Living copolymerization of octadecyl vinyl ether with isobutyl vinyl ether: copolymerization parameters and crystallization behaviour of the copolymers

Zhang, Xiaochun; Reyntjens, Wouter; Goethals, Eric J.

doi:10.1002/(sici)1097-0126(200003)49:3<277::aid-pi360>3.0.co;2-k

Cited by 9 publications

(5 citation statements)

References 13 publications

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“…There are few examples of living random copolymers in cationic polymerization. − Thus, the feasibility of the synthesis of random copolymers with a narrow molecular weight distribution (MWD) was first examined by living cationic polymerization in the presence of an added base. The monomers employed in copolymerization were BMSiVE, a would-be water-soluble unit after deprotection, and four different hydrophobic monomers as shown in Scheme .…”

Section: Introductionmentioning

confidence: 99%

Thermosensitive Random Copolymers of Hydrophilic and Hydrophobic Monomers Obtained by Living Cationic Copolymerization

2004

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Thermosensitive random copolymers of hydrophilic and hydrophobic monomers are synthesized via living cationic copolymerization. The synthesis starts with the copolymerization of isobutyl vinyl ether (IBVE) and 2-(tert-butyldimethylsilyloxy)ethyl vinyl ether (BMSiVE) using the cationogen/Et1.5AlCl1.5 initiating system in the presence of an added base to give a copolymer with a narrow molecular weight distribution. The relative reactivities determined by the Fineman−Ross method indicate that the product copolymer has a highly random sequence distribution. Subsequent desilylation gave a well-defined amphiphilic random copolymer of hydrophobic (IBVE) and hydrophilic units (2-hydroxyethyl vinyl ether: HOVE). On heating, an aqueous solution of the product random copolymer undergoes thermally induced phase separation at a critical temperature. This phase separation is quite sensitive and reversible on heating and cooling. The randomness of the sequence distribution is indispensable to realizing such highly sensitive phase separation. For example, diblock copolymers are soluble and form micelles over a wide range of temperature, whereas copolymers with both block and random segments exhibit only slightly sensitive phase separation behavior with hysteresis. The critical temperature of the random copolymer presented here can be controlled by the composition of IBVE and HOVE. In addition to the composition, the structure of the hydrophobic repeating unit is a major factor determining the critical temperature.

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Section: Introductionmentioning

confidence: 99%

Thermosensitive Random Copolymers of Hydrophilic and Hydrophobic Monomers Obtained by Living Cationic Copolymerization

2004

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“…To examine the inuence of the properties of the hydrophobic segments on the physical gelation behavior, we synthesized block copolymers with ODVE possessing a long alkyl chain that enhances crystallinity [32][33][34][35] or PhOVE, which has an aromatic ring, 26 as the hydrophobic segments. The block copolymerization of ODVE and CEVE was rst examined in toluene at 0 C because side reactions such as the elimination of 2-chloroethanol from the main chain of the CEVE block can occur in the polymerization using only Et 1.5 AlCl 1.5 at 30 C, as demonstrated in a previous study.…”

Section: Precise Synthesis Of Various Precursor Copolymers By Living mentioning

confidence: 99%

Precise synthesis of amphiphilic diblock copolymers consisting of various ionic liquid-type segments and their influence on physical gelation behavior in water

2020

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“…The aqueous solutions of such polymers were expected to undergo physical gelation upon cooling, induced by the crystallinity‐driven aggregation of ODVE. Although Goethals and coworkers17, 18 recently reported the living cationic polymerization of ODVE with HI/ZnI 2 , including the crystallinity of its copolymers and the physical networks of the copolymers in water, no investigation was made into the influence of the sequence distribution on physical network properties such as viscoelasticity.…”

Section: Introductionmentioning

confidence: 99%

Stimuli‐responsive reversible physical networks. I. Synthesis and physical network properties of amphiphilic block and random copolymers with long alkyl chains by living cationic polymerization

Yoshida

Seno

Kanaoka

et al. 2005

J. Polym. Sci. A Polym. Chem.

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The living cationic polymerization of octadecyl vinyl ether (ODVE) was achieved with an 1-(isobutoxy)ethyl acetate [CH 3 CH(OiBu)OCOCH 3 ]/EtAlCl 2 initiating system in hexane in the presence of an added weak Lewis base at 30°C. In contrast to conventional polymers, poly(octadecyl vinyl ether) underwent upper-critical-solution-temperature-type phase separation in various solvents, such as hexane, toluene, CH 2 Cl 2 , and tetrahydrofuran, because of the crystallization of octadecyl chains. Amphiphilic block and random copolymers with crystallizable substituents of ODVE and 2-methoxyethyl vinyl ether (MOVE) were synthesized via living cationic polymerization under similar conditions. Aqueous solutions of the copolymers yielded physical gels upon cooling because of strong interactions between ODVE units, regardless of the copolymer structure. The product gels, however, exhibited different viscoelastic properties: A 20 wt % solution of a block copolymer (400/20 MOVE/ODVE) became a soft physical gel that behaved like a typical gel, whereas the corresponding random copolymer gave a transparent but stiff gel with a certain relaxation time. Differential scanning calorimetry analysis confirmed that the crystalline-amorphous transition of the octadecyl chains was a key step for inducing such physical gelation.

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Living copolymerization of octadecyl vinyl ether with isobutyl vinyl ether: copolymerization parameters and crystallization behaviour of the copolymers

Cited by 9 publications

References 13 publications

Thermosensitive Random Copolymers of Hydrophilic and Hydrophobic Monomers Obtained by Living Cationic Copolymerization

Thermosensitive Random Copolymers of Hydrophilic and Hydrophobic Monomers Obtained by Living Cationic Copolymerization

Precise synthesis of amphiphilic diblock copolymers consisting of various ionic liquid-type segments and their influence on physical gelation behavior in water

Stimuli‐responsive reversible physical networks. I. Synthesis and physical network properties of amphiphilic block and random copolymers with long alkyl chains by living cationic polymerization

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