Polyferrocenylsilanes: Metal-Containing Polymers for Materials Science, Self-Assembly and Nanostructure Applications

Kulbaba, Kevin; Manners, Ian

doi:10.1002/1521-3927(20010701)22:10<711::aid-marc711>3.0.co;2-c

Cited by 230 publications

(58 citation statements)

References 39 publications

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“…7 The degree of crystallinity has been observed to increase with time, particularly once the selected polymer has been annealed above its T g . PFSs symmetrically substituted at silicon with small alkyl groups (Me, Et, n-Pr, n-Bu, and n-pentyl) are able to crystallise, as evidenced by a variety of analytical methods.…”

Section: Morphology In the Solid State: Crystalline And Amorphous Matmentioning

confidence: 99%

“…The initial ROP approach involved thermal treatment of the monomer (ca. [4][5][6][7][8] This article, while aiming to be comprehensive, has a particular focus on more recent developments over the past decade although key work from earlier is also discussed. This has permitted molar mass control, access to materials with narrow molecular weight distributions and desired end-group functionalisation, and also the formation of PFS block copolymers and other controlled architectures.…”

Section: Introductionmentioning

confidence: 99%

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Polyferrocenylsilanes: synthesis, properties, and applications

et al. 2016

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This in-depth review covers progress in the area of polyferrocenylsilanes (PFS), a well-established, readily accessible class of main chain organosilicon metallopolymer consisting of alternating ferrocene and organosilane units. Soluble, high molar mass samples of these materials were first prepared in the early 1990s by ring-opening polymerisation (ROP) of silicon-bridged [1]ferrocenophanes (sila[1]ferrocenophanes). Thermal, transition metal-catalysed, and also two different living anionic ROP methodologies have been developed: the latter permit access to controlled polymer architectures, such as monodisperse PFS homopolymers and block copolymers. Depending on the substituents, PFS homopolymers can be amorphous or crystalline, and soluble in organic solvents or aqueous media. PFS materials have attracted widespread attention as high refractive index materials, electroactuated redox-active gels, fibres, films, and nanoporous membranes, as precursors to nanostructured magnetic ceramics, and as etch resists to plasmas and other radiation. PFS block copolymers form phase-separated iron-rich, redox-active and preceramic nanodomains in the solid state with applications in nanolithography, nanotemplating, and nanocatalysis. In selective solvents functional micelles with core-shell structures are formed. Block copolymers with a crystallisable PFS core-forming block were the first to be found to undergo "living crystallisation-driven self-assembly" in solution, a controlled method of assembling block copolymers into 1D or 2D structures that resembles a living covalent polymerisation, but on a longer length scale of 10 nm-10 μm.

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Section: Morphology In the Solid State: Crystalline And Amorphous Matmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Polyferrocenylsilanes: synthesis, properties, and applications

et al. 2016

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“…Anionic polymerization proceeds under milder conditions (25 C) with good MW control (PDI <1.2) [Kulbaba and Manners, 2001;Ni et al, 1996]. A variety of other metallocenophanes have also been studied, including ferrocenophanes with GeR 2 , S, CH 2 CH 2 , and CH 2 S bridges and the chromium and ruthenium analogs.…”

Section: -11c Metallocenophanesmentioning

confidence: 99%

Ring‐Opening Polymerization

Odian

2004

Principles of Polymerization

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A wide variety of cyclic monomers have been successfully polymerized by the ring-opening process [Frisch and Reegan, 1969; Ivin and Saegusa, 1984;Saegusa and Goethals, 1977]. This includes cyclic amines, sulfides, olefins, cyclotriphosphazenes, and N-carboxy-a-amino acid anhydrides, in addition to those classes of monomers mentioned above. The ease of polymerization of a cyclic monomer depends on both thermodynamic and kinetic factors as previously discussed in Sec. 2-5.The single most important factor that determines whether a cyclic monomer can be converted to linear polymer is the thermodynamic factor, that is, the relative stabilities of the cyclic monomer and linear polymer structure [Allcock, 1970;Sawada, 1976]. Table 7-1 shows the semiempirical enthalpy, entropy, and free-energy changes for the conversion of cycloalkanes to the corresponding linear polymer (polymethylene in all cases) [Dainton and Ivin, 1958;Finke et al. 1956]. The lc (denoting liquid-crystalline) subscripts of ÁH, ÁS, and ÁG indicate that the values are those for the polymerization of liquid monomer to crystalline polymer.Polymerization is favored thermodynamically for all except the 6-membered ring. Ringopening polymerization of 6-membered rings is generally not observed. The order of thermodynamic feasibility is 3,4 > 8 > 5,7 which follows from the previous discussion (Sec. 2-5c) on bond angle strain in 3-and 4-membered rings, eclipsed conformational strain in the 5-membered ring, and transannular strain in 7-and 8-membered rings. One notes that RING-OPENING POLYMERIZATION RING-OPENING POLYMERIZATION

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“…Studies of high molecular weight M w > 10 5 analogues have not reproduced this behavior (137). Thin films of the homopolymers and block copolymers with organic or inorganic co-blocks are attracting attention for numerous applications, such as chemomechanical sensors, electrochromic materials, electrode mediators, variable refractive index materials, hole transport layers, charge dissipation coatings for dielectrics, lithographic resists, and photonic band-gap materials (133,(138)(139)(140)(141)(142)(143)(144).…”

Section: Polyferrocenylsilanesmentioning

confidence: 99%

Inorganic Polymers

Bourke¹,

Manners²

2001

Encyclopedia of Polymer Science and Technology

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The thermal ROP route requires the synthesis and careful purification of the cyclic trimer [Cl 2 PN] 3 and the use of elevated temperatures where control of molecular weight is very difficult and cross-linking can take place at high conversion, which can limit the yield. INORGANIC POLYMERSVol. 3to phosphazene polymers, which may well facilitate more rapid and extensive commercialization.Monomer Synthesis. Both the ROP and condensation routes to poly(dichlorophosphazene) require high purity monomers. For the traditional ROP process, ultrahigh purity [NPCl 2 ] 3 is required. The most common method for its preparation is through the reaction of PCl 5 with NH 4 Cl in a high boiling halogenated solvent, such as chlorobenzene or tetrachloroethane, at 150 • C. The yields can approach 70-80% under specialized conditions, but 50% is more typical (25). The phosphoranimine most commonly used in the aforementioned condensation route to poly(dichlorophosphazene) is Cl 3 P NSi(CH 3 ) 3 . The synthesis of this compound has been described (21) and is based on a modification of an earlier procedure (26) involving the reaction of PCl 5 with LiN(Si(CH 3 ) 3 ) 2 at −78 • C in hexane. However, the purification required by this method is a challenge and leads to an overall yield of <40%.It has also been reported that the reaction of N(Si(CH 3 ) 3 ) 3 with PCl 5 can be manipulated to maximize yields of either the cyclic trimer (76%) or the pure phosphoranimine monomer (40%) through variations in reaction conditions (25). These reactions use milder conditions than previously reported methods, with higher yields. In addition, the major side product, (CH 3 ) 3 SiCl, can be recycled to form one of the starting materials, N(Si(CH 3 ) 3 ) 3 .N-Silylphosphoranimines with alkyl and aryl substituents can be synthesized by reaction of commercial starting materials such as PCl 3 , ((CH 3 ) 3 Si) 2 NH, and Grignard reagents by way of a three-step process, with typical yields of 60-70%. These precursors are also accessible via a "one-pot" synthesis, which requires only isolation of the final product with yields of about 75% (3).Uses. Some of the most useful polyphosphazene derivatives are fluoroalkoxy derivatives, and amorphous copolymers are very useful as flame-retardant, hydrocarbon-solvent, and oil-resistant elastomers and have found aerospace and automotive applications. Polymers such as the amorphous comb polymer poly[bis(methoxyethoxyethoxy)phosphazene] (8) are of considerable interest as components of polymeric electrolytes in battery technology (1). Vol. 3 INORGANIC POLYMERS 35Polyphosphazenes are also of interest as biomedical materials and bioinert, bioactive, membrane-forming, and bioerodable materials (1).

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Polyferrocenylsilanes: Metal-Containing Polymers for Materials Science, Self-Assembly and Nanostructure Applications

Cited by 230 publications

References 39 publications

Polyferrocenylsilanes: synthesis, properties, and applications

Polyferrocenylsilanes: synthesis, properties, and applications

Ring‐Opening Polymerization

Inorganic Polymers

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