seen in the works of Harth, Dove, He, Siegwert, and Theato. [35][36][37][38][39][40] However, these backbones are outside the scope of the present review as we limit ourselves to PGMA polymers only.…”

“…In fact, PGMA can be easily synthesised from its commercially available and inexpensive monomer, glycidyl methacrylate, by free radical polymerization processes (Scheme 1). [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] Stability-wise, the puried homopolymer can be stored at room temperature and under ambient conditions for years without compromising its structural integrity. In this way, it differs from other reactive scaffolds like alkene and alkynecarrying which can crosslink during polymerisation if the Ezzah M. Muzammil is a Master student from Nanyang Technological University (NTU) in the Division of Chemistry and Biological Chemistry.…”

“…Of course, co-polymerization is possible with any other acrylate or methacrylate monomer to further diversify the range of structures and applications of the nal materials. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] When required, the epoxy side chains of PGMA can be subjected to a nucleophilic ring-opening reaction under a variety of conditions to afford functionalised polymers (Scheme 2). The wide range of chemistry available allows one to freely choose the nature of the functional group and the manner of the ring-opening reaction.…”

Recent Developments in Organophosphorus Flame Retardants Containing P-C Bond and Their Applications

“…Diethyl bromoethylphosphonate ( 16 , Figure 10 ) has been synthesized from 1,2-dibromoethane and triethyl phosphite to improve flame resistance of several polymers [ 68 ]. Compound 16 was used to synthesize other monomers for ROMP homopolymerization.…”

Ring opening metathesis polymerization (ROMP) and thio‐bromo “click” chemistry approach toward the preparation of flame‐retardant polymers

“…In addition to ROMP's countless applications, some groups have become interested in utilizing ROMP as a tool for the preparation of PCPs and a few have even investigated its use for preparing flame‐resistant materials . However, most of these examples rely on the synthesis and polymerization of specially designed, unique phosphorus‐containing monomers.…”