Substituent effects in free radical copolymerization of substituted styrenes with acrylates and methacrylates

Faber, J. W. H.; Fowler, W. F.

doi:10.1002/pol.1970.150080714

Cited by 10 publications

(4 citation statements)

References 8 publications

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“…The molecular structure of 2,5‐dichloro styrene (M 2 ) is similar to MPCS if we take MPCS as styrene substituted by two [(4‐methoxy)phenyl]oxycarbonyl groups at the ortho and meta positions, respectively. The reactivity ratio of styrenic monomer is affected by the distance of the substituent to the vinyl double bond, the size of the substituent, and the number of unshared electron pairs in the substituent 29, 30. Though MPCS has a large substituent, MPCS is more reactive than St and MMA.…”

Section: Resultsmentioning

confidence: 99%

Copolymers of 2,5‐bis[(4‐methoxyphenyl) oxycarbonyl]styrene with styrene and methyl methacrylate: Synthesis, monomer reactivity ratios, thermal properties, and liquid crystalline behavior

Zhao

Fan

et al. 2005

J. Polym. Sci. A Polym. Chem.

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Copolymers of a liquid crystalline monomer, 2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene (MPCS), with St and MMA were prepared by free radical polymerization at low conversion in chlorobenzene with 2,2 0 -azobisisobutyronitrile (AIBN) as initiator. The copolymers of poly(MPCS-co-St) and poly(MPCS-co-MMA) were characterized by 1 H NMR and GPC. The monomer reactivity ratios were determined by using the extended Kelen-Tudos (EKT) method. Structural parameters of the copolymers were obtained from the possibility statistics and monomer reactivity ratios. The influence of MPCS content in copolymers on the glass transition temperatures of copolymers was investigated by DSC. The thermal stabilities of the two copolymer systems increased with an increase of the molar fraction of MPCS in the copolymers. The liquid crystalline behavior of the copolymers was also investigated using DSC and POM. The results revealed that the copolymers with high MPCS molar contents exhibited liquid crystalline behaviors. V V C 2005 Wiley Periodicals, Inc. J Polym Sci Part A:

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Section: Resultsmentioning

confidence: 99%

Copolymers of 2,5‐bis[(4‐methoxyphenyl) oxycarbonyl]styrene with styrene and methyl methacrylate: Synthesis, monomer reactivity ratios, thermal properties, and liquid crystalline behavior

Zhao

Fan

et al. 2005

J. Polym. Sci. A Polym. Chem.

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“…r;=kiijkii (i=FJ) (2) where Fobs and F,.,m are the observed and calcu- 16 under the same conditions. They determined the copolymer compositions by ultraviolet (UV) absorption analysis and evaluated r1, r2 by the Fineman and Ross method.…”

Section: Analysis Based On the Terminal Modelmentioning

confidence: 99%

“…15 In this paper, we examine the composition equation of the bulk-copolymerization of p-chlorostyrene (pCS) and methyl acrylate (MA). 16 Originally, we were interested in the composition distribution of the copolymers produced in a continuous stirred tank reactor (CSTR), as a measure for fluid mixing in the reactor. 17 -19 To this end, the pCS-MA system appeared to be beneficial in several technical aspects.…”

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confidence: 99%

Free-Radical Copolymerization I. Reactivity Ratios in Bulk-Copolymerization of p-Chlorostyrene and Methyl Acrylate

Fukuda

Inagaki

1982

Polym J

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ABSTRACT:In order to establish the composition equation for the bulk-copolymerization of p-chlorostyrene (monomer I) and methyl acrylate (monomer 2) at 40°C, an extraordinarily large number of careful polymerization runs were carried out covering a wide range of feed composition. The samples were analyzed for composition by both potentiometric titration for chlorine and combustion analysis for carbon. The optimum set of terminal-model parameters evaluated by a least-squares curve-fitting procedure are r 1 = 1.21 and r 2 =0.144, quite at variance with the literature values, but conform to the Q-e scheme. However, the chlorine and carbon sets of data consistently indicate failure of the terminal model to accurately represent this system. The penultimate model parameters r1 =0.92, r1 ' =2.3, and r2 ( =r/)=0.18 represent the system almost perfectly. This indicates the presence of significant penultimate effects on type-! radicals. The question as to the penultimate effects on type-2 radicals remains to be answered.

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“…Both the composition and placement of monomers are dependent on the relative reactivity of each monomer in the system toward the growing polymer radicals, and vice versa. The reactivity ratios of vinylic monomer is affected by the distance of the substituent to the vinyl double bond, the size of the substituent, and the number of unshared electron pairs in the substituent (51,52). Though MPPA has a large substituent, MPPA is more reactive than TSEM.…”

Section: Copolymer Composition and Monomer Reactivity Ratiosmentioning

confidence: 98%

Preparation of Organic/Inorganic Hybrid Materials Using Agregates of Poly{2-methyl-N-[2-(phenylthio)phenyl] Acrylamide-co-2-(Trimethylsyloxy)Ethyl Methacrylate} as Precursor and Vibrational Investigation of the Polymerization

Arı¹,

Soykan²,

Özpozan³

2013

Journal of Macromolecular Science, Part A

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Acrylamide based monomer, 2-methyl-N-[2-(phenylthio)phenyl]acrylamide (MPPA) was synthesized by reacting 2-(phenylthio) aniline with methacryloylchloride. The copolymerization of MPPA, with 2-(trimethylsyloxy)ethyl methacrylate(TSEM) was carried out with different monomer-to-monomer ratios in the feed. All the compounds were characterized by IR, Raman and 1 H-and 13 C-NMR techniques and SEM analysis. The elemental analysis of the copolymer composition led to the determination of reactivity ratios employing Fineman-Ross, Kelen-Tüdös and Extended Kelen-Tüdös linearization methods. These parameters were also estimated using a non-linear computational fitting procedure, known as reactivity ratio errors in variable model. The molecular weights and polydispersity index of polymers was determined by gel permeation chromatography. Thermal stability of the copolymers were found to increase with increasing mole fraction of MPPA from thermogravimetric analysis. The vibrational analysis of MPPA and poly(MPPA) were also performed to explain the vibrational spectra and to confirm the polymerization on the basis of a theoretical and experimental aproach.

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Substituent effects in free radical copolymerization of substituted styrenes with acrylates and methacrylates

Cited by 10 publications

References 8 publications

Copolymers of 2,5‐bis[(4‐methoxyphenyl) oxycarbonyl]styrene with styrene and methyl methacrylate: Synthesis, monomer reactivity ratios, thermal properties, and liquid crystalline behavior

Copolymers of 2,5‐bis[(4‐methoxyphenyl) oxycarbonyl]styrene with styrene and methyl methacrylate: Synthesis, monomer reactivity ratios, thermal properties, and liquid crystalline behavior

Free-Radical Copolymerization I. Reactivity Ratios in Bulk-Copolymerization of p-Chlorostyrene and Methyl Acrylate

Preparation of Organic/Inorganic Hybrid Materials Using Agregates of Poly{2-methyl-N-[2-(phenylthio)phenyl] Acrylamide-co-2-(Trimethylsyloxy)Ethyl Methacrylate} as Precursor and Vibrational Investigation of the Polymerization

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