Effects of complex formation and cyclization in radical copolymerization of allyl(metha)acrylates with maleic anhydride

Abstract

Radical copolymerization of allyl acrylate (AA) and allyl methacrylate (AMA) as bifunctional monomers of donor (allyl)–acceptor (acryl) type with maleic anhydride (MA) as an acceptor monomer were carried out in metrhyl ethyl ketone (MEK) at 50–70°C in the presence of 2,2′‐azoisobutyronitrile (AIBN) as initiator. Constants of complex formation (Kc), cyclization (kcl), and copolymerization (r1, r2, r1c, r1c1, and r1c2) as well as energies of activation for cyclization (Eac) and copolymerization reactions (Ea), and orders for the monomer (m) and initiator (n) concentrations were determined. The following values were found, for AA and AMA, respectively: Kc = 0.038 and 0.11 L/mol in deutered acetone at 35 ± 0.1°C, kcl = 6.45 and 6.53, r1 = 0.083 ± 0.005 and 0.028 ± 0.002, r2 = 0.027 ± 0.002 and 0.063 ± 0.003 (by the Kelen–Tüdös method), r1c = 0.04 and 0.025, r1c1 = 0.128 and 0.176, r1c2 = 0.127 and 0.177 (by the Seiner–Litt equation), Eac = 28.9 and 28.7 kJ/mol, Ea = 67.0 and 87.9 kJ/mol, m = 1.53 and 1.45, and n = 0.50 and 0.52. The presence of cyclic, unsaturated, and anhydride fragments in the macromolecules was confirmed with FTIR data and chemical (iodometrical and potentiometric titrations) analysis. It was established that complex formation in the monomer systems studied is the main factor for alternating cyclocopolymerization leading to formation of copolymers containing lactone and linear‐unsaturated fragments in the macromolecular chain. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1501–1508, 1998

Maleic Anhydride and Its Derivatives: A Brief Review of Reactivity and Properties in Radical (Co)Polymerizations

“…The use of MAnh in a copolymerization reaction leads to a copolymer with regularly spaced functional handles for post‐polymerization functionalization [13] and imparts crosslinking ability [13, 18]. Some monomers that have been copolymerized via conventional radical copolymerization with MAnh include methacrylates [28, 29], methyl methacrylate [30], styrenics [31–41], olefins [24, 34, 42–45], vinyl ethers [24, 46–53], furans [24], vinyl acetate [54–56], phenylethyne [57], stilbenes [26, 27, 58], acrylamides [59, 60], N ‐vinylpyrrolidone [61], acrylonitrile [62], dienes [63–65], norbornene [14, 66, 67], and aromatic compounds [25, 68, 69]. MAnh is copolymerized under conventional radical conditions at temperatures ranging from 60°C to 140°C [41], where the majority of copolymerizations utilize 70°C.…”

“…The use of MAnh in a copolymerization reaction leads to a copolymer with regularly spaced functional handles for post‐polymerization functionalization [ 13 ] and imparts crosslinking ability [ 13 , 18 ]. Some monomers that have been copolymerized via conventional radical copolymerization with MAnh include methacrylates [ 28 , 29 ], methyl methacrylate [ 30 ], styrenics [ 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 ], olefins [ 24 , 34 , 42 , 43 , 44 , 45 ], vinyl ethers [ 24 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 ], furans [ 24 ], vinyl acetate [ 54 , 55 , 56 ], phenylethyne [ 57 ], stilbenes [ 26 , 27 , 58 ], acrylamides [ 59 , 60 ], N ‐vinylpyrrolidone [ 61 ], acrylonitrile [ 62 ], dienes [ 63 , 64 , 65 ], norbornene [ 14 , 66 , 67 ], and aromatic comp...…”

Quantum Chemical Calculation of Maleic Anhydride Ring-Opening Reaction

“…Nowadays the MAH multipolymers were studied extensively.Because of C=C double bond has double substitutions and the great Spatial steric hindrance, MAH was always regarded as representative that couldn't carry out homopolymerization [1,2] . Much attention has been paid to MAH polymerization(Homopolymerization [4] and Copolymerization [5][6][7][8][9][10][11][12][13][14][15] )gradually Long and his colleagues [3] published papers on MAH homopolymerization in 1963. The related reports have been increased since MAH multipolymer was found to possess anti-tumor and biological activity [16] .…”

Complex-Radical Terpolymerization of Maleic Anhydride (Styrene), Allyl Propionate and Methyl Methacrylate

“…In Table 4 are summarized the values of the apparent reactivity ratios for the monomer systems studied. From the values of copolymerization constants it follows that alternating copolymerization reactions occur mainly in the MA-AP, MA-AMA [20] and St-AMA [22] Table 2 Continued Table 3 Experimental data used for determination of copolymerization constants for MA(M 1 )-AP(M 2 ) and MMA(M 1 )-AP(M 2 ) monomer pairs. Reaction conditions as in Table 1. * Calculated for alternating copolymer with 1 : 1 composition: AN 495.9 mg KOH/g.…”