Solvent effects on the overall rate of copolymerization for the methyl methacrylate‐styrene system

Madruga, Enrique López

doi:10.1002/marc.1993.030140909

Cited by 21 publications

(16 citation statements)

References 33 publications

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“…That means that the k p value must be significantly larger for PMMA than for PS. This is, in turn, is in accordance with to the literature data [23] …”

Section: "Raw" Molecular Weight Distributionssupporting

confidence: 95%

Analysis of molecular weight distributions of styrene‐methyl methacrylate copolymers using size exclusion chromatography data

Matusinović

Tomić²,

Šegudović³

et al. 2005

J of Separation Science

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Analysis of molecular weight distributions of styrene-methyl methacrylate copolymers using size exclusion chromatography data Size exclusion chromatography (SEC) is a common method for the determination of molecular weight distributions (MWD) of polymers. Using appropriate normalization procedures, MWD data may be put in a form suitable for the description by different theoretical distribution functions. In this paper such a procedure is described and applied to a model system. Statistical copolymers of styrene and methyl methacrylate (SMMA) of different compositions were synthesized by radical copolymerization in a batch isothermal reactor with toluene as solvent and azobisisobutyronitrile as initiator. Copolymer MWDs were obtained by SEC and average copolymer composition by elemental analysis. MWDs of SMMA copolymers were correlated with the lognormal, Flory, Schulz, and Tung theoretical function. The best match between experimental and calculated data was obtained by the Schulz distribution. The a-parameter of Schulz's function was related to the average molecular weight and showed its maximum at the midpoint of the copolymer composition range, in connection with the observed minimal copolymerization rate. The variation of the b-parameter was found to be less pronounced; the parameter was related to the polydispersity index. This feature indicated that there was no significant change in the copolymerization reaction mechanism throughout the entire copolymer composition range.

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“…That means that the k p value must be significantly larger for PMMA than for PS. This is, in turn, is in accordance with to the literature data [23] …”

Section: "Raw" Molecular Weight Distributionssupporting

confidence: 95%

Analysis of molecular weight distributions of styrene‐methyl methacrylate copolymers using size exclusion chromatography data

Matusinović

Tomić²,

Šegudović³

et al. 2005

J of Separation Science

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“…However, when radical-solvent or radical-monomer complexes do not propagate, the effect of complexation is to alter the effective radical or monomer concentrations, thereby causing a bootstrap effect. This may be the case of the bootstrap effect observed in the MMA/S system [3][4][5] .…”

Section: Resultsmentioning

confidence: 99%

“…However, when the copolymers are produced in a solvent with a relatively high polarity (benzonitrile), an enrichment in MMA and a depletion of MMA around the growing polymer radical is noted for F MMA lower or higher than 0.5, respectively. When the behaviour of the copolymerization systems, such as S-MMA, can be explained by a bootstrap effect mechanism [3][4][5] and the monomers implicated have different polarities, a preferential sorption of the less polar monomer is noted when the copolymerization is carried out in the more polar solvent. However, in the BA/MMA system both monomers have similar polarities, i. e., the dipole moments are 1.93 D and 1.67 D for BA and MMA, respectively, and the opposite is observed when the copolymerization is carried out in benzene or benzonitrile.…”

Section: Resultsmentioning

confidence: 99%

“…This model has been successful in explaining solvent effects in copolymerization. Most of the systems analyzed are formed by comonomers with relatively large differences in polarity, i. e., methyl methacrylate/styrene [3][4][5] , styrene/acrylonitrile 6) , styrene/ methacrylic acid 2) , etc., but only a few systems formed by comonomers of similar polarity such as methyl methacrylate/butyl acrylate system have been studied.…”

Section: Introductionmentioning

confidence: 99%

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Solvent effects on the free-radical copolymerization of butyl acrylate with methyl methacrylate

Fuente

Madruga²

1999

Macromol. Chem. Phys.

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SUMMARY: Free-radical copolymerization of butyl acrylate with methyl methacrylate was carried out at 50 8C in a 3 mol/L benzonitrile solution. Differences between the apparent reactivity ratios determined in this work with those previously reported in bulk, toluene and benzene indicate noticeable solvent effects. This fact can be explained through different models, but independent of the chemistry of the system, to obtain the same copolymer composition in bulk or in solution, the monomer feed that should be used is determined by solvent polarity.

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“…Monomer-monomer, monomer-solvent, or radical-solvent (which may be not only a solvent but also one or both comonomers) complexes and the so-called boot-strap model also could explain the apparent variations of the co-polymerization parameters in the different solvents. To date, there is experimental evidence [34][35][36][37][38] that the bootstrap model is the most appealing as a general model. The dipole moments, 1.7 D and 1.55 D, respectively, of PA and HA are nearer values, and the dielectric constants (ε), 13.9 and 13.3 (both at 25 • C), respectively, of PA and HA are not much different values to show variations in apparent reactivity ratios of pMSTY and MMA in the present study.…”

Section: ] and Mayo-lewis Integration (M-l-i) [23] Methods (Figs 3 mentioning

confidence: 99%

Microemulsion and Conventional Emulsion Co-polymerizations of p-Methyl Styrene with Methyl Methacrylate

Reddy

Thomas

Radhakrishnan

2008

Designed Monomers and Polymers

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Microemulsion (ME) and conventional emulsion (CE) co-polymerization of p-methyl styrene (pMSTY) with methyl methacrylate (MMA) are carried out at 70 • C using n-pentanol (PA) and n-hexanol (HA), respectively, as co-surfactants along with sodium lauryl sulphate (SLS) as surfactant in the reaction media, and potassium persulphate (KPS) as initiator. The co-polymers are characterized by NMR and GPC techniques. The reactivity ratios are evaluated by employing Fineman-Ross (F-R), Kelen-Tüdös (K-T) and Mayo-Lewis integration (M-L-I) methods. The K-T method yields the reactivity ratios 0.68 ± 0.02 (r pMSTY ), 0.40 ± 0.02 (r MMA ), 0.68 ± 0.02 (r pMSTY ) and 0.68 ± 0.02 (r MMA ), respectively, for the ME and CE co-polymerizations of pMSTY and MMA with PA as co-surfactant in the reaction media. The K-T method yields the reactivity ratios 1.09 ± 0.02 (r pMSTY ), 0.37 ± 0.02 (r MMA ) and 0.78 ± 0.02 (r pMSTY ) and 0.54 ± 0.02 (r MMA ), respectively, for the ME and CE co-polymerization of pMSTY and MMA with HA as co-surfactant in the reaction media.  Koninklijke Brill NV, Leiden, 2008

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Solvent effects on the overall rate of copolymerization for the methyl methacrylate‐styrene system

Cited by 21 publications

References 33 publications

Analysis of molecular weight distributions of styrene‐methyl methacrylate copolymers using size exclusion chromatography data

Analysis of molecular weight distributions of styrene‐methyl methacrylate copolymers using size exclusion chromatography data

Solvent effects on the free-radical copolymerization of butyl acrylate with methyl methacrylate

Microemulsion and Conventional Emulsion Co-polymerizations of p-Methyl Styrene with Methyl Methacrylate

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