Radical copolymerization of 2-vinyl pyridine and oligo(ethylene glycol) methyl ether methacrylates: Monomer reactivity ratios and thermal properties

Driva, Paraskevi; Bexis, Panagiotis; Pitsikalis, Marinos

doi:10.1016/j.eurpolymj.2010.09.032

Cited by 31 publications

(20 citation statements)

References 30 publications

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“…It is well known that copolymer properties are correlated to copolymer structure, so, the elucidation and manipulation of structure (composition, monomer sequence distribution) and kinetics (propagation rate coefficients and reactivity ratios) are of major importance. An enormous amount of work, both experimental and theoretical, describes the significance of copolymerization in the field of polymer science …”

Section: Introductionmentioning

confidence: 99%

Statistical copolymers of N‐vinylpyrrolidone and 2‐(dimethylamino)ethyl methacrylate via RAFT: Monomer reactivity ratios, thermal properties, and kinetics of thermal decomposition

Roka

Kokkorogianni

Pitsikalis

2017

J. Polym. Sci. Part A: Polym. Chem.

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Statistical copolymers of N‐vinylpyrrolidone (NVP) with 2‐(dimethylamino)ethyl methacrylate (DMAEMA) were prepared by Reversible Addition‐Fragmentation chain Transfer Polymerization (RAFT), employing three different RAFT agents: [(O‐ethylxanthyl)methyl]benzene, [1‐(O‐ethylxanthyl)ethyl]benzene, and O‐ethyl S‐(phthalimidylmethyl) xanthate. The reactivity ratios were estimated using the Fineman‐Ross, inverted Fineman‐Ross, Kelen‐Tüdos, and extended Kelen‐Tüdos graphical methods, along with the computer program COPOINT. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions and the mean sequence length. All the methods indicate that the DMAEMA reactivity ratio is much greater than the one of NVP, thus, the statistical copolymers are in fact pseudo‐diblocks. The glass‐transition temperature (Tg) values of the copolymers were measured by Differential Scanning Calorimetry. Furthermore, a systematic and detailed investigation has been done, on the thermal degradation of the copolymers compared with the respective homopolymers, by Thermogravimetric Analysis, within the framework of the Ozawa‐Flynn‐Wall and Kissinger methodologies. Apparently, the thermal stability of the copolymers is influenced by both monomers and by the structure of the thiocarbonylthio end groups due to the RAFT agents. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3776–3787

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Section: Introductionmentioning

confidence: 99%

Statistical copolymers of N‐vinylpyrrolidone and 2‐(dimethylamino)ethyl methacrylate via RAFT: Monomer reactivity ratios, thermal properties, and kinetics of thermal decomposition

Roka

Kokkorogianni

Pitsikalis

2017

J. Polym. Sci. Part A: Polym. Chem.

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“…Reactivity ratios for this system were not available in the literature. However, there are related systems: 2VP with OEGMA (300 and 1100) had r2VP = 0.99-1.13, rOEGMA300 = 0.16-0.25 [68]. Regardless, tuning for this system is relatively predictable.…”

Section: Nitroxide Mediated Polymerizationmentioning

confidence: 99%

Poly(methacrylic acid-ran-2-vinylpyridine) Statistical Copolymer and Derived Dual pH-Temperature Responsive Block Copolymers by Nitroxide-Mediated Polymerization

2017

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Nitroxide-mediated polymerization using the succinimidyl ester functional unimolecular alkoxyamine initiator (NHS-BlocBuilder) was used to first copolymerize tert-butyl methacrylate/ 2-vinylpyridine (tBMA/2VP) with low dispersity (Đ = 1.30-1.41) and controlled growth (linear number average molecular M n versus conversion, M n = 3.8-10.4 kg·mol −1 ) across a wide composition of ranges (initial mol fraction 2VP, f 2VP,0 = 0.10-0.90). The resulting statistical copolymers were first de-protected to give statistical polyampholytic copolymers comprised of methacrylic acid/2VP (MAA/2VP) units. These copolymers exhibited tunable water-solubility due to the different pKas of the acidic MAA and basic 2VP units; being soluble at very low pH < 3 and high pH > 8. One of the tBMA/2VP copolymers was used as a macroinitiator for a 4-acryloylmorpholine/4-acryloylpiperidine (4AM/4AP) mixture, to provide a second block with thermo-responsive behavior with tunable cloud point temperature (CPT), depending on the ratio of 4AM:4AP. Dynamic light scattering of the block copolymer at various pHs (3, 7 and 10) as a function of temperature indicated a rapid increase in particle size >2000 nm at 22-27 • C, corresponding to the 4AM/4AP segment's thermos-responsiveness followed by a leveling in particle size to about 500 nm at higher temperatures.

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“…The synthesis of the statistical copolymers has been described in detail elsewhere [10], [11]. Briefly, all manipulations were performed using high vacuum techniques.…”

Section: Methodsmentioning

confidence: 99%

“…The monomer structures are given in Scheme 1. It was found that the reactivity ratios of 2VP, r 2VP were higher in all statistical copolymers (r 2VP =3.04 and r BuOEMA =0.48 for the P2VP-co-PBuOEMA copolymers [10], r 2VP =1.57 and r DEGMA =0.92 for the P2VP-co-PDEGMA copolymers [10], whereas r 2VP =1.08 and r OEGMA300 =0.23 for the P2VP-co-POEGMA300 copolymers [11]) indicating a kinetic preference for the incorporation of the 2VP units in the copolymer structure. These findings prompted the present study of the kinetics of the thermal decomposition of these statistical copolymers by Thermogravimetric Analysis (TGA) and Differential Thermogravimetry (DTG).…”

Section: Introductionmentioning

confidence: 99%

Thermal Degradation of Statistical Copolymers of 2-Vinyl Pyridine with Functional Methacrylates

2016

International Journal of Advanced Research in Chemical Science

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Radical copolymerization of 2-vinyl pyridine and oligo(ethylene glycol) methyl ether methacrylates: Monomer reactivity ratios and thermal properties

Cited by 31 publications

References 30 publications

Statistical copolymers of N‐vinylpyrrolidone and 2‐(dimethylamino)ethyl methacrylate via RAFT: Monomer reactivity ratios, thermal properties, and kinetics of thermal decomposition

Statistical copolymers of N‐vinylpyrrolidone and 2‐(dimethylamino)ethyl methacrylate via RAFT: Monomer reactivity ratios, thermal properties, and kinetics of thermal decomposition

Poly(methacrylic acid-ran-2-vinylpyridine) Statistical Copolymer and Derived Dual pH-Temperature Responsive Block Copolymers by Nitroxide-Mediated Polymerization

Thermal Degradation of Statistical Copolymers of 2-Vinyl Pyridine with Functional Methacrylates

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