Novel Amphiphilic Graft Copolymers Prepared by Ring-Opening Metathesis Polymerization of Poly(ethylene glycol)-Substituted Cyclooctene Macromonomers

Breitenkamp, Kurt; Simeone, Jennifer; Jin, Eunha; Emrick, Todd

doi:10.1021/ma021094v

Cited by 56 publications

(56 citation statements)

References 28 publications

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“…For this to occur, we believe, the PEG branch must be inducing a fold in the PE backbone, thereby allowing for the clustering of the branches and allowing the backbone to form small, isolated paraffin-like crystallites ( Figure 1). While the domain sizes that would result from this model are quite small in comparison to other amphiphilic PE-co-PEG block and graft copolymer systems, [11][12][13][16][17][18] this behavior is well documented for alternating block oligomers [19][20][21] of PEG and PE having blocks of similar size to the branch-tobranch distance and PEG branch lengths of our polymers.…”

Section: Introductionmentioning

confidence: 51%

“…possess a perfectly uniform distribution of hydrophilic branches (poly(ethylene glycol), PEG) along a hydrophobic (PE) backbone, architecture of which is typically inaccessible for PE-g-PEG systems. [11][12][13] The distance between branches (14 and 20 backbone carbons apart from this study) is tunable synthetically by altering the size and symmetry of the diene monomer. Second, the length of the graft is precisely defined, thereby differing from traditional amphiphilic graft copolymers.…”

Section: Introductionmentioning

confidence: 99%

“…Second, the length of the graft is precisely defined, thereby differing from traditional amphiphilic graft copolymers. [11][12][13][14] Precise placement of hydrophilic branches on the hydrophobic backbone induces a phase separated morphology that may be desirable in advanced applications.…”

Section: Introductionmentioning

confidence: 99%

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Probing the Effects of Hydrophilic Branch Size, Distribution, and Connectivity in Amphiphilic Polyethylene

Berda

Wagener

2008

Macro Chemistry & Physics

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Acyclic diene metathesis (ADMET) polymerization/hydrogenation methodology was used to synthesize a family of amphiphilic polyethylenes (PEs) with precisely placed poly(ethylene glycol) branches. Four structural parameters are varied in this report: size of the hydrophilic pendant group, manner in which the pendant group is connected to the backbone, distance between the pendant moieties along the backbone, and saturation of the polyolefin backbone. Varying the branch size with other parameters held constant results in negligible effects on thermal behavior. However, when either the distribution of branches or manner of connection of the branches is altered, changes in the thermal behavior become clear. These slight structural changes allow tunability of the structural morphology from fully amorphous to semicrystalline materials melting over a range of temperatures above 60 °C.magnified image

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Section: Introductionmentioning

confidence: 51%

Section: Introductionmentioning

confidence: 99%

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Probing the Effects of Hydrophilic Branch Size, Distribution, and Connectivity in Amphiphilic Polyethylene

Berda

Wagener

2008

Macro Chemistry & Physics

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“…Flash chromatography (20:1 hexane/EtOAc) afforded 338 mg (58 %) of the product as a bright yellow solid. TLC R f = 0.43 (10:1 hexane/EtOAc); 1 Salen cyclooctene ester 8: [10] Salen ligand 4 (500 mg, 0.987 mmol), acid 6 [35] General procedure for the synthesis of macrocyclic oligomeric salen: In a scintillation vial equipped with a magnetic stir bar, a solution of Grubbs third-generation initiator (0.04 equiv) in deoxygenated CH 2 Cl 2 was added to a solution of monomer (1 equiv) in deoxygenated CH 2 Cl 2 (final solution concentration 0.1 m with respect to monomer). The reaction mixture was stirred at RT for 30 min, followed by the addition of a few drops of ethyl vinyl ether to quench the reaction.…”

Section: Salen Ligand 4: (Rr)-12-diaminocyclohexane Monohydrochloridementioning

confidence: 99%

Macrocyclic Cyclooctene‐Supported AlCl–Salen Catalysts for Conjugated Addition Reactions: Effect of Linker and Support Structure on Catalysis

Madhavan

Takatani

Sherrill

et al. 2009

Chemistry A European J

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AlCl-salen (salen=N,N'-bis(salicylidene)ethylenediamine dianion) catalysts supported onto macrocyclic oligomeric cyclooctene through linkers of varying length and flexibility have been developed to demonstrate the importance of support architecture on catalyst activity. The role played by the support and the linkers in dictating catalyst activity was found to vary for reactions with contrasting mechanisms, such as the bimetallic cyanide and the monometallic indole addition reactions. While the flexible support significantly enhanced the cyanide addition reaction, most likely by improving salen-salen interactions in the transition state, it lowered the reaction rate for the monometallic indole reaction. For both reactions, significant increase in catalytic activity was observed for catalysts with the longest linkers. The effect of the flexible macrocyclic support on catalysis was further exemplified by the enhanced activity of the supported catalyst in comparison with its unsupported analogue for the conjugate addition of tetrazoles, which is known to be catalyzed by dimeric mu-oxo-salen catalysts. Our studies with the cyclooctene supported AlCl-salen catalysts provides significant insights for rationally designing highly efficient AlCl-salen catalysts for a diverse set of reactions.

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“…No T g s were observed upon the formation of the metal complex functionalized copolymers 2a-c. Copolymers 2a-c underwent 5% weight loss at 290 8C. The synthesis of Ir(ppy) 3 containing monomer 5 is based on the coupling of 3 [29] with 4 [17] (Scheme 2). All polymerizations of 5 were carried out using Grubbs' thirdgeneration catalyst.…”

Section: Synthesismentioning

confidence: 99%

Poly(cyclooctene)s with Pendant Fluorescent and Phosphorescent Metal Complexes

Kimyonok

Weck

2007

Macromol. Rapid Commun.

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Poly(cyclooctene)s with pendant Alq3 and fac‐Ir(ppy)3 were synthesized. Carbazole‐based comonomers were used to increase the solubility of the polymers and to transfer the energy into metal complexes. Excitation spectra of all polymers provided evidence of energy transfer. We established that the polymer backbone does not interfere with the optical properties of the metal complexes. All copolymers retained the optical properties of their small molecule metal complex analogs in solution and the solid state, making these polymers promising materials for potential electro‐optical applications.

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Novel Amphiphilic Graft Copolymers Prepared by Ring-Opening Metathesis Polymerization of Poly(ethylene glycol)-Substituted Cyclooctene Macromonomers

Cited by 56 publications

References 28 publications

Probing the Effects of Hydrophilic Branch Size, Distribution, and Connectivity in Amphiphilic Polyethylene

Probing the Effects of Hydrophilic Branch Size, Distribution, and Connectivity in Amphiphilic Polyethylene

Macrocyclic Cyclooctene‐Supported AlCl–Salen Catalysts for Conjugated Addition Reactions: Effect of Linker and Support Structure on Catalysis

Poly(cyclooctene)s with Pendant Fluorescent and Phosphorescent Metal Complexes

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