Copolymerization of N‐phenyl maleimide with methyl acrylate, ethyl acrylate, methyl methacrylate, and butyl methacrylate

Abstract

N-phenyl maleimide (NPMI) was copolymerized with methyl acrylate (MA), ethyl acrylate (EA), methyl methacrylate (MMA), and butyl methacrylate (BMA). The composition diagrams for the copolymerization were determined. An azeotropic monomer composition was found in the range 0.55 to 0.65 of the acrylate feed ratio for the systems MA, EA, and MMA with NPMI with a maximum initial rate ofcopolymerization at 10 mole-% acrylate, whereas neither an azeotropic composition nor a maximum rate was found with the system BMA-NPMI. High concentration of maleimide in the monomer feed affects the intrinsic viscosity negatively. Degradative chain transfer to maleimide is assumed to cause the decrease in molecular weight. Copolymerisation von N-Phenylmaleinimid mit Methylacrylat, Ethylacrylat. Methylmethacrylat und ButylmethacrylatN-Phenylmaleinimid (NPMI) wurde mit Methylacrylat (MA), Ethylacrylat (EA), Methylmethacrylat (MMA) und Butylmethacrylat (BMA) copolymerisiert. Die Zusammensetzungsdiagramme der Copolymerisation wurden bestimmt. Fur die Systeme MA, EA und MMA mit NPMI wurden eine azeotrope Monomerzusammensetzung bei einem Acrylatanteil von 0.55 bis 0.65 in der Ausgangsmischung sowie eine maximale Anfangsgeschwindigkeit der Copolymerisation bei 10 Mol-Yo Acrylat gefunden. Dagegen traten beirn System BMA-NPMI weder eine azeotrope Zusammensetzung noch ein Geschwindigkeitsmaximum auf. Eine hohe Maleinimidkonzentration in der Ausgangsmischung beeinfluI3t die Grenzviskositiit negativ. ES wird angenommen, daD die Kettenubertragung zum Maleinimid die Abnahme der Molekiilmasse verursacht.

Correlation between molecular structure and copolymer composition and the Mark-Houwink constants of methyl methacrylate/N-phenylmaleimide copolymers

“…Homopolymers of NPI show the greater stiffness caused by the five-membered planar ring of NPI, which hinders the rotation of the imide residues around the backbone chain of the macromolecule 21) . The steric factors and the limited chain mobility are the reasons that the coils are less penetrated 11,13) . The determination of the Mark-Houwink constants is possible neither with the GPC nor with the Ubbelohde capillary viscosimeter, because of the great deviations from a linear correlation.…”

“…When the maleimide unit, which has a rigid structure, is introduced into the flexible vinyl polymer chain of MMA, the intra-and intermolecular interactions which differ from those of homopolymers are expected to play an important role on the flow properties of the copolymers. Investigation of intrinsic viscosities of MMA/NPI copolymers shows that the intrinsic viscosity increases proportionally with the NPI content of up to 50 mol-% NPI 11) . High maleimide concentrations result in a decrease of the intrinsic viscosities 11,12) .…”

“…Investigation of intrinsic viscosities of MMA/NPI copolymers shows that the intrinsic viscosity increases proportionally with the NPI content of up to 50 mol-% NPI 11) . High maleimide concentrations result in a decrease of the intrinsic viscosities 11,12) . Large values of a in the Mark-Houwink relation indicate the less flexible chain structure of maleimides as is the case of poly(Ntert-butylmaleimide) (tBMI) in dilute solutions of benzene 13) .…”

Free Radical Copolymerization of Methyl methacrylate and N‐Phenyl maleimide in 1‐Butyl‐3‐methylimidazolium tetrafluoroborate

“…The Q-and e-values of MMA are Q ¼ 0.78 AE 0.06 and e ¼ 0.40 AE 0.08 [29] . There are different opinions whether MMA in the case of the copolymerization with NPI acts as a donor monomer [30,31] or a neutral monomer [32,36] . Elsabee et al [30] found that the copolymerization of MMA/NPI is dependent on the type of solvent.…”