Catalytic chain transfer copolymerization of methyl methacrylate and methyl acrylate

Pierik, B.; Masclee, Désirée; Herk, Alex van

doi:10.1002/1521-3900(200103)165:1<19::aid-masy19>3.0.co;2-7

Cited by 22 publications

(35 citation statements)

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“…For MA it has been shown previously, [23] that first cobaltcarbon bond formation takes place, after which the polymerization sets in. Therefore, it was assumed that a steady-state concentration of organocobalt(III) species exists from which a relation between [Co(II)] and [[Co(III)]-PBA] can be derived according to…”

Section: Model For Cct Copolymerization Of Ba and Mmamentioning

confidence: 99%

“…For comparison, earlier results for MMA-methyl acrylate are presented in Figure 6. [23] It can be seen that hC T i 0 increases with both increasing f MMA and decreasing initiator concentration. Although hC T i 0 is in-between 150 and 25 000, which is lower than for the MMA homopolymerization, it is still substantially higher than for conventional chain transfer agents.…”

Section: Cct In Ba-mma Copolymerizationsmentioning

confidence: 99%

“…The synthesis of acrylate-(amethylvinyl) macromonomers has been described by Moad et al [21] and Chiefari et al [22] Recently, we reported on the kinetics of the CCT copolymerization of MMA and methyl acrylate. [23] It has been shown that for this methacrylateacrylate copolymerization CCT is a very efficient way of controlling molecular weight in spite of the fact that for CCT homopolymerizations of acrylates both inhibition [24,25] and some sort of living character [26][27][28] have been reported. In this paper, the CCT copolymerization of MMA and BA will be discussed to a deeper extent including the effect of CCT on reactivity ratios and the effect of conversion on the molecular weight distribution in the CCT copolymerization.…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Chain Transfer Copolymerization of Methyl Methacrylate and Butyl Acrylate

Pierik

Herk

2003

Macro Chemistry & Physics

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In this work it is shown that catalytic chain transfer is a very efficient way of controlling molecular weight in the copolymerization of methyl methacrylate (MMA) and butyl acrylate (BA). The experimental data are compared to a previously developed model based on copolymerization kinetics and the mechanisms for catalytic chain transfer and for cobalt‐mediated living radical polymerization that can describe the observed transfer constants. Secondly, it is shown that the presence of a catalytic chain transfer agent does not affect the reactivity ratios within the concentration range studied. Finally, the effect of conversion and therewith composition drift on the catalytic chain transfer polymerization of MMA and BA is investigated and it is shown that under the conditions employed in the experiments a certain degree of macromer copolymerization is present at high partial conversions of MMA.

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Section: Model For Cct Copolymerization Of Ba and Mmamentioning

confidence: 99%

Section: Cct In Ba-mma Copolymerizationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Catalytic Chain Transfer Copolymerization of Methyl Methacrylate and Butyl Acrylate

Pierik

Herk

2003

Macro Chemistry & Physics

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“…[1][2][3] The catalyst is usually a low spin Co(II) species, which is able to catalyze the chain transfer to monomer reaction in the free-radical homopolymerization [4][5][6] of methacrylates, amethylstyrene, and styrenes, and also copolymerization with other monomers, such as acrylates. [7] Cobaloxime boron fluoride (CoBF) (Scheme 1) is a typical example of a highly active CCT catalyst that is frequently used in academic studies.…”

Section: Introductionmentioning

confidence: 99%

“…[11] We performed experiments for different methacrylates in solution as well, and will compare our results with theoretical calculations for different levels of diffusion control, and also with results reported by Heuts et al [17][18][19] and by Roberts et al [20] A final point for discussion is the possible effect of the formation of covalent bonds between the polymeric radical and the cobalt complex, as has been reported in CCT polymerizations with e.g. acrylates, [7,21,22] styrene [23][24][25] and maleic anhydride. [22] When cobalt-carbon bond formation occurs, the amount of Co complex available for chain transfer decreases and only an apparent C T can be determined.…”

Section: Introductionmentioning

confidence: 99%

Solvent Effects, Diffusion Control and Mechanistic Aspects of Catalytic Chain Transfer Polymerization

Pierik¹,

Vollmerhaus²,

Herk³

2003

Macro Chemistry & Physics

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In the catalytic chain transfer polymerization of methyl methacrylate, butyl methacrylate and 2‐ethylhexyl methacrylate in toluene, it was found that the chain transfer constants (CT) were independent of solvent concentration and therefore of solution viscosity, and did not differ from the bulk polymerization values. For a diffusion controlled system, theoretical calculations predict an increase in CT when the solution viscosity is lowered. This points at a non‐diffusion controlled catalytic chain transfer step. These results were obtained when the solvent was thoroughly purified using a Grubbs‐type set‐up, whereas a large reduction in CT was found in unpurified solvent. Similar results were obtained for butyl acetate. Therefore it is concluded that the decrease of CT in non‐purified solvents is not related to the solvent itself, but to solvent impurities. Further we found that methyl methacrylate ended radicals do not covalently bind to the cobalt complex, in contrast to styrene and acrylate ended radicals.Chain transfer constant for the CCT polymerization of 2‐ethylhexyl methacrylate in toluene, and predictions for diffusion controlled systems.magnified imageChain transfer constant for the CCT polymerization of 2‐ethylhexyl methacrylate in toluene, and predictions for diffusion controlled systems.

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High‐conversion catalytic chain transfer polymerization of methyl methacrylate

Pierik

Herk

2003

J of Applied Polymer Sci

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ABSTRACT:In this work the effects of conversion on the apparent catalyst activity in the catalytic chain transfer polymerization of methyl methacrylate are reported. Several mechanisms are discussed that may explain the experimental observations. The discussion is supported with computer simulations using Predici software. It is shown that the experimental decrease in weight average molecular weight with conversion is smaller than the decrease obtained in simulations. The most likely cause for this discrepancy is slow catalyst deactivation. The half-life of CoBF under the reported conditions was determined to be about 10 h. Furthermore, the effect of acetic acid (HAc) and benzoyl peroxide (BPO) on the evolution of the molecular weight distribution is investigated. Both HAc and BPO enhance catalyst deactivation. For HAc, catalyst deactivation scales with the square root of its concentration. BPO-enhanced deactivation depends linearly on its concentration.

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Catalytic chain transfer copolymerization of methyl methacrylate and methyl acrylate

Cited by 22 publications

References 0 publications

Catalytic Chain Transfer Copolymerization of Methyl Methacrylate and Butyl Acrylate

Catalytic Chain Transfer Copolymerization of Methyl Methacrylate and Butyl Acrylate

Solvent Effects, Diffusion Control and Mechanistic Aspects of Catalytic Chain Transfer Polymerization

High‐conversion catalytic chain transfer polymerization of methyl methacrylate

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