Science of Determining Copolymerization Reactivity Ratios

Tidwell, Paul W.; Mortimer, George A.

doi:10.1080/15321797008068151

Cited by 163 publications

(18 citation statements)

References 39 publications

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“…This result can be explained on the grounds that short sequence lengths of' this monomer in the copolymer have greater enthalpies of polymerization and correspondingly higher ceiling temperatures than high molecular weight homopolymer (2, 3). Other discrepancies between the results reported and those found by other workers can be ascribed to use of more modern analytical procedures and data-handling methods (3, 4,6).…”

Section: Introductioncontrasting

confidence: 56%

“…This conclusion is probably valid for all analytical methods in current use, and is a factor in the lack of agreement which is often noted between results from different laboratories (6 merization~ reported here. The extrapolated mer com~osition are taken from the corresponding best-fit value for initial weight fraction of MAN in Fig.…”

Section: Analytical Accuracymentioning

confidence: 76%

“…The model should also be shown to give estimates which are independent of extent of reaction or feed composition (6). In this connection, Figs.…”

Section: Resultsmentioning

confidence: 99%

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Terpolymerization of Methacrylonitrile, Styrene, and α-Methylstyrene

Rudin¹,

Chiang²,

Johnston³

et al. 1972

Can. J. Chem.

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The free radical copolymerization of methacrylonitrile, styrene, and a-methylstyrene was studied at 60 OC in toluene solution. Copolymer composition was calculated from the composition of the unreacted monomers, as measured by g.1.c. Reactivity ratios measured previously for the three monomer pairs involved were used with the simple terpolymerization equation to predict polymer composition. Agreement between predicted and experimental polymer compositions was satisfactory. The behavior of a-methylstyrene can be described by a simple model without reference to ceiling temperature or penultimate effects because sequence lengths of this monomer in the terpolymers are short.A true azeotropic feed composition was not investigated, but several monomer mixtures produced copolymers with compositions which varied so little from that of the feed that the systems could be considered to be azeotropic for practical synthetic purposes. This behavior is in accord with expectations.Analytical accuracy of the gas chromatographic techniques was examined and means are suggested to make the best use of this method in copolymerization studies.La copolymCrisation par radicaux libres de methacrylonitrile, styrene, et a-methylstyrene a ete etudiee a 60 "C en solution dans le toluene. La composition du copolymere a ett calculee a partir de celle des monomeres restants par c.g.1. Les rapports de reactivite precedemment mesurts pour les trois monomeres impliques pris deux a deux, ont CtC utilises dans la simple equation de terpolymtrisation pour prtvoir la composition du polymtre. Un accord satisfaisant entre les compositions calculee et trouvte a etC obtenu. Le comportement de I'a-mCthylstyrene peut itre decrit par un modele simple sans faire reference a la temperature "de plafond" ou a des effets prtterminaux car !es longueurs des sequences de ce monomtre dans les terpolymeres sont courtes. La composition d'une alimentation azeotropique vraie n'a pas Ctt recherchee car de nombreux melanges de monomeres ont donne des copolymtres dont la composition differe tellement peu de celle de I'alimentation, qu'il est possible de considtrer ces systtmes comme Ctant azeotropiques, a des fins de synthese pratique. Cette attitude est conforme aux previsions.La precision analytique des techniques de chromatographie en phase gazeuse a ete examinee et des moyens ont ett proposes afin de faire le meilleur usage de cette methode a des etudes de copolymtrisation.

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Section: Introductioncontrasting

confidence: 56%

Section: Analytical Accuracymentioning

confidence: 76%

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Terpolymerization of Methacrylonitrile, Styrene, and α-Methylstyrene

Rudin¹,

Chiang²,

Johnston³

et al. 1972

Can. J. Chem.

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“…In the presence of reinitiation, it is possible to obtain the stoichiometric coefficient, if the data are corrected by the following equation 9 : even more complicated or equation 4 fails because the linearization modifies the distribution of errors since the independent variable is mixed with the dependent one as has been observed in copolymerization systems 10 . Thus, it is not possible to calculate a value of the stoichiometric coefficient for this inhibitor.…”

Section: Resultsmentioning

confidence: 99%

Kinetic and structural features of furan compounds as inhibitors of the radical polymerization of vinyl acetate

Vega

Rieumont

1997

Polímeros

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Some furan compounds bearing a double bond in the side group have been examined as inhibitors of the radical polymerization of vinyl acetate initiated by AIBN in ethyl acetate at 60 ºC. The inhibition effect was found to follow the order: furfurylidenacetone > furylacrolein > furanacrylic acid > furylacrylmorpholinamide as a consequence of the greater stabilization of the radical formed. The site of radical attack can be considered either as the C-5 position of the furan ring or as the double bond of the side group. The compounds taken as models such as 5-methylfuranacrylic acid and furfurylidenbutanal indicate that both positions can participate in the inhibitory process

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“…In order to check the validity of different methods based on the terminal model, the reactivity ratios have been obtained, from f and F values, by linear methods (KelenTudös) [14], non-linear methods (Tidwell-Mortimer) [15,16], as well as one statistical method, the Error in Variables Method (EVM) [17][18][19][20][21][22] one. The reactivity ratios allows to estimate the theoretical distribution of sequences in the copolymer by calculating the probability of alternating (P 12 ) and homogeneus (P 11 ) diads: being P 12 =1-P 11 and P 21 =1-P 22 .…”

Section: Reactivity Ratiosmentioning

confidence: 99%

Copolymerization of acenaphthylene with methacrylic monomers

et al. 2011

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Abstract:The copolymerization of acenaphthylene with methylmethacrylate, ethylmethacrylate, butylmethacrylete, iso-butylmethacrylate and cyclohexylmethacrylate has been carried out in tetrahydrofuran at 323 K and the composition of the copolymers has been determined by size exclusion chromatography using a double RI-UV detector system. Several methods have been applied to obtain the reactivity ratios of the copolymerization process. The glass transition temperature of the copolymers has been obtained by DSC and the thermal stability has been studied by thermogravimetry. Analysis of the degradation volatile products reveals that copolymers degrade mainly by depolymerization.

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Science of Determining Copolymerization Reactivity Ratios

Cited by 163 publications

References 39 publications

Terpolymerization of Methacrylonitrile, Styrene, and α-Methylstyrene

Terpolymerization of Methacrylonitrile, Styrene, and α-Methylstyrene

Kinetic and structural features of furan compounds as inhibitors of the radical polymerization of vinyl acetate

Copolymerization of acenaphthylene with methacrylic monomers

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