Facile and selective synthesis of aldehyde end-functionalized polymers using a combination of catalytic chain transfer and rhodium catalyzed hydroformylation

Smeets, Nmb Niels; Meuldijk, J.; Heuts, Johan P. A.; Koeken, Acj Ard

doi:10.1039/c0py00111b

Cited by 13 publications

(15 citation statements)

References 57 publications

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“…Therefore, the application of catalytic CCT agents in preference to single event CTAs can allow; (a) the isolation of product polymers with very low Mwt's, (b) a set target Mwt to be achieved using very low CTA concentrations, and/or (c) the Mwt to be finely tuned by varying the concentration of the CTA present in the reaction mixture. [8][9][10][11][12][13] Furthermore, CCTP also results in the synthesis of low Mwt polymers that are terminated by a vinylic functionality which allows these product materials to be used as macromonomers in subsequent polymerisations/post-functionalisation processes. For example, they can be used in the synthesis of graft copolymers, [14][15][16] or as single event chain transfer agents in polymerisations.…”

Section: Introductionmentioning

confidence: 99%

Direct ‘in situ’, low VOC, high yielding, CO₂expanded phase catalytic chain transfer polymerisation: towards scale-up

et al. 2013

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The successful application of catalytic chain transfer polymerisation (CCTP) by adopting an 'in situ' catalyst preparation methodology in several polymerisation media is described. More specifically, this study is focused on reporting the development of 'in situ' CCTP within a CO(2) expanded phase polymerisation process, which achieved high yields of polymer whilst minimising both VOC footprint and CO(2) compression costs. The 'in situ' method is shown to be effective in controlling polymerisations conducted in both conventional solvents and bulk under inert atmosphere, delivering molecular weight reductions and a Cs value of appropriate similar magnitude to those achieved by the benchmark, commercially sourced CoPhBF catalyst. The 'in situ' effect has been achieved with equal efficiency when both using catalysts with different axial ligands and where the complex is required to undergo a facile ligand dissociation in order to create the required catalyst necessary to achieve CCTP control. Furthermore, both catalysts are shown to effectively control polymerisations in a CO(2) expanded phase process, in which a small amount of compressed CO(2) is introduced to reduce the viscosity of the reaction mixture, allowing for easy heat transfer and good catalyst diffusion during reaction. In this way, yield limitations imposed to avoid the Trommsdorff effect required in bulk processing and the need for post precipitation have been successfully overcome. Both of these factors further improve the sustainability of such a polymerisation process. However, the 'in situ', high pressure expanded phase environment was observed to retard the ligand dissociation required for catalyst activation.

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Section: Introductionmentioning

confidence: 99%

Direct ‘in situ’, low VOC, high yielding, CO₂expanded phase catalytic chain transfer polymerisation: towards scale-up

et al. 2013

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“…Recently, this has been successfully demonstrated in the hydroformylation of poly(styrene) and poly(methyl methacrylate) macromonomers performed in scCO 2 . 33 scCO 2 swells the macromonomer phase, reduces its viscosity and thus facilitates a good contact between the CQC double bonds in the macromonomer, the rhodium catalyst, CO and H 2 . Furthermore, although this is outside the scope of the current paper, scCO 2 can be used to extract the catalyst and other possible solvent impurities from the macromonomer phase.…”

Section: Introductionmentioning

confidence: 99%

“…The disubstituted CQC double bond, which is formed through the CCTP-mediated free-radical polymerization of monomers such as styrenics and methacrylates, can also be converted into an aldehyde by hydroformylation. 33 The aldehyde functional group allows for a number of further transformations including reduction to alcohols, oxidation to carboxylic acids, and reductive amination. 48 In this paper we report the hydroformylation of sterically hindered alkenes and macromonomers in the presence of supercritical carbon dioxide.…”

Section: Introductionmentioning

confidence: 99%

A bulky phosphite modified rhodium catalyst for efficient hydroformylation of disubstituted alkenes and macromonomers in supercritical carbon dioxide

Koeken

Smeets

2013

Catal. Sci. Technol.

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The hydroformylation of disubstituted alkenes and related macromonomers in supercritical CO 2 is demonstrated. Higher turnover frequencies were observed for the 1,2-disubstituted alkenes than for the 1,1-disubstituted alkenes. The turnover frequency for poly(styrene) macromonomer hydroformylation compares well with that observed for cyclohexene. The turnover frequency observed for poly(methyl methacrylate) macromonomer hydroformylation is considerably lower than that observed for methyl methacrylate. Unprecedented turnover frequencies are observed in comparison with previous studies where CO 2 has been applied as a solvent. This is achieved using rhodium modified with a readily available bulky phosphite ligand without the need of ligand modification to improve solubility in supercritical CO 2 .

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“…Catalytic chain transfer polymerization (CCTP) is very powerful to produce vinyl terminated methacrylic oligomers, 29 which have been successfully modified using hydroformylation reactions 30 and (small-molecule) thiol-ene reactions, [31][32][33] and converted into initiators for anionic polymerization. 34 In this study, we first tried to design block copolymers poly(ethylene)-bpoly(methyl methacrylate) by reaction of poly(methyl methacrylate) macromonomers (PMMA 10 -MM) obtained by CCTP with PE-SH.…”

Section: A Introductionmentioning

confidence: 99%

Polyethylene end functionalization using thia-Michael addition chemistry

Mazzolini¹,

Boyron²,

Monteil³

et al. 2012

Polym. Chem.

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International audienceThiol end functionalized polyethylenes (PE-SH, Mn around 1000 g mol−1, Đ \textless 1.3) were used as nucleophiles in thia-Michael additions with different acrylic molecules. It was found that under commonly used practical conditions the addition to methacrylates was very difficult, whereas addition to acrylates was very efficient. First, block copolymers based on PE and poly(methyl methacrylate) (PMMA) were targeted by reaction of PE-SH with PMMA obtained by catalytic chain transfer polymerization (CCTP). The reaction however failed and detailed model experiments using butanethiol and a dimer of MMA showed that the solubilization temperature of PE-SH was an impediment to the success of the reaction. The lack of reactivity towards PMMA obtained by CCTP and methacrylate functions was advantageously used to react molecules containing both an acrylate and a methacrylate group in the presence of tributyl phosphine (PBu3) to produce methacrylate-type PE macromonomers. The presence of a hydroxyl function on 3-(acryloyloxy)-2-hydroxypropyl methacrylate induced side trans-esterification reactions catalyzed by PBu3. This was overcome by using the hydroxyl free 2-(acryloyloxy) ethyl methacrylate. With the latter, the desired PE macromonomer exhibited a functionality as high as 85%. Alternatively, 2-isocyanatoethyl methacrylate could also be reacted with PE-SH to produce a highly functionalized methacrylate type PE macromonomer (functionality 89%). Eventually, the efficiency of the thia-Michael addition of PE-SH onto poly(ethylene glycol) acrylate (PEG-acrylate) was used to synthesize the PE-b-PEG block copolymer

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Facile and selective synthesis of aldehyde end-functionalized polymers using a combination of catalytic chain transfer and rhodium catalyzed hydroformylation

Cited by 13 publications

References 57 publications

Direct ‘in situ’, low VOC, high yielding, CO₂expanded phase catalytic chain transfer polymerisation: towards scale-up

Direct ‘in situ’, low VOC, high yielding, CO₂expanded phase catalytic chain transfer polymerisation: towards scale-up

A bulky phosphite modified rhodium catalyst for efficient hydroformylation of disubstituted alkenes and macromonomers in supercritical carbon dioxide

Polyethylene end functionalization using thia-Michael addition chemistry

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Facile and selective synthesis of aldehyde end-functionalized polymers using a combination of catalytic chain transfer and rhodium catalyzed hydroformylation

Cited by 13 publications

References 57 publications

Direct ‘in situ’, low VOC, high yielding, CO2expanded phase catalytic chain transfer polymerisation: towards scale-up

Direct ‘in situ’, low VOC, high yielding, CO2expanded phase catalytic chain transfer polymerisation: towards scale-up

A bulky phosphite modified rhodium catalyst for efficient hydroformylation of disubstituted alkenes and macromonomers in supercritical carbon dioxide

Polyethylene end functionalization using thia-Michael addition chemistry

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Direct ‘in situ’, low VOC, high yielding, CO₂expanded phase catalytic chain transfer polymerisation: towards scale-up

Direct ‘in situ’, low VOC, high yielding, CO₂expanded phase catalytic chain transfer polymerisation: towards scale-up