Functionalized rod-like polymers: one-dimensional rigid matrices

Freudenberger, R.; Claussen, Wilhelm; Schlüter, A. Dieter; Wallmeier, Holger

doi:10.1016/0032-3861(94)90794-3

“…It was recognized that if dendritic fragments (dendrons) could be attached to polymers with functional groups instead of to small, "dot-like" core molecules, it would be possible to form a new kind of macromolecule [2]. The architecture of this macromolecule would then be characterized by a rigid [2, 31 or flexible [4] backbone which is wrapped about by wedges that increasingly branch as they go from the inner to the outer regions.…”

Section: Introduction 2 Results and Discussionmentioning

confidence: 99%

Polymerization of styrenes and acrylates carrying dendrons of the first and second generation

Neubert¹,

Klopsch²,

Claussen³

et al. 1996

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“…

Some years ago Newkome and Vögtle proposed the concept of dendritic networks [1] whereby simple dendrimer/dendron subunits could be connected together to form macromolecular assemblies with nanoscopic dimensions.[2] At about the same time, Schlüter and co-workers began to report their pioneering works on the synthesis and characterization of a special kind of dendritic networks, also known as cylindrical dendronized polymers, [3,4] based on an inner-sphere-innersphere connection [2] approach, that is, the resulting dendronized polymers may be viewed as constructed from the connection of individual dendrons through their internal focal-point functional groups. A large number of such innersphere-inner-sphere connected dendronized polymers were reported.

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mentioning

confidence: 99%

Synthesis and Characterization of Dendritic Necklaces: A Class of Outer‐Sphere–Outer‐Sphere Connected Dendronized Organoplatinum Polymers

Chow

¹

,

Leung

²

,

Li

³

et al. 2003

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Some years ago Newkome and Vögtle proposed the concept of dendritic networks [1] whereby simple dendrimer/dendron subunits could be connected together to form macromolecular assemblies with nanoscopic dimensions.[2] At about the same time, Schlüter and co-workers began to report their pioneering works on the synthesis and characterization of a special kind of dendritic networks, also known as cylindrical dendronized polymers, [3,4] based on an inner-sphere-innersphere connection [2] approach, that is, the resulting dendronized polymers may be viewed as constructed from the connection of individual dendrons through their internal focal-point functional groups. A large number of such innersphere-inner-sphere connected dendronized polymers were reported. Some of them were shown to have cylindrical geometry [4] while some were known to self-assemble into spherical nanostructures.[5] To our surprise, examples of dendritic networks created by the alternative outer-sphere-outer-sphere connection strategy [2] are less studied. A few examples were already reported but invariably they all involve a random polymerization of dendrimer subunits that have a large number of reactive functional groups on the dendrimer surface.[6] We report herein a new variant of the outer-sphere-outer-sphere connection strategy that allows us to prepare a novel class of nanoscopic dendritic networks (hereafter called dendritic necklaces because of their structural resemblance to untied necklaces) by the controlled polymerization of dendrimer subunits containing only two reactive surface functional moieties (Figure 1). [7] We also show that the resulting dendritic necklaces, in contrast to randomly connected dendritic networks, can be fully characterized by solution techniques such as NMR, MS, GPC and laser light scattering (LLS) to enable a thorough assessment of their structural identity and purity. Employing organoplatinum coordination chemistry as a method for the polymerization of bis(ethynyl) surface-functionalized G1-G3 dendritic beads 1-3, we demonstrate that higher-order 1D dendritic necklaces with high degree-of-polymerization values (DP, from 30-880) could be prepared in high yields. We also describe a general synthetic protocol for the construction of dendrimers that contain a limited number of functional groups on the surface sector.Because bis(ethynyl) polyether-based dendrimers readily form trans-dialkynyl organoplatinum(ii) complexes upon treatment with trans-[(Et 3 P) 2 PtCl 2 ], this reaction was chosen to link the dendrimers 1-3 together.[8] To avoid random polymerization of the dendritic beads, only two of the surface moieties were functionalized with "reactive" long chain 10-(4-ethynylphenoxy)decyloxyl residues while the rest were decorated with "inert" 3-(4-tert-butylphenoxy)propoxy groups.The synthesis of the target dendritic monomers 1-3 required the availability of three bromo-dendrons 10, 11, and 12[9] (Scheme 1). Hence, the G1-dendrimer 4 and G2-

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“…The second one, grafting-to approach, is to attach dendrons or linear oligomers with end functionality directly to a backbone-to-be polymer containing anchor groups via coupling reaction. [10,11] However, its disadvantage is obvious: i.e., it is difficult to ensure complete coverage. Therefore, the coupling chemistry selection and the effect of characterization method on the coupling efficiency are rather important.…”

Section: Introductionmentioning

confidence: 98%

Novel Hybrid Polymer Brushes with Alternating Dendritic Wedges and Linear Side Chains

Zhang

¹

,

Li

²

,

Deng

³

et al. 2006

Macro Chemistry & Physics

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Summary: Novel hybrid polymer brushes with alternating dendritic wedge and linear chain as side chains were reported in this paper. Firstly, dendronized polymer initiators of generation one to three, GnMIBr (n = 1, 2, 3), were synthesized through the alternating copolymerization of styryl dendrons and maleimide derivative initiated by AIBN. The linear side chains were then generated through grafting‐from approach using ATRP of tBA initiated with the above‐mentioned macroinitiators. By combining such macromonomers and grafting‐from approach, a new kind of polymer brushes with alternating dendron and linear chain as side chains, GnMI‐g‐PtBA, were thus synthesized and characterized with 1H NMR, SEC, AFM, etc. Morphology studies made by AFM indicate the polymer brushes display a uniform worm‐like structure with a very long contour length. After the hydrolysis of PtBA branches under acidic conditions, amphiphilic dendronized polymer brushes with hydrophilic linear PAA side chains and hydrophobic dendritic side chains of three generations have been prepared.Schematic structure and AFM image of G1MI‐g‐PtBA‐2 dendronized polymer brushes.magnified imageSchematic structure and AFM image of G1MI‐g‐PtBA‐2 dendronized polymer brushes.

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Functionalized rod-like polymers: one-dimensional rigid matrices

Cited by 95 publications

References 17 publications

Polymerization of styrenes and acrylates carrying dendrons of the first and second generation

Polymerization of styrenes and acrylates carrying dendrons of the first and second generation

Synthesis and Characterization of Dendritic Necklaces: A Class of Outer‐Sphere–Outer‐Sphere Connected Dendronized Organoplatinum Polymers

Novel Hybrid Polymer Brushes with Alternating Dendritic Wedges and Linear Side Chains

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