Copolymerization of 2-isothiocyanatoethyl methacrylate and 2-hydroxyethyl methacrylate or methacrylic acid based on a nucleophile-tolerant property of the isothiocyanato group

Abstract

Radical copolymerizations of 2-isothiocyanatoethyl methacrylate (ITEMA) and 2-hydroxyethyl methacrylate (HEMA) or methacrylic acid (MAA) were examined, and fundamental properties of the obtained copolymers were investigated. The copolymerizations of various ITEMA=HEMA or ITEMA=MAA compositions proceeded effectively in THF or DMF by using 2,2 0 -azobisbutyronitrile (AIBN) as an initiator, keeping the isothiocyanato groups and hydroxyl or carboxyl groups unchanged. Glass transition temperatures (T g )s of poly(ITEMAco-HEMA)s ranged from 68 to 100 C, and they were thermally stable up to 200 C. Meanwhile, T g s of poly(ITEMA-co-MAA)s (ITEMA=MAA 5 91=9, 76=24) were determined to be 91 and 109 C, respectively. However, poly(ITEMA-co-MAA)s were thermally unstable, and significant weight loss was observed around 180 C, which may be due to an addition of carboxyl groups to isothiocyanato groups followed by an elimination of COS to form amide structure in the copolymers. V C 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 5221-5229

Crosslinking and ozone degradation of thermosetting resins based on maleic anhydride/diene copolymer and polyfunctional alcohols

“…The quantitative ring‐opening reaction of the anhydride groups required the harder reaction conditions, such as reflux in toluene for 5 h. The peak due to the anhydride moiety was not observed in the spectrum of the isolated product [Figure (c)]. In the literature, the reactivity of functional groups, such as anhydride, acyl chloride, and isocyanate groups, was reduced when they were incorporated as a part of the polymer repeating structure …”

“…In the literature, the reactivity of functional groups, such as anhydride, acyl chloride, and isocyanate groups, was reduced when they were incorporated as a part of the polymer repeating structure. [25][26][27][28][29][30]…”

Selective nucleophilic additions to poly(methacrylate)s containing isothiocyanate moieties in the side chains and their application in cross-linking

“…Taking advantage of these characteristics, we copolymerized ITEMA with 2-hydroxyethyl methacrylate (HEMA) or methacrylic acid (MAA) to obtain corresponding copolymer, poly (ITEMA-co-HEMA) or poly(ITEMA-co-MAA). 16 In this study, we demonstrated that an isothiocyanatecontaining polymethacrylate reacted with an amine, an alcohol, and a thiol to obtain the corresponding thiourea, thiouretane, and dithiocarbamate. These reactions were applied to crosslink the polymers to prepare networked polymers using bifunctional compounds.…”

“…Furthermore, isothiocyanate‐containing monomers can be copolymerized with monomers containing free hydroxyl or carboxyl groups, which are difficult to be copolymerized with isocyanate‐containing monomers. Taking advantage of these characteristics, we copolymerized ITEMA with 2‐hydroxyethyl methacrylate ( HEMA ) or methacrylic acid ( MAA ) to obtain corresponding copolymer, poly (ITEMA‐ co ‐HEMA) or poly(ITEMA‐ co ‐MAA) …”

Synthesis of polydithiourethanes and their thermal, optical, and mechanical properties originated from monomers structure

“…[8][9][10] Recently, the environmentally friendly polyurethanes have also been synthesized from the bio-based monomers such as sugar and vegetable oil and the multifunctional cyclic carbonates. [11][12][13] On the other hand, the diisothiocyanates, which are less reactive toward several nucleophilic agents and more stable in ambient moisture and air atmosphere than that of the diisocyanate, [14][15][16] can be used for the polyaddition of various diols, diamines, and dithiols as well as the diisocyanates. [17][18][19][20][21] The polyaddition of diisothiocyanates with diols and/or diamines affords polythiourethanes and/or polythioureas, which are especially utilized as the optical materials due to high refractive index and transparency.…”