Copolymerization and copolymers of <i>N</i>‐(2,4,6‐tribromophenyl)maleimide with methyl acrylate and methyl methacrylate

Janović, Zvonimir; Matusinović, Tomislav; Ranogajec, Franjo

doi:10.1002/macp.1993.021940706

Cited by 13 publications

(10 citation statements)

References 14 publications

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“…M have been known for some time and have been widely used in organic synthesis 2, in polymer chemistry 3, and in biochemistry 4. During the past few years, M with functional groups have received increasing attention due to their ion‐exchange properties, optical and catalytic activities, fire‐resistance characteristics, high sensitivity and versatility in lithographic applications, or due to their ability to function as a photoinitiator 5–8. IM are also compounds of wide interest.…”

Section: Introductionmentioning

confidence: 99%

Computational study of maleamic acid cyclodehydration with acetic anhydride

Constantinescu

Ivanov

2005

Int J of Quantum Chemistry

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ABSTRACT:The reaction mechanisms of N-substituted maleamic acids (MA) cyclodehydration (CDH) to the corresponding maleimides (M) and isomaleimides (IM) and IM rearrangement to M were studied by the PM3 Hamiltonian with charge model 1 (CM1P) of the AMSOL computational method with solvation effect in order to establish the most probable pathways. CDH was considered in the presence of acetic anhydride in the presence of an acetate anion or triethylamine as the dehydrating agent in CH 2 Cl 2 as the solvent. In the first step, our computational results supported carboxylic proton losses, provided by a nucleophilic center on the dehydrating agent. In the next step, maleamic acid anion could either add a molecule of a dehydrating agent (path A) or cyclicize (path B). Our results indicate the path B to require more energy than path A, so path B is considered less likely to occur. The formation (path A) of an anion complex I2 between the anion of MA and the dehydration agent was supported as well as acetate anion loss to form the neutral mixed anhydride I3. The ring closure to M or IM occurs only after I3 amide proton loss, meaning that the dehydrating agent necessitate another nucleophilic center. The cyclization of I4 anion over amide nitrogen or oxygen to the reaction outcome depends on the electronic effect of amide nitrogen substituent. The same results were obtained studying CDH of N-substituted ophthalmic acids with acetic anhydride and for MA with N,NЈ-dicyclohexylcarbodiimide as dehydrating agent, in the same solvent. In such circumstances, one can consider them the common features of a general CDH reaction mechanism of MA. Our computational results found the IM to M rearrangement to correspond to the reversible final path of synthesis mechanism although the other investigators considered it to take place under a different reaction. They also supported the importance of the acetate anion in both cyclization and rearrangement mechanisms; the presence of tertiary amine blocks the acetic acid formed during reaction, determines I3 amide proton loss and prevents rearrangement. The theoretical conclusions are consistent with the experimental results.

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Section: Introductionmentioning

confidence: 99%

Computational study of maleamic acid cyclodehydration with acetic anhydride

Constantinescu

Ivanov

2005

Int J of Quantum Chemistry

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“…The susceptibility of N-substituted maleimides to homo-and co-polymerization by a free radical mechanism has been known for some time [1]. During the last few years, N-substituted maleimides with functional groups have received increasing attention due to their ion-exchange properties, optical and catalytic activities, fire-resistance characteristics, high sensitivity and versatility in lithographic applications or due to their ability to function as a photoinitiator [2][3][4][5]. In addition, the widespread use of copolymers demonstrates the vast potential of copolymerization as a tool for producing materials of intermediate properties to meet the requirements for new applications under unusual working conditions.…”

Section: Introductionmentioning

confidence: 99%

Functional Copolymers of N-(4-Formyl-Phenoxy-4′-Carbonylphenyl) Maleimide with Styrene

Hulubei¹,

Morariu²

2000

High Performance Polymers

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A new reactive N-substituted maleimide monomer containing an aldehyde function, N-(4-formyl-phenoxy-4 -carbonylphenyl) maleimide (MI-CHO), was synthesized. The radical copolymerization of MI-CHO with styrene was performed at 60 • C in the presence of 2,2azoisobutyronitrile as an initiator in dimethylsulfoxide. The copolymerization of MI-CHO with styrene yielded the 'nearly equimolar' alternating copolymers for the mole fractions of MI-CHO in the feed ranging from 0.2 to 0.7. The monomer reactivity ratios (r 1 , r 2 ) in the polymerization of MI-CHO (M 1 ) with styrene (M 2 ) and the Alfrey-Price Q 1 and e 1 parameters were determined. The thermal properties of the copolymers were investigated by using thermogravimetric analysis and differential scanning calorimetry.

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“…Alternative copolymerization is a special case in which both reactivity ratios of the monomer pair approach zero 6–8. In 1946 Bartlett and Nozaki9 prepared alternative copolymers of styrene (St) and maleic anhydride and proposed a simple idea of a charge‐transfer complex (CTC) formation resulting from the interaction of electropositive and electronegative monomers in the copolymerization.…”

Section: Introductionmentioning

confidence: 99%

Novel generalized rate equation for free radical copolymerization

Shan

Wang

Huang

et al. 1999

J. Appl. Polym. Sci.

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A generalized copolymerization rate equation is proposed. The North equation of copolymerization is a special case that can be derived from the generalized equation. According to the mass balance and charge‐transfer complex (CTC) equilibrium equation, the free monomer concentration is differentiated from the feed monomer concentration. The effects on the copolymerization rate (the equilibrium constant, total monomer concentration, homopropagation constants, and reactivity ratios) are quantitatively calculated and discussed. The generalized equation may be applied to not only the systems with the participation of CTC, such as styrene/N‐phenylmaleimide (PMI), but also those without the participation of CTC, such as methyl methacrylate/PMI. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2635–2639, 1999

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Copolymerization and copolymers of N‐(2,4,6‐tribromophenyl)maleimide with methyl acrylate and methyl methacrylate

Cited by 13 publications

References 14 publications

Computational study of maleamic acid cyclodehydration with acetic anhydride

Computational study of maleamic acid cyclodehydration with acetic anhydride

Functional Copolymers of N-(4-Formyl-Phenoxy-4′-Carbonylphenyl) Maleimide with Styrene

Novel generalized rate equation for free radical copolymerization

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