Catalytic polymerization of 1,3‐disilacyclobutane derivatives

Kriner, William A.

doi:10.1002/pol.1966.150040218

Cited by 49 publications

(17 citation statements)

References 3 publications

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“…The difficulty of polyin the 29 Si NMR spectrum [ Fig. 1(d 4,5 The molecular weight of all the polymers are listed in Table I. Unlike obtained with a higher average molecular weight, the 1,1,3,3-tetraalkyl-1,3-disilacyclobutanes, 10c the steric bulk of the longer alkyl groups in the 1,3-dialkyl-1,3-dimethyl-1,3-disilacyclobutanes did not seem to affect the chain propagation during the polymerization.…”

Section: Preparation Of 13-dichloro-13-dimethyl-13-disilacyclobutanementioning

confidence: 99%

“…After their initial preparation as of the corresponding DSCB monomers. 4,5 Of these low molecular weight oligomers in 1949-50 by polymers, only the symmetrically disubstituted active metal coupling of chlorocarbosilanes, 2 the poly(dimethylsilylenemethylene) was characterfirst high molecular weight polymers of this type ized in detail, leading to information concerning were obtained in the late 1950s by thermally inits thermal stability 6a in nitrogen and in air as well as values for its glass and melting transitions…”

Section: Introductionmentioning

confidence: 99%

“…3 Later efforts by Kriner 4 and Bamford et al 5 established The poly ( silylenemethylene ) s ( PSM's ) are the ''reverse Grignard route'' to substituted disilaemerging as a novel class of polymers that are cyclobutanes and the metal complex-catalyzed structurally related to both the all-carbon back-ROP method for their conversion to high molecubone polyolefins and such inorganic polymers as lar weight linear polymers. These early efforts the polysilanes and polysiloxanes.…”

Section: Introductionmentioning

confidence: 99%

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Preparation and thermal properties of asymmetrically substituted poly(silylenemethylene)s

Shen

Interrante

1997

J. Polym. Sci. A Polym. Chem.

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Section: Preparation Of 13-dichloro-13-dimethyl-13-disilacyclobutanementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Preparation and thermal properties of asymmetrically substituted poly(silylenemethylene)s

Shen

Interrante

1997

J. Polym. Sci. A Polym. Chem.

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“…1,3‐Disilacyclobutanes (DSCBs) are known to undergo thermally, or catalytically, induced ring opening polymerization (ROP) to produce linear polymers containing alternating silicon and carbon atoms in the backbone, due to the substantial strain energy of the four‐membered (Si‐C) 2 ring . We previously reported the use of DSCB rings embedded in a cyclolinear polycarbosilane (CLPCS) as a thermosetting polymer .…”

Section: Introductionmentioning

confidence: 99%

“…1,3-Disilacyclobutanes (DSCBs) are known to undergo thermally, or catalytically, induced ring opening polymerization (ROP) to produce linear polymers containing alternating silicon and carbon atoms in the backbone, due to the substantial strain energy of the four-membered (Si-C) 2 ring. [1][2][3][4][5] We previously reported the use of DSCB rings embedded in a cyclolinear polycarbosilane (CLPCS) as a thermosetting polymer. 6,7 A series of CLPCSs with DSCB rings alternating with bridging alkylene groups were prepared via acyclic diene metathesis (ADMET) polymerization of diolefin-terminated DSCB monomers, followed by in-situ reduction of the internal double bonds.…”

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confidence: 99%

Grignard condensation routes to 1,3‐disilacyclobutane‐containing cyclolinear polycarbosilanes

Liu

Rathore

Dubois

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Alkylene‐ and arylene‐bridged cyclolinear polycarbosilanes (CLPCS) with 1,3‐disilacyclobutane (DSCB) rings incorporated in the main chain of the polymer were prepared by polycondensation between corresponding di‐functional DSCB derivatives and di‐Grignard reagents. Well‐defined, low molecular weight (Mn = 3–5K; DP = 17–26), hexylene‐ and phenylene‐bridged CLPCS polymers were obtained without appreciable ring opening of the DSCB rings. Large exothermic peaks were observed in the DSC for these CLPCSs, which indicated, along with the IR spectra, that crosslinking occurred on heating to about 250 °C via the ring opening of the embedded, alternating, DSCB rings. Moreover, PB‐CLPCS undergoes photochemically induced crosslinking on UV irradiation to form crosslinked polycarbosilane network films. The spin‐cast, cured, films of these CLPCSs exhibit relatively low dielectric constants and promising thermal and mechanical properties for applications in electronics, for example, directly UV‐photoimprinted low‐k dielectrics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1547–1557

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Linear and hyperbranched polycarbosilanes with Si-CH2-Si bridging groups: A synthetic platform for the construction of novel functional polymeric materials

Interrante

Rushkin

Shen

1998

Appl. Organometal. Chem.

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Work carried in the authors' laboratory on Si-CH 2-Si bridged polycarbosilanes is reviewed. In pursuit of high-yield polymeric precursors to silicon carbide, convenient synthetic routes to both linear and hyperbranched polycarbosilanes having a '[SiH 2 CH 2 ] n ' compositional formula have been developed. The linear [SiH 2 CH 2 ] n polymer was prepared by ring-opening polymerization of a substituted disilacyclobutane, and was studied both as an analogue of polyethylene and as a high-yield precursor to SiC. Elaboration of the methods employed to prepare this polymer has yielded a wide range of new poly(silylenemethylene)s (PSMs) of the type [SiRR'CH 2 ] n , where R and R' can be a wide range of different groups, including a series of symmetrically disubstituted polymers with R = R' = F, alkyl and alkoxy which form crystalline solid phases and various amorphous, atactic polymers having different R and R' groups. By using (Si)-Cl replacement reactions analogous to those developed previously for polydichlorophosphazene, as well as hydrosilation reactions similar to those used for [Si(H)(Me)O] n , a series of side-chain polymers having various groups attached to Si through Si-C or Si-O bonded linkages were obtained. Similar polymer modification reactions have recently been developed for the branched oligomer/polymer analogue of these linear polycarbosilanes, leading to hyperbranched species with functional substituents, including a di(ethyleneoxy) methyl ether-terminated derivative which readily dissolves lithium salts. The results of studies of these novel 'inorganic/organic' hybrid polycarbosilanes are described and their properties are compared with those of related carbon-backbone and siloxane polymers.

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Catalytic polymerization of 1,3‐disilacyclobutane derivatives

Cited by 49 publications

References 3 publications

Preparation and thermal properties of asymmetrically substituted poly(silylenemethylene)s

Preparation and thermal properties of asymmetrically substituted poly(silylenemethylene)s

Grignard condensation routes to 1,3‐disilacyclobutane‐containing cyclolinear polycarbosilanes

Linear and hyperbranched polycarbosilanes with Si-CH2-Si bridging groups: A synthetic platform for the construction of novel functional polymeric materials

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