Block copolymers with Zwitterionic groups at specific sites: Synthesis and aggregation behavior in dilute solutions

Pispas, Stergios; Hadjichristidis, Nikos

doi:10.1002/1099-0518(20001015)38:20<3791::aid-pola100>3.0.co;2-#

Cited by 10 publications

(8 citation statements)

References 27 publications

(10 reference statements)

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“…Although both functional polymers and star-shaped polymers are prevalent in the literature, the combination of well-defined thermoreversible chain-end interactions, such as multiple hydrogen-bonding interactions, and star-shaped macromolecules is limited. Hadjichristidis et al studied the synthesis and characterization of well-defined linear and star-shaped polystyrenes, polyisoprenes, and polybutadienes bearing sulfo- and phosphoro-zwitterionic groups capable of thermoreversible association. − Although these studies contributed significantly to the understanding of structure−property relationships, the reversible interaction is electrostatic, and the behavior of polymers that interact through multiple hydrogen bonding is expected to differ significantly. Meijer et al recently reported the synthesis of model low-molecular-weight poly(ethylene oxide- co -propylene oxide) three-arm star-shaped polymers with pendant 2-ureido-4[1 H ]-pyrimidinone (UPy) quadruple hydrogen-bonding functionalities .…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Star-Shaped Poly(ethylene-co-propylene) Polymers Bearing Terminal Self-Complementary Multiple Hydrogen-Bonding Sites

2006

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The polymerization of isoprene was initiated with 3-(tert-butyldimethylsilyloxy)-1-propyllithium (TBDMSPrLi), which contained a silyl-protected hydroxyl functionality. Living poly(isoprenyllithium) with controlled molecular weight and narrow molecular weight distribution coupled efficiently with divinylbenzene to form well-defined star-shaped polymers. Both linear and star-shaped polymers were subsequently hydrogenated to poly(ethylene-co-propylene) and deprotected quantitatively to yield terminal primary hydroxyl functionality. High conversions of hydroxyl functionality to the 2-ureido-4[1H]-pyrimidinone (UPy) quadruple hydrogen-bonding group were achieved using isocyanate coupling and subsequent reaction with 6-methylisocytosine. Nonfunctionalized and UPy-functionalized linear and star-shaped poly(ethylene-co-propylene)s were characterized using 1H NMR spectroscopy, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), tensile testing, and melt rheology. The observed glass transition temperatures were independent of molecular architecture for the UPy-functionalized polymers and nonfunctionalized analogues using both DSC and DMA. Tensile testing revealed the UPy-functionalized star polymers (UPy-Star) exhibited a higher Young's modulus and lower percent elongation at failure compared to the UPy-telechelic polymers with M n of 24 000 g/mol (UPy-24K-T) analogues. UPy-Star polymer exhibited a rubbery plateau region over a well-defined frequency range, and in contrast, the UPy-functionalized linear polymers were in the terminal flow regime, which suggested greater association for the star-shaped polymers. In addition, complex viscosity data revealed a non-Newtonian behavior for the star-shaped polymers in contrast to linear analogues, which is also consistent with a highly associated structure.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Star-Shaped Poly(ethylene-co-propylene) Polymers Bearing Terminal Self-Complementary Multiple Hydrogen-Bonding Sites

2006

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“…Abbreviations of the copolymers were given according to the positions of zwitterionic groups. Complete details for the synthesis of these copolymers are given elsewhere. − Briefly, for the synthesis of ZwIS and ZwSI ( α -functionalized copolymer), 3-(dimethylamino)propyllithium (DMAPLi) was used as an initiator to introduce a dimethylamino group at the end of the chain. For the synthesis of ZwISZw ( α , ω -functionalized copolymer), isoprene was polymerized first using DMAPLi as initiator followed by addition of the styrene monomer.…”

Section: Methodsmentioning

confidence: 99%

“…In our previous papers, the association and micellization of poly(styrene- b -isoprene) (PS- b -PI) copolymers functionalized with zwitterionic groups at various positions in two nonpolar solvents, CCl 4 and n -decane, were studied but not their adsorption behavior. − Thus, adsorption studies of these block copolymers are of great interest from the viewpoint of structural characteristics as adsorbed “copolymer brushes”. In this study, PS- b -PI copolymers were synthesized and functionalized with zwitterionic groups at different positions along the backbone.…”

Section: Introductionmentioning

confidence: 99%

Adsorption Behavior of Polystyrene−Polyisoprene Diblock Copolymers with Zwitterionic Groups Using Quartz Crystal Microbalance: Effect of Different Microstructures

et al. 2002

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The adsorption behavior of poly(styrene-b-isoprene) (PS-b-PI) copolymers functionalized with polar sulfobetaine zwitterionic groups at different positions along the backbone was investigated. Using dilute solutions in toluene, adsorption onto gold surface was investigated using a quartz crystal microbalance (QCM). ZwIS and ZwSI, ZwISZw, and SZwI are PS-b-PI copolymers functionalized at the α-position (zwitterionic group is attached to isoprene or styrene), at the α , ω-positions, and at the junction-point in the chain, respectively. The copolymers showed interesting adsorption behavior according to the zwitterion position. The adsorption isotherms for the copolymers exhibited typical Langmuir isotherm behavior. They showed different adsorbing amounts, which was explained by possible conformational states of copolymers on the surface. It was found that the position of zwitterionic groups has a major role on adsorption kinetics despite similar molecular weight and composition for the copolymers.

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“…The presence even of a small number of these polar groups can dramatically change the solution and aggregation behavior of nonpolar macromolecules. There are examples of such kind of functionalization at the beginning of the chain, the terminus of the chain, in‐chain, or to prepare telechelic copolymers . The carboxyl functionality can also be added to a polymer chain through a DPE carboxyl derivative, after protection with an oxazoline group or a diisopropylamide.…”

Section: Introductionmentioning

confidence: 99%

End‐Functionalized Chains via Anionic Polymerization: Can the Problems with Using Diphenylethylene Derivatives be Solved by using Bisphenol F?

Pagliarulo

2017

Macro Chemistry & Physics

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The controlled functionalization of polymers via anionic polymerization draws great attention not only because of the importance of introducing functionality into otherwise unfunctionalized polymers, but also because of the possibility to use the resulting macromonomers to make a variety of complex architectures. The versatile family of 1,1‐diphenylethylene (DPE) derivatives is widely used to produce many different functionalized (co)polymers. DPE can be added either as an end‐capping agent or be activated by butyllithium to initiate the polymerization. However, each approach faces potential problems in gaining precise control over the number of DPE moieties per chain. In this work, for the first time, the effectiveness of each approach is compared by the characterization of 1,1‐bis(4‐tert‐butyldimethylsiloxyphenyl)ethylene functionalized polystyrene, synthesized via both the procedures. A combination of NMR, size exclusion chromatography, matrix‐assisted laser desorption ionization‐time of flight (MALDI‐ToF) mass spectrometry, and interaction chromatography is used. To overcome the limitations of DPE derivatives, the use of a novel (protected) bisphenol F potassium initiator is proposed.

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Block copolymers with Zwitterionic groups at specific sites: Synthesis and aggregation behavior in dilute solutions

Cited by 10 publications

References 27 publications

Synthesis and Characterization of Star-Shaped Poly(ethylene-co-propylene) Polymers Bearing Terminal Self-Complementary Multiple Hydrogen-Bonding Sites

Synthesis and Characterization of Star-Shaped Poly(ethylene-co-propylene) Polymers Bearing Terminal Self-Complementary Multiple Hydrogen-Bonding Sites

Adsorption Behavior of Polystyrene−Polyisoprene Diblock Copolymers with Zwitterionic Groups Using Quartz Crystal Microbalance: Effect of Different Microstructures

End‐Functionalized Chains via Anionic Polymerization: Can the Problems with Using Diphenylethylene Derivatives be Solved by using Bisphenol F?

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