Synthesis and characterization of poly(amide‐amine) polymers

Abstract

INTRODUCTIONAmino polymers have been extensively used in industry. The addition of primary or secondary mines to vinyl double bonds activated by electron attracting groups is well known.' Hulse2 obtained a water-soluble poly(amide-mines) by the reaction of NJV-methylenebisacrylamide with piperazine in water. Later on, Danusso et al.34 synthesized linear poly(amide-amines) by the polyaddition of primary monoamines or bis(secondary) diamines to bisacrylamides. They further confirmed that the polymerization is a nucleophilic polyaddition with an anionic mechanism and is not influenced by the presence of the inhibitors of radical polymerization. The polyaddition reaction of bisacrylamide with bis(secondary) diamine or primary amine that leads to poly(amide-amines) may be accomplished with acrylic diesters or divinyl sulfone instead of bisacrylamide.6 Yoda et al." obtained transparent poly(amide-amines) from acrylates with diamines. Ferruti3s8 prepared linear poly(amide-amines) from hydrazine and bisacrylamides. However, they observed that the linear polymers could be obtained from equimolar amounts of hydrazine and bisacrylamide, whereas crosslinked polymers were obtained with higher amounts of bisacrylamides. Imai et aL9 have studied the polyaddition of aromatic diamines with N,N'-methylenebisacrylamide. They have also studied the effect of solvent and acidic catalyst on the molecular weight of poly(amide-amines).A series of poly(amide-amines) with sulfone and ether linkages was prepared in the present study and their structure property relationship was examined. EXPERIMENTAL MaterialsAcrylamide (Cyanamide, USA) was recrystallized twice from methanol before use. Paraformaldehyde (BDH, England) was used as received. n-Butyraldehyde (BDH, England) and benzaldehyde (local market) were purified by distillation before use. 4,4'-Methylene dianiline (Bayer, A. G., West Germany), and 4,4'-oxydianiline (EGA Chemie, West Germany) were recrystallized from benzene and tetrahydrofuran (THF), respectively before use. m-Cresol, ethylene dichloride, and glacial acetic acid were purified by standard methods. Bisacrylamides were prepared by the method described by Feuer and Lynch.lo Sulfone ether diamines were prepared by the method described by Kawakami and co-workers.ll PolymerizationA typical example of polycondensation in the synthesis of poly(amide-amine) from N,N'-methylenebisacrylamide and 4,4'-bis(4-amino phenoxy) diphenyl sulfone is given below:Into a 50-mL, three-necked, round-bottomed flask equipped with a thermometer, nitrogen gas inlet, reflux condenser, and magnetic stirrer were placed 0.77 g (0.05 mol) of N,N'-methylenebisacrylamide, 2.16 g (0.05 mol) of 4,4'-bis(4-amino phenoxy) diphenyl sulfone, 0.4 cm3 of glacial acetic acid, and 10 cm3 of m-cresol. The reaction mixture was stirred at 100°C for 24 h in a nitrogen at-

CLEAR: A Novel Family of Highly Cross-Linked Polymeric Supports for Solid-Phase Peptide Synthesis1,2

“…The fact that amino groups could be introduced directly rather than by transformation of another functional group, or by deprotection of a protected amino monomer, was an unanticipated yet advantageous discovery in the CLEAR family. Incorporation of amines into synthetic polymers has been reported to be difficult due to (i) addition of the amine to activated vinylic double bonds 20 and (ii) O f N acyl migration resulting in hydroxylated acrylamides when starting with amino acrylates. 21 For this work, the amine precursors were used in sufficiently high excess to achieve the required final substitution levels.…”

Thermal analysis

“…The thermal degradation E values were in accordance with the thermal behavior. Poly(amide-amine) polymers were prepared from bis(acrylamides) and sulfone ether diamines and were characterized by TA and other techniques (43). Introduction of methyl groups on the diamine lowered the thermal stability of the polymers.…”