Synthesis and binary copolymerizations of 2‐pyrimidyl acrylamide with different alkyl acrylates, vinyl acetate and acrylonitrile

Abstract

2-Pyrimidyl acrylamide (2PA) monomer was prepared by the reaction of 2-aminopyrimidine with acryloyl chloride. Its structure was confirmed by IR, 'H NMR, and MS spectroscopy. Binary copolymerizations of this new monomer with methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BuA), methyl methacrylate (MMA), vinyl acetate (VA), and acrylonitrile (AN) were performed in tetrahydrofuran, using 1 mol% azobisisobutyronitrile as initiator at 65°C. N analysis and 'H NMR spectroscopy were used to determine the composition of the copolymers. Copolymerization parameters for each system were calculated by both the Fineman & Ross and Kelen & Tudos methods. The monomer reactivity ratios for the systems 2PA-MA, 2PA-EA, ~PA-BuA, 2PA-MMA, 2PA-VA, and 2PA-AN were found by the Kelen & Tudos method to be rl = 0.58 f 0.042, r2 = 1.26 f 0-086; rl = 0.63 f 0.041, r2 = 1.04 0.072; rl = 0.88 f 0.051, r2 = 0.99 f 0.069; rl = 0.43 f 0.021, r2 = 1.60 f 0.094, rl = 0.69 f 0.051, r2 = 0-084 f 0.088; and r1 = 0.065 f 0.008, r2 = 2.54 f 0.220, respectively. The average Q and e values for 2PA were found to be 0.51 and 0.66, respectively.

Structure and thermal degradation of poly(N‐phenyl acrylamide) and poly(N‐phenyl methacrylamide)

“…A strong triplet at 1.032 ppm was attributed to –CH 3 groups, the broad peak centered at 1.95 ppm was attributed to the –CH 2 – protons, and the three singlets at 7.0–7.7 ppm were attributed to aromatic protons on the phenyl ring. A weak peak at 9.05 ppm was attributed to the –NH– proton 4. A combination of IR with 1 H‐NMR spectra confirmed the presence of the macromolecular structure of poly( N ‐phenyl methacrylamide) (PPMA) shown in Scheme .…”

“…We maintain that the properties of the polyacrylamides may be greatly manipulated by varying the substituents on the nitrogen atoms, to offer exciting possibilities for the development of new polymers. Although numerous investigations on the synthesis, structure, properties, and applications of the liquid crystalline poly(cyano‐biphenyl (meth)acrylate) and poly(alkoxy‐biphenyl (meth)acrylate) are cited in the literature,3 only a few studies on the synthesis of poly( N ‐cyano‐/alkoxy‐biphenyl (meth)acrylamide), N ‐2‐pyrimidyl, and N ‐2‐pyridyl acrylamide copolymers have been reported 3–5. Furthermore, very few reports concerning poly( N ‐phenyl (meth)acrylamide) have been found.…”

“…Although numerous investigations on the synthesis, structure, properties, and applications of the liquid crystalline poly(cyano-biphenyl (meth)acrylate) and poly(alkoxy-biphenyl (meth)acrylate) are cited in the literature, 3 only a few studies on the synthesis of poly(N-cyano-/alkoxy-biphenyl (meth)acrylamide), N-2-pyrimidyl, and N-2-pyridyl acrylamide copolymers have been reported. [3][4][5] Furthermore, very few reports concerning poly(N-phenyl (meth)acrylamide) have been found. To our knowledge no data about the thermal degradation and kinetics of poly(N-phenyl (meth)acrylamide) have been reported in the literature.…”

Preparation and characterization of the copolymer containing N‐pyridyl bi(methacryl)imide unit

“…A strong peak between 0.93 and 1.35 ppm should be attributed to CH 3 groups; another strong peak centered at 1.77 ppm is ascribed to the CH 2 – protons in the main chain; and the four singlets at 7.79–8.00 ppm and weak peaks ranging from 6.13 to 7.35 ppm are attributed to the aromatic protons on the pyridyl ring 9–11. The peak at 5.67 ppm might be related to the protons on the double bonds 4. It can be seen that the imidization degree of polymethacrylic acid by pyridylamine is not high.…”

“…Poly(cyano‐/alkoxy‐/alkyl‐biphenyl methacrylate) as a side‐chain liquid crystalline polymer with versatile properties has received increasing attention 1–3. There have also been a few investigations on the synthesis of 2‐pyrimidyl acrylamide copolymer,4 p ‐ n ‐diblock copolymer containing a bipyridylene unit,5 and poly(butyl methacrylate‐ co ‐vinylpyridine),6 and on gas permselectivity through polyvinylpyridine,7, 8 which could be one of the good gas‐separation membranes. The polyvinylpyridine crosslinked by divinylbenzene has been widely used as an ion exchanger.…”