New applications of catalytic chain transfer polymerization to waterborne binders for automotive paint systems

Huybrechts, Jos; Bruylants, P.; Kirshenbaum, Ken; Vrána, Jiří; Šňupárek, Jaromı́r

doi:10.1016/s0300-9440(02)00042-5

Cited by 18 publications

(20 citation statements)

References 13 publications

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“…[17][18][19] In earlier studies also, amphiphilic macromonomers were synthesized and subsequently used as stabilizers in emulsion polymerization. 20,21 In the current study, methacrylic acid macromonomers (synthesized via the Co-mediated CCT polymerization of t-butyl methacrylate followed by acidolysis of the t-butyl groups) are used as precursors to stabilizing agents in the emulsion polymerization of methacrylates and acrylates. Both acrylates and methacrylates were used because it is known that methacrylic macromonomers react differently with these two classes of monomers 14,22 and will yield reactive surfactants with different architectures.…”

Section: Introductionmentioning

confidence: 99%

In situ stabilizer formation from methacrylic acid macromonomers in emulsion polymerization

Schreur-Piet

Heuts

2017

Polym. Chem.

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Section: Introductionmentioning

confidence: 99%

In situ stabilizer formation from methacrylic acid macromonomers in emulsion polymerization

Schreur-Piet

Heuts

2017

Polym. Chem.

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“…Furthermore, these cobalt(II) complexes are relatively stable in aqueous environment and as such allow for implementation of CCTP in emulsion polymerization. [7][8][9][10][11][12][13][14][15] CCTP in homogeneous bulk and solution polymerization results in a uniform distribution of the CCTA and as such ensures the production of polymer with a predetermined molecular weight, a monomodal molecular weight distribution (MWD), and a polydispersity index (D) of approximately 2. In a heterogeneous emulsion polymerization, this is not necessarily the case.…”

Section: Introductionmentioning

confidence: 99%

Mass transport by collisions in emulsion polymerization: why it is possible to use very hydrophobic catalysts for efficient molecular weight control

et al. 2011

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An alternative mass transport mechanism, based on collisions between different entities, is used to explain the performance of an extremely hydrophobic catalytic chain transfer agent (i.e. COPhBF) in emulsion polymerization. Mass transport in emulsion polymerization is generally accepted to proceed via the aqueous phase. COPhBF possesses no detectable water-solubility and would therefore be expected to be inefficient for molecular weight control in emulsion polymerization. However, proper molecular weight control using COPhBF has been demonstrated and results are presented that are consistent with the existence of an alternative mass transport mechanism in emulsion polymerization that circumvents the aqueous phase.

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“…In catalytic chain transfer polymerization (CCTP), a small amount of cobalt chain transfer (CCT) agent is added to radical polymerization to produce polymers containing unsaturated end groups with the so‐called macromonomer used for further post‐reaction . As the chains are produced continuously during the reaction by decomposition of a thermal initiator, the macromonomers synthesized by CCTP chemistry have a dispersity (Ð) close to 2 …”

Section: Introductionmentioning

confidence: 99%

Modeling the Synthesis of Butyl Methacrylate Macromonomer by Sequential ATRP‐CCTP

Zhang

Hutchinson

2018

Macro Reaction Engineering

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The atom transfer radical polymerization of butyl methacrylate mediated by Cu(I)Br/N,N,N′,N″,N″‐pentamethyldiethylenetriamine in anisole at 70 °C with the subsequent addition of bis(difluoroboryldiphenylglyoximato)cobalt(II) after 2 h is modeled using Predici software, to gain additional insight to the system used experimentally to produce macromonomer chains with narrow dispersity. The mechanistic model, using kinetic coefficients from the literature and activation and deactivation rate coefficients estimated from this work, provides a good representation of experimental results. The simulations demonstrate that the time (conversion) at which cobalt chain transfer agent is added to the system is critical to control the number‐average molar mass of the final product and also confirm that chains of higher length in the final product are more likely to be nonfunctionalized, in agreement with experimental observations. The model predicts the production of a significant fraction of macromonomer oligomers with lengths of 1–3 units, also consistent with experiments.

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New applications of catalytic chain transfer polymerization to waterborne binders for automotive paint systems

Cited by 18 publications

References 13 publications

In situ stabilizer formation from methacrylic acid macromonomers in emulsion polymerization

In situ stabilizer formation from methacrylic acid macromonomers in emulsion polymerization

Mass transport by collisions in emulsion polymerization: why it is possible to use very hydrophobic catalysts for efficient molecular weight control

Modeling the Synthesis of Butyl Methacrylate Macromonomer by Sequential ATRP‐CCTP

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