Copolymerization of Indene with N-Phenylmaleimide

Mokhtar, S. M.; Mikhael, Michael G.; Aly, Raouf O.; Elsabeé, Maher Z.

doi:10.1295/polymj.20.979

Cited by 3 publications

(1 citation statement)

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“…Moreover, most maleimide and Ind monomers have also been reported to be nonhomopolymerizable or have low k p values through radical processes, which limits the formation of homopolymer side products . In addition, maleimide monomers are electron accepting, while Ind monomers are electron donating, leading to formation of a charge transfer complex and allowing for alternating copolymerization to occur with high reaction rates, although there has been debate of the mechanism on alternating copolymerization in the literature. , Maleic anhydride (MAn, Scheme a) presents similar reaction behavior to maleimides; however, there is a high potential for hydrolysis and thus ring opening during the reaction. Meanwhile, although maleate, fumarate, and trans-β-methylstyrene ( trans -MeSt, Scheme b) have low k p (∼0), their reaction yields for SUMI into RAFT agents are very low (SI, see Section 2.3), suggesting addition rates of these monomers are not as high as maleimides and Ind, and thus they are not ideal monomers for the SUMI process used in this study.…”

Section: Resultsmentioning

confidence: 99%

Discrete and Stereospecific Oligomers Prepared by Sequential and Alternating Single Unit Monomer Insertion

et al. 2018

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Natural biopolymers, such as DNA and proteins, have uniform microstructures with defined molecular weight, precise monomer sequence, and stereoregularity along the polymer main chain that affords them unique biological functions. To reproduce such structurally perfect polymers and understand the mechanism of specific functions through chemical approaches, researchers have proposed using synthetic polymers as an alternative due to their broad chemical diversity and relatively simple manipulation. Herein, we report a new methodology to prepare sequence-controlled and stereospecific oligomers using alternating radical chain growth and sequential photoinduced RAFT single unit monomer insertion (photo-RAFT SUMI). Two families of cyclic monomers, the indenes and the N-substituted maleimides, can be alternatively inserted into RAFT agents, one unit at a time, allowing the monomer sequence to be controlled through sequential and alternating monomer addition. Importantly, the stereochemistry of cyclic monomer insertion into the RAFT agents is found to be trans-selective along the main chains due to steric hindrance from the repeating monomer units. All investigated cyclic monomers provide such trans-selectivity, but analogous acyclic monomers give a mixed cis- and trans-insertion.

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Section: Resultsmentioning

confidence: 99%

Discrete and Stereospecific Oligomers Prepared by Sequential and Alternating Single Unit Monomer Insertion

et al. 2018

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Polymerisation von n‐substituierten maleimiden in epoxidverbindungen, 1

Lüders

Merker

Raubach

1990

Angew. Makromol. Chem.

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ZUSAMMENFASSUNGN-substituierte Maleimide polymerisieren in Glycidethern rnit einer Reaktion erster Ordnung, ausgelirst durch eine Startreaktion zweiter (pseudo-erster) Ordnung. Die Aktivierungsenergie der Startreaktion liegt rnit fast 70 kJ/mol oberhalb, die der Polymerisation mit 48 kJ/mol weit unterhalb der Werte der rein thermischen Maleimidpolymerisation von etwa 60 kJ/mol. Die Werte werden durch DSC-Untersuchungen von Bismaleimiden in Diepoxiden bestatigt. Die Startreaktion verlluft ab 100 "C mit deutlicher Exothermie unter Epoxidverbrauch, Rotfarbung und Bildung von Radikalen rnit g = 2.0034.Die Polymerisation wird durch SBuren und nicht durch Radikalfanger abgebrochen.Es werden Maleimid-Oligomere rnit P, = 5 -7 erhalten, die glycidether-spezifische Gruppen tragen und katalytisch wirken. Eine anionische Initiierung wird diskutiert. SUMMARY:The polymerization of N-substituted maleimides takes place in epoxy compounds according to a first-order reaction initiated by a starting reaction of second (pseudofirst) order. The activation energy of this starting reaction is nearly 70 kJ/mol and is much more as the value of the pure thermal polymerization of maleimides (60 kJ/mol). However, the value of the polymerization reaction of 48 kJ/mol lies far below the pure thermal polymerization. The results were obtained by dilatometry and DSC measurements. The starting reaction shows above 100 OC exothermic effects, consumption of epoxide, red coloration and formation of radicals of g = 2.0034. The polymerization breaks off by acids but not by radical trapping. The obtained maleimide-oligomers with a degree of polymerization P, = 5 -7 contain specific groups of the origin epoxidecompounds and they show catalytic activity. Anionic initiation is discussed. EinleitungN-substituierte Maleimide zeigen das charakteristische Verhalten von 1 ,Zdisubstituierten Ethylenen' -3. Die beiderseits nachbarstiindigen Carbo-0 1990 Huthig t Wepf Verlag, Basel CCC 0003-3 146/90/$03.00

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