Thermal analysis and NMR studies of methyl methacrylate (MMA)-methacrylic acid copolymers synthesized by an unusual polymerization of MMA

Abstract

Methyl methacrylate-methacrylic acid (MMA-MAA) copolymers were prepared from the polymerization reaction of the methyl methacrylate (MMA) monomer with concentrated nitric acid (65% HNO 3 ) at different reaction times in the absence of other reagents in the reaction mixture. The hydrolysis degrees of the MMA-MAA (sodium salts) copolymers estimated by thermogravimetry (TG) corroborated the data obtained by chemical titration. By calorimetry (DSC), a relationship between the glass transition temperature (T g ) and the hydrolysis degree was obtained. The results presented a deviation from linear behavior and it was related to the strength of the interactions involved in the copolymer chains. The equation that relates the glass transition temperature to the interaction parameter, , for miscible binary polymer blends was applied for the MMA-MAA copolymers and demonstrated the composition dependence of . The molecular mobility was determined by nuclear magnetic resonance (NMR) in the solid state and through the proton spin-lattice relaxation time in the rotating frame. The NMR data were in a good agreement with the results obtained by calorimetry.

Rhodium-Mediated Stereospecific Carbene Polymerization: From Homopolymers to Random and Block Copolymers

“…After heating, the signal for the tert -butyl CH 3 groups has decreased in intensity and the quaternary carbon signal has almost disappeared. If carboxylic acid groups are formed, the corresponding carbonyl signal should be observed more downfield around 180 ppm . The spectra do not reveal such signals.…”

Preparation and Properties of Four-component Copolymers Applied in Negative-type Photoresists

“…For example, the T g of the polymer binder (M25-S25-I50-P0) was 154.58C, whereas that of another binder (M25-S25-I0-P50) was 212.68C. The T g of pure poly(MAA), poly(STY), poly(IBMA), and poly(PMI-co-STY) were 166, 97, 180, and 2258C, respectively, as obtained from literature [19][20][21][22]. The results showed that T g increased with the PMI content due to the rigid characteristics of the PMI molecular structure.…”

“…The properties of acrylic copolymers, such as their photosensitivity [5], thermal stability [6][7][8][9][10][11][12], pattern resolution [9,13], glass transition temperature [14], nanosilica modified [8,[15][16][17], and physical characteristics [18], have been investigated in negative-type photoresists. The T g values of pure poly(methacrylic acid), polystyrene, poly(isobornyl methacrylate), and poly(phenylmaleimide-costyrene) were obtained from literature [19][20][21][22]. However, the preparation and thermal properties of four-component copolymers have not been studied sufficiently.…”

Preparation of blends of poly(methyl methacrylate) copolymers with high glass transition temperatures and low hydrophilicity

“…Copolymerization with monomers that can form hydrogen bonds with the carbonyl groups of PMMA such as acrylamide (AM), methacrylamide (MAAM), acrylic acid (AA), or methacrylic acid (MAA) was another efficient method to raise the T g of PMMA . However, water absorbability of the copolymers increased because of the existence of polarity groups of —CONH 2 or —COOH.…”