Radical-addition-fragmentation and co-polymerization of methyl methacrylate macromonomers from catalytic chain transfer polymerization (CCTP)

Haddleton, David M.; Maloney, Darren R.; Clarke, Kevin G. Suddaby Adam; Richards, Stuart N.

doi:10.1016/s0032-3861(97)00180-8

Cited by 40 publications

(34 citation statements)

References 10 publications

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“…The use of cobalt(II) macrocycles as catalytic chain‐transfer (CCT) agents in free‐radical polymerization is a convenient method for the synthesis of low molecular weight polymers with vinyl‐end functionality 1, 2. This type of macromonomer is useful in the synthesis of block3–6 and telechelic polymers 7, 8. To date, most research9–13, 6, 14, 15 has dealt with the use of such systems in organic solution/bulk and emulsion systems.…”

Section: Introductionmentioning

confidence: 99%

Cobalt‐mediated catalytic chain‐transfer polymerization (CCTP) in water and water/alcohol solution

Haddleton

Depaquis

Kelly

et al. 2001

J. Polym. Sci. A Polym. Chem.

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This article describes the use of cobalt‐mediated catalytic chain transfer in aqueous solution under fed conditions for the preparation of macromonomers of acidic, hydroxy, and zwitterionic functional monomers. Use of a batch reaction leads to hydrolysis of catalyst, a mixture of mechanisms and poor control of the reaction. A feed process is described that adds catalyst as a solution in monomer over the course of the reaction. The feed process is applied to a range of monomers of methacrylic acid (2), 2‐aminoethyl methacrylate hydrochloride (3), 2‐hydroxyethyl methacrylate (4), 2‐methacryloxyethyl phosphoryl choline (5), glycerol monomethyl methacrylate (6), and 3‐O‐methacryloyl‐1,2:5,6‐di‐O‐isopropylidene‐D‐glucofuranose (7). Use of the feed process for water‐soluble monomers in conjunction with 1 as a catalytic chain‐transfer agent gives high‐conversion, > 90%, water‐soluble macromonomers. The number‐average molecular mass (Mn was determined by integration of the 1H NMR spectrum comparing the vinylic end group with the remainder of the backbone. Pseudo‐Mayo plots were constructed by measuring the Mn at high conversion as a function of [monomer]/[catalyst] to give observed chain‐transfer constants of 1120, 958, and 1058 for 4, 6, and 2, respectively. All products were obtained as relatively high‐solid, homogeneous, low‐viscosity aqueous solutions. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2378–2384, 2001

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Section: Introductionmentioning

confidence: 99%

Cobalt‐mediated catalytic chain‐transfer polymerization (CCTP) in water and water/alcohol solution

Haddleton

Depaquis

Kelly

et al. 2001

J. Polym. Sci. A Polym. Chem.

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“…This is primarily due to the relatively low chain transfer activity of macromonomers, which in turn demands specific conditions to increase it to give the desired effect. 27,28,33 Taking into account an ability of macromonomers to undergo the β-scission reaction (fragmentation) depending on their chain length and ester group of employed monomer, the chain transfer constant (C S E ) of the employed macromonomer is a subject of interest. 24,28,33,[60][61][62][63] Assuming that macromonomers are CTA's in SF-RAFT, the C S E can be estimated using a pseudoMayo plot method.…”

Section: Synthesis Of Block Copolymersmentioning

confidence: 99%

“…27,28,33 Taking into account an ability of macromonomers to undergo the β-scission reaction (fragmentation) depending on their chain length and ester group of employed monomer, the chain transfer constant (C S E ) of the employed macromonomer is a subject of interest. 24,28,33,[60][61][62][63] Assuming that macromonomers are CTA's in SF-RAFT, the C S E can be estimated using a pseudoMayo plot method. [40][41][42] As in the case with CoBF, this method allows determination of an effective constant C S E rather than an absolute value.…”

Section: Synthesis Of Block Copolymersmentioning

confidence: 99%

Methacrylic block copolymers by sulfur free RAFT (SF RAFT) free radical emulsion polymerisation

et al. 2017

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A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP url' above for details on accessing the published version and note that access may require a subscription. We demonstrate the use of sulfur free reversible addition-fragmentation chain transfer polymerisation (RAFT as a versatile tool for the controlled synthesis of methacrylic block and comb-like copolymers. Sulfur free RAFT (SF-RAFT) utilises vinyl terminated macromonomers obtained via catalytic chain transfer polymerisation (CCTP) of methacrylates as a chain transfer agent (CTA), and thus precluding adverse aspects of the RAFT such as toxicity of dithioesters. We have synthesised a range of narrow dispersity block copolymers (Đ < 1.2) and comb-like macromolecules by employing emulsion polymerisation allowing for the preparation of relatively large quantities (~50 g) of the above mentioned copolymers promptly and straightforwardly. Copolymers were characterised using 1 H NMR, size exclusion chromatography (SEC), thermogravimetric analysis (TGA) and matrix-assisted laser desorption/ionization time of flight mass spectroscopy (MALDI-TOF-MS) techniques.

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“…These macromonomer products may then undergo copolymerization with nonsterically hindered monomers, such as acrylates and styrenics, resulting in highly branched polymer structures (73)(74)(75)(76)(77).…”

Section: Polymerizationmentioning

confidence: 99%

Methacrylic Acid and Derivatives

Wilczynski

Juliette

2003

Kirk-Othmer Encyclopedia of Chemical Technology

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Methacrylic acid (MAA) and its derivatives exhibit a rich array of chemistries and have found wide use in commercial applications, especially as monomers for making various types of polymer products. The predominant manufacturing route to the two simplest methacrylates continues to be via the conversion of acetonecyanohydrin (ACH) in sulfuric acid to methacrylamide followed by either hydrolysis to MAA or esterification with methanol to give methyl methacrylate (MMA). Alternative routes have reached or are now approaching commercialization. These include processes based on either ethylene (C‐2), propylene (C‐3), methylacetylene (C‐3), or isobutylene (C‐4) feedstocks, as well as a separate ACH process which does not involve sulfuric acid. The later route, which starts with catalyzed hydration of ACH to hydroxyisobutyramide followed by esterification and dehydration steps to MMA, has an added benefit of recycling HCN as a raw material. The ethylene‐based routes typically involve formaldehyde condensation on either a propionaldehyde or propionic acid intermediate. The isobutylene‐based routes involve oxidation processes to reach the methacrylate backbone, often passing through methacrolein as an intermediate. The propylene‐based routes typically involve isobutyric acid or isobutyraldehyde intermediates. The methylacetylene‐based process appears to be the most selective overall, where a single reaction with carbon monoxide and methanol leads directly to MMA. All of the synthetic routes require various types of catalysts to promote the separate steps involved. In addition to providing more details on each of these processes, the following article also provides information on volumes, costs, health and safety for methacrylic acid and its derivatives.

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Radical-addition-fragmentation and co-polymerization of methyl methacrylate macromonomers from catalytic chain transfer polymerization (CCTP)

Cited by 40 publications

References 10 publications

Cobalt‐mediated catalytic chain‐transfer polymerization (CCTP) in water and water/alcohol solution

Cobalt‐mediated catalytic chain‐transfer polymerization (CCTP) in water and water/alcohol solution

Methacrylic block copolymers by sulfur free RAFT (SF RAFT) free radical emulsion polymerisation

Methacrylic Acid and Derivatives

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