Copolymerization of 4-chlorophenyl acrylate with methyl acrylate: synthesis, characterization, reactivity ratios, and their applications in the leather industry

Abstract

4-Chlorophenyl acrylate (CPA) was prepared by reacting 4-chlorophenol and acryloyl chloride in the presence of triethylamine in ethyl acetate solution. Poly(4-chlorophenyl acrylate) and copoly(4-chlorophenyl acrylate-methyl acrylate) were synthesized by the free radical polymerization in ethyl acetate at 70°C. All the polymers were characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopic techniques. The composition of the copolymers was determined by the 1 H-NMR spectroscopic technique, that is, by integrating the aromatic peaks corresponding to the 4-chlorophenyl acrylate unit against the carbomethoxy group in the methyl acrylate unit. The reactivity ratios were calculated by Fineman-Ross, Kelen-Tudos (K-T), and the extended Kelen-Tudos methods. The values of r 1 and r 2 obtained by these methods were in close agreement with each other; that is, r 1 (CPA) ϭ 0.64 and r 2 (MA) ϭ 0.13 by the K-T method. The number-average molecular weight (M n ϭ 1.55 ϫ 10 3 ), the weight-average molecular weight (M w ϭ 8.39 ϫ 10 3 ), and the polydispersity index (M w /M n ϭ 5.42) of poly(CPA) were determined by gel permeation chromatography (GPC). Thermal properties of the polymers were studied in a nitrogen atmosphere using thermogravimetric analysis (TGA). As the CPA increases in the copolymer, thermal stability of the copolymer increases (e.g., 90% weight loss occurs at 480°C for 20 mol % CPA, whereas the same weight loss occurs at 571°C for 80 mol % CPA). Acrylic binders, based on the CPA-MA-BA terpolymer, of different glass transition temperatures were prepared for applications in leather industry as top coat and base coat materials. These acrylic emulsions were cast into thin films, and their characteristics were tested for physical properties. These acrylic emulsions were applied as a base coat on leather, and the compositions having T g values of 1.08 and 9.25°C were found to have excellent properties as base coats for leather when compared with commercial samples.

Synthesis of N-(2,4,5-trichlorophenyl) Acrylamide Copolymer Emulsions and their Antibacterial, Thermal and Mechanical Properties

“…Acrylic polymers are used in various fields such as thin films, fibers, coatings, lithography, lacquers, adhesives, printing inks, and binders (3)(4)(5). Nowaday's acrylic emulsion received much attention because of environmental legislation imposing restrictions on emission of volatile organic component (VOC), these restrictions forced manufacturers to formulate coatings comprised of low or zero VOC.…”

Development and Applications of Novel Acrylic Copolymers

“…These chemicals find applications as biocides. A copolymer of chlorophenylmethacrylate was used as base coat for leather [8]. Copolymers based on halogenated phenylacrylate have been utilized for synthesizing electroactive polymers for the preparation of polymeric reagents carrying piperazine and isonitrile functionalities [9,10].…”

Synthesis and Characterization of Novel Methacrylic Copolymers: Determination of Monomer Reactivity Ratios

“…Therefore, they find a wide range of application in the preparation of materials such as photo luminescent (7), photo resist (8), adhesives for leather (9)(10)(11), photosensitive (12), biomaterials (13,14), optical telecommunication materials (15), polymer catalyst (16), etc. Methyl methacrylate (MMA) copolymers are mainly used in the production of primers for automotive finishes, lacquers for polishing metals, enamels for household appliances, formulations of base and top coats for leather and a binder in protective coatings, due to their durability and transparency (17,18). Reactivity ratios are one among the most important parameters for the copolymer equation, which gives very good information regarding relative reactivity of the monomer pairs and copolymer composition determination.…”