Emulsion co‐ and terpolymerization of styrene, methyl methacrylate and methyl acrylate. II. Control of emulsion terpolymer microstructure with optimal addition profiles

Schoonbrood, Harold A. S.; Eijnatten, Ronald C. P. M. van; German, Anton L.

doi:10.1002/(sici)1099-0518(19960430)34:6<949::aid-pola3>3.3.co;2-n

Cited by 5 publications

(6 citation statements)

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“…In order to avoid composition drift, feeding of monomers should be applied, based on the important reactivity. 20,33 This family-like behavior is confirmed by the difference of reactivity of vinyl monomers toward CKA and toward other vinyl monomers. This is shown in Table S7 in the Supporting Information.…”

Section: Industrial and Engineering Chemistry Researchmentioning

confidence: 64%

Toward Biodegradable Chain-Growth Polymers and Polymer Particles: Re-Evaluation of Reactivity Ratios in Copolymerization of Vinyl Monomers with Cyclic Ketene Acetal Using Nonlinear Regression with Proper Error Analysis

Lena

Herk

2019

Ind. Eng. Chem. Res.

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Recycling and biodegradability of chain-growth polymers is an important and growing topic. Introducing ester bonds in polymers via cyclic ketene acetals (CKAs) is an interesting route to create (bio)degradability. Incorporation of CKA monomers is controlled by reactivity ratios. Reactivity ratios of different CKA/vinyl monomer systems published in the literature were re-evaluated with the nonlinear least-squares method, taking into account the error in the 1H NMR measurements of monomer fractions in copolymers. This study confirms that the nonlinear least-squares method should be used instead of Fineman–Ross or Kellen–Tudos methods. Re-evaluated values suggest that reactivity ratios of CKA/vinyl monomer systems follow a family-like behavior.

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Section: Industrial and Engineering Chemistry Researchmentioning

confidence: 64%

Toward Biodegradable Chain-Growth Polymers and Polymer Particles: Re-Evaluation of Reactivity Ratios in Copolymerization of Vinyl Monomers with Cyclic Ketene Acetal Using Nonlinear Regression with Proper Error Analysis

Lena

Herk

2019

Ind. Eng. Chem. Res.

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“…The slope of ln P (M copol ) versus M copol is also determined partly by termination, but as can be seen in Figure , this does not contribute much at the initiator concentrations used (i.e., the slope in Figure is not large). Note that these systems display zero−one kinetics. ,, It has been argued that the only intraparticle termination event operating in zero−one systems is instantaneous termination between a long radical and a monomeric radical (formed by chain transfer) . This monomeric radical can only have entered the particle already containing the long radical, after having escaped from another particle first (exit).…”

Section: Resultsmentioning

confidence: 99%

“…In this paper we will present results of the determination of the total rate of chain transfer to monomer as a function of monomer composition in two (emulsion) copolymerization systems (styrene−methyl acrylate and styrene−methyl methacrylate). These data are also interpreted in terms of the rates of transfer to the individual monomers (homo- and cross-chain transfer constants), which are important when studying the kinetics of these systems. − The chain transfer constants will be discussed using some recently developed theoretical understanding of propagation and transfer reactions in free-radical polymerization.…”

Section: Introductionmentioning

confidence: 99%

Cross-Chain Transfer Rate Constants of Styrene-Terminated Radicals to Methyl Acrylate and Methyl Methacrylate

et al. 1996

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The chain transfer-to-monomer dominated regime of the molar mass distribution of lowconversion emulsion copolymers of styrene and methyl acrylate and of styrene and methyl methacrylate of various compositions, prepared with varying initiator concentrations, was analyzed with size exclusion chromatography. By extrapolation of the values of the slope of the natural logarithm of the number molar mass distribution to zero initiator concentration, it was possible to determine the average chaintransfer coefficient as a function of composition. By calculation of the ratio of the concentrations of styreneterminated radicals and methyl (meth)acrylate-terminated radicals with an appropriate propagation model, the values of the cross-chain transfer rate constants of styrene-terminated radicals to methyl acrylate and methyl methacrylate could be deduced. These values were interpreted in the light of newly gained insights into radical propagation and transfer reactions.

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“…Effective commercial processes are usually based on one or a combination of these feed policies. Some additional promising derivations of these policies have been presented (Arzamendi and Asua, 1989, 1990, 1991Arzamendi et al, , 1992van Doremaele et al, 1992;Leiza et al, 1993;Schoonbrood et al, 1993Schoonbrood et al, , 1996Canegallo et al, 1994;Canu et al, 1994;Urretabizkaia et al, 1994a;de la Cal et al, 1995;Echevarria et al, 1995). These feed policies (Policy I and Policy II) are described below using binary copolymerization as an example.…”

Section: Semibatch Monomer Feed Policiesmentioning

confidence: 99%

Mathematical Modeling of Multicomponent Chain-Growth Polymerizations in Batch, Semibatch, and Continuous Reactors: A Review

Dubé

Soares

Penlidis

et al. 1997

Ind. Eng. Chem. Res.

185

122

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A practical methodology for the computer modeling of multicomponent chain-growth polymerizations, namely, free-radical and ionic systems, has been developed. This is an extension of a paper by Hamielec, MacGregor, and Penlidis (Multicomponent free-radical polymerization in batch, semi-batch and continuous reactors. Makromol. Chem., Macromol. Symp. 1987, 10/ 11, 521). The approach is general, providing a common model framework which is applicable to many multicomponent systems. Model calculations include conversion of the monomers, multivariable distributions of concentrations of monomers bound in the polymer chains and molecular weights, long- and short-chain branching frequencies, chain microstructure, and cross-linked gel content when applicable. Diffusion-controlled termination, propagation, and initiation reactions are accounted for using the free-volume theory. When necessary, chain-length-dependent diffusion-controlled termination may be employed. Various comonomer systems are used to illustrate the development of practical semibatch and continuous reactor operational policies for the manufacture of copolymers with high quality and productivity. These comprehensive polymerization models may be used by scientists and engineers to reduce the time required to develop new polymer products and advanced production processes for their manufacture as well as to optimize existing processes.

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Emulsion co‐ and terpolymerization of styrene, methyl methacrylate and methyl acrylate. II. Control of emulsion terpolymer microstructure with optimal addition profiles

Cited by 5 publications

References 0 publications

Toward Biodegradable Chain-Growth Polymers and Polymer Particles: Re-Evaluation of Reactivity Ratios in Copolymerization of Vinyl Monomers with Cyclic Ketene Acetal Using Nonlinear Regression with Proper Error Analysis

Toward Biodegradable Chain-Growth Polymers and Polymer Particles: Re-Evaluation of Reactivity Ratios in Copolymerization of Vinyl Monomers with Cyclic Ketene Acetal Using Nonlinear Regression with Proper Error Analysis

Cross-Chain Transfer Rate Constants of Styrene-Terminated Radicals to Methyl Acrylate and Methyl Methacrylate

Mathematical Modeling of Multicomponent Chain-Growth Polymerizations in Batch, Semibatch, and Continuous Reactors: A Review

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