Cyclodextrin in polymer chemistry: Kinetic studies on the free-radical polymerization of cyclodextrin-complexed styrene from homogeneous aqueous solution

Ritter, Helmut; Steffens, Christopher; Storsberg, Joachim

doi:10.1515/epoly.2005.5.1.353

Cited by 3 publications

(4 citation statements)

References 20 publications

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“…Therefore, these monomers do not meet the required criteria for a controlled radical polymerization in homogenous aqueous media. Their behavior was similar to that of other hydrophobic monomers, for example, styrene and methyl methacrylate in CD‐mediated free radical polymerization, which have previously been described in the literature . We believe that the early precipitation effect occurs due to the increasing steric hindrance for the complexed polymer side chains with increasing length of the propagating polymer chains which leads to partial decomplexation.…”

Section: Resultssupporting

confidence: 80%

“…In particular, the ability of CDs to form supramolecular host/guest complexes with hydrophobic molecules gives access to a variety of possible utilizations in polymer chemistry . There are several examples where CDs were used to polymerize hydrophobic monomers in water, for example, in radical polymerization and CRP . In addition, CDs were used for the formation of supramolecular block copolymers, CD/guest networks, supramolecular star polymers, or graft polymers and also to solubilize chain transfer agents (CTAs) in emulsion polymerizations and homogenous aqueous polymerization …”

Section: Introductionmentioning

confidence: 99%

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Limitations of cyclodextrin‐mediated RAFT homopolymerization and block copolymer formation

Hetzer¹,

Schmidt

Barner‐Kowollik

et al. 2013

J. Polym. Sci. Part A: Polym. Chem.

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ABSTRACT:The design and synthesis of a new hydrophobic monomer, that is, 4-(tert-butyl)phenyl 6-acrylamidohexanoate (TBP-AA-HO) and its ability to form supramolecular host/guest complexes with b-cyclodextrin (CD) is described. The aqueous CD-mediated reversible addition fragmentation chain transfer (RAFT) polymerization affords molecular masses up to 8600 g mol 21 with polydispersities between 1.2 and 1.4. The surprisingly low molecular weights for higher monomer/chain transfer agent (CTA) ratios are investigated by comparing results obtained from free radical and RAFT radical polymerization in aqueous and organic media. The results indicate a steric hindrance caused by attached CD molecules on the growing polymer chain leading to stagnation of the polymerization process due to a restricted accessibility of the reactive chain end. This hypothesis is supported by matrix-assisted laser desorption/ionization time of flight mass spectrometry. Furthermore, the CD-mediated synthesis of amphiphilic diblock copolymers in variable aqueous media is described. Hydrophilic poly(N,N-dimethylacrylamide) macroCTAs with different molecular weights are used to polymerize TBP-AA-HO at 50 C. The diblock copolymers are analyzed by 1 Hnuclear magnetic resonance spectroscopy and size exclusion chromatography. The results confirm the polymer structure and reveal similar limitations of chain growth as observed for the CDmediated homopolymerization with a limit of 7000 g mol 21 for efficient chain extension.

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Section: Resultssupporting

confidence: 80%

Section: Introductionmentioning

confidence: 99%

Limitations of cyclodextrin‐mediated RAFT homopolymerization and block copolymer formation

Hetzer¹,

Schmidt

Barner‐Kowollik

et al. 2013

J. Polym. Sci. Part A: Polym. Chem.

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“…Vulcanization of the persulfate-initiated polymyrcene led to rubbery materials, with a cross-linking density of 2.50 × 10 −4 mol/cm 3 , where the formation of the polysulfide linkages was supported by the microstructural defects [20]. Similar to emulsion polymerization, the radical polymerization of β-myrcene was also possible with a K 2 S 2 O 8 /Na 2 S 2 O 5 redox initiating system in cyclodextrin solution, where the macrocycle solubilizes the monomer [21]. This emulsion-like, detergent-free polymerization resulted in low molar mass polymyrcene with dispersity around 2 and mostly 1,4 microstructure.…”

Section: Myrcenementioning

confidence: 97%

Terpene Based Elastomers: Synthesis, Properties, and Applications

2020

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The limited source of fossil-fuel and the predominance of petroleum-based chemistry in the manufacturing of commodity polymers has generated tremendous interest in replacing the fossil source-based polymers with renewable counterparts. The field of sustainable elastomers has grown in the past three decades, from a few examples to a plethora of reports in modern polymer science and technology. Applications of elastomers are huge and vital for everyday living. The present review aims to portray a birds-eye view of various sustainable elastomers obtained from the wide family of acyclic terpenes (renewable feedstocks from different plant oils) via various polymerization techniques and their properties, as well as plausible developments in the future applications of sustainable polymers. Not only the homopolymers, but also their copolymers with both green and commercial fossil based comonomers, are reviewed.

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“…The hydrophobic cavity of CDs binds suitable organics by hydrophobic interactions and/or H-bonds, while the hydrophilic outer shell provides the water solubility. Ritter et al successfully polymerized various hydrophobic monomers, such as styrene [33][34][35][36][37][38], (meth)acrylates [33,34,[39][40][41][42][43][44], phenol derivatives [45,46], fumarates [47,48], dienes [49,50], halo-olefins [51][52][53], and other non-commercial ones [54][55][56][57][58][59][60][61] in water, solubilized by CD, via free radical polymerization methods. During the polymerization, the CD, every time, slips off from the last monomeric unit of the polymer, and the product precipitates, resulting in a pure product, or simple purification.…”

Section: Introductionmentioning

confidence: 99%

New, Aqueous Radical (Co)Polymerization of Olefins at Low Temperature and Pressure

Hero

Kali

2020

Processes

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In this communication, we describe our preliminary results for the development of a new method of ethylene and propene (co)polymerization at low pressure at room temperature, using cyclodextrin-assisted aqueous radical polymerization for the first time. For polypropylene homopolymerization, the cyclodextrin was entirely removed, and the partially soluble polymer was characterized. The purification of polyethylene was not complete, since the threaded cyclodextrins remained on the polymer chain, enhancing its solubility and enable to analyze the sample. With this environmentally benign method, polyolefines could be produced, for the first time. The estimated yield was low, and therefore the conditions should be further tuned for industrial application. This straightforward approach could also be applied to synthesize poly(ethylene-co-vinyl acetate) copolymer with an ethylene content of 20 mol% and enhanced yield. Although the procedure in this stage of research has some limitations, the theory behind can later be applied to develop new, energy-efficient, and versatile industrial processes for olefin copolymerizations for a wide range of comonomers.

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Cyclodextrin in polymer chemistry: Kinetic studies on the free-radical polymerization of cyclodextrin-complexed styrene from homogeneous aqueous solution

Cited by 3 publications

References 20 publications

Limitations of cyclodextrin‐mediated RAFT homopolymerization and block copolymer formation

Limitations of cyclodextrin‐mediated RAFT homopolymerization and block copolymer formation

Terpene Based Elastomers: Synthesis, Properties, and Applications

New, Aqueous Radical (Co)Polymerization of Olefins at Low Temperature and Pressure

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