Radical polymerization of methyl methacrylate initiated by pyridine dicyanomethylide

Shukla, Prerna; Srivastava, Archana

doi:10.1016/0014-3057(88)90074-2

Cited by 12 publications

(3 citation statements)

References 12 publications

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“…Briefly, β obtained for di-M as 0.59 ± 0.03 (95% confidence) was considered as statistically different from the ideal value of β = 0.5 but independent of the di-M concentration in the investigated range. Analyzing the data according to Deb and Meyerhoff [60,61] as well as Ghosh, Mitra and Shukla [62,63] lead to the conclusion that neither PRT nor DCT took place, or were significant. Contrary to the predicted negative slopes for PRT and DCT, positive slopes were obtained plotting log( R P 2 /[I][M] 2 ) = f ( R P /[M] 2 ) and log( R P 2 /[I][M] 2 ) = f ([I]/[M]), respectively [21].…”

Section: Discussionmentioning

confidence: 99%

Effect of Very High Charge Density and Monomer Constitution on the Synthesis and Properties of Cationic Polyelectrolytes

2016

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Abstract:The free-radical homopolymerization of 1,3-bis(N,N,N-trimethylammonium)-2-propylmethacrylate dichloride (di-M) and 1,3-bis(N,N,N-trimethylammonium)-2-propylacrylate dichloride (di-A) in aqueous solution yields cationic polyelectrolytes (PEL) with theoretical/structural charge spacing of only «0.12 nm. The high charge density causes condensation of «82% of the chloride counterions. The high level of counterion condensation reduces the ionic strength in the polymerizing batch when the monomer molecules connect to PEL chains. This has the consequence that the hydrodynamic and excluded volume of the PEL molecules will change. Studies of the free radical polymerization revealed non-ideal polymerization kinetics already at low conversion and additionally autoacceleration above a certain monomer concentration and conversion. Similar autoacceleration was not observed for monomers yielding PEL with charge spacing of 0.25 or 0.5 nm. Coulomb interactions, monomer association, steric effects, and specific features of the monomer constitution have been evaluated concerning their contributions to the concentration dependence and conversion dependence of kinetic parameters. The different backbone constitutions of di-M and di-A not only influence the polymerization kinetics but also equip poly(di-M) with higher hydrolytic stability. The experimental results confirm the impact of electrochemical parameters and the necessity to reconsider their inclusion in kinetic models.

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Section: Discussionmentioning

confidence: 99%

Effect of Very High Charge Density and Monomer Constitution on the Synthesis and Properties of Cationic Polyelectrolytes

2016

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“…[14][15][16][17] In absence of PRT, considering only DCT, the kinetic data can be analyzed based on a relationship of Deb further simplified by Ghosh and Mitra. [13,15] Again, a positive slope of a plot, for which a negative one was expected in case of DCT, identified no measurable DCT to the initiator. Consequently, DCT to the monomer remained to explain the elevated initiator exponent.…”

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confidence: 99%

Non‐Ideal Polymerization Kinetics of a Cationic Double Charged Acryl Monomer and Solution Behavior of the Resulting Polyelectrolytes

Losada

Wandrey

2008

Macromol. Rapid Commun.

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The radical polymerization of bis‐1,3(N,N,N‐trimethylammonium)‐2‐propylmethacrylate dichloride revealed non‐ideality with 0.59 and 4.4 for the reaction orders of the initiator and monomer concentration, respectively. Further, autoacceleration was observed from less than 10% conversion onwards. Degradative chain transfer to the monomer was concluded to explain the initiator exponent. Monomer association and electrostatic effects are hypothesized to govern the monomer exponent and autoacceleration. The exponential concentration dependent increase of the viscosity of the monomer solution and the relatively low overall activation energy Ea = 31.5 kJ · mol−1 support the hypothesis. Counterion activity measurements confirmed strong counterion condensation as expected for a charge distance of 0.12 nm.magnified image

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“…[135] The system followed non-ideal kinetics owing to the primary radical termination as well as the degradative chain transfer reaction. [135] The system followed non-ideal kinetics owing to the primary radical termination as well as the degradative chain transfer reaction.…”

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confidence: 99%

Photopolymerization: A Review

Kaur

Srivastava

2002

Journal of Macromolecular Science, Part C: Polymer Reviews

124

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Radical polymerization of methyl methacrylate initiated by pyridine dicyanomethylide

Cited by 12 publications

References 12 publications

Effect of Very High Charge Density and Monomer Constitution on the Synthesis and Properties of Cationic Polyelectrolytes

Effect of Very High Charge Density and Monomer Constitution on the Synthesis and Properties of Cationic Polyelectrolytes

Non‐Ideal Polymerization Kinetics of a Cationic Double Charged Acryl Monomer and Solution Behavior of the Resulting Polyelectrolytes

Photopolymerization: A Review

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