Synthesis And Characterization Of N-[4-(Aminosulfonyl) Phenyl] Acrylamide Copolymers

The property of pre-sensitized plate(PS) is an important factor of affecting the printing quality and relates to the structure and properties of applied resin. The synthesis, structure and properties of ASPAA copolymers applied in high-performance PS plate were studied on the basis of the synthesized N-[4-(aminosulfonyl)phenyl]acrylamide(ASPAA) in this article, providing the basic theory for industrial production and application of resins.ASPAA was synthesized through the reaction of acryloyl chloride with sulfanilamide. The structure of ASPAA was confirmed by elemental analysis, IR and 1H-NMR spectrography. It showed that relative higher yield of ASPAA was achieved when the reaction conditions were optimized as follows: the molar ratio of sulfonamide to acryloyl chloride was 1:1.2, and sodium hydrogen carbonate to acryloyl chloride was 1.1:1, reaction temperature was 0-2℃, reaction time was 3h, the reaction mixture precipitated in methanol/water( 1:10,v/v).Several copolymers of ASPAA with acrylonitrile(AN) and methyl methacrylate (MMA) having different copolymer compositions were synthesized in N,N-dimethylformamide(DMF) using benzoyl peroxide as a initiator at 70±0.5℃. The composition of copolymer system was determined by using elemental analysis. The reactivity ratios were calculated by employing Fineman-Ross and Kelen-Tudos methods. The values of r1 and r2 obtained by two methods fitted well, i.e. r1=l .43 , r2=0.44 by Fineman-Ross method and r1=1.39 , r2=0.43 by Kelen-Tudos method for the ASPAA/AN copolymerization system, and r1=0.88 , r2=1.42 by Fineman-Ross method and r1=0.83 , r2=1.35 by Kelen-Tudos method for the ASPAA/MMA copolymerization system. The glass transition temperature (Tg) of ASPAA/AN and ASPAA/MMA copolymers increased as ASPAA content in ASPAA/AN and ASPAA/MMA copolymers increased.ASPAA/MMA/AN terpolymers were prepared by free radical polymerization in DMF and characterized by IR and 1H-NMR spectrography. Effects of polymerizationtemperature and initiator concentration on conversion-time curves for ASPAA/MMA/AN copolymerization were studied. It showed that relative higher polymerization rates were achieved at the early stage of copolymerization process at polymerization temperature of 85 and 95 ℃ and with the initiator concentration of 1.0-1.5wt%. After 2-3 hours, the polymerization rates decreased. The higher conversion (>95%) was achieved after 7 hours. Meanwhile, it showed that the polymerization rates were relative lower at polymerization temperature of 70℃ and it had no obvious auto-acceleration .Effects of temperatures, initiator concentrations, chain transfer agent on Mw, [ η ] and Mw/Mn for ASPAA/MMA/AN terpolymer were studied. Mw and [ η ] of terpolymer decreased as polymerization temperature and the concentration of initiator increased from 6.7X 104,22.52ml/g at 75℃ to 3.3 X104,17.35ml/g at 105 ℃, from 5.4 X104, 20.3ml/g with the initiator concentration of 0.5 % to 3.8 X104, 17.67ml/g with the initiator concentration of 2.0 % . Mw/Mn of terpolymer reached max at 85℃ from 75℃ to 105℃. Mw of terpolymer ASPAA/MMA/AN decreased as dodecylmercaptan concentrations increased at 85 ℃ . Mw and Mw/Mn ofterpolymer ASPAA/MMA/AN at 95℃ after 3 hours went stably.At last, the sensitivity, development latitude, printing durability of the experimental lithographic printing plate made from copolymers prepared by this work, were compared to those of the lithographic printing plate A and B. It showed that the alkaline resistance; development latitude and printing durability of the plate were improved by using copolymers synthesized in this work.