Silicones

Brown, Scott S. D.; Kendrick, Tom C.; McVie, James L.; Thomas, Dave R.

doi:10.1016/b978-008046519-7.00016-2

Cited by 12 publications

(5 citation statements)

References 107 publications

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“…In comparison, when poly[(hydridomethyl)siloxane] was hydrosilated under the same conditions, the SiH peak disappeared completely from the IR spectrum after 2 h of refluxing. These observations are consistent with the results of earlier studies which have found that the rate of hydrosilation is retarded by electron-donating, and accelerated by electron-accepting, groups on the silicon. In this context, it is understandable that the less polar character of the SiC backbone in the PSMs, as compared to the polysiloxanes, causes the hydrosilation of 1 to proceed with greater difficulty than the hydrosilation of poly[(hydridomethyl)siloxane].…”

Section: Resultssupporting

confidence: 93%

“…The 29 Si NMR spectra of these polymers consists of a major peak at 2.3−2.6 ppm, due to the [Si(Me)(C 3 H 6 R)CH 2 ] unit, along with, in some cases, a very minor peak at 16.5−17 ppm due to the [Si(Me)(H)CH 2 ] unit. As expected, all of the NMR spectra were consistent with α (anti-Markovnikov) addition of the olefins, with no sign of a β (Markovnikov) addition product in either the 1 H or 13 C NMR spectra.…”

Section: Resultssupporting

confidence: 79%

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Synthesis of Poly(silylenemethylenes) through Reactions Carried Out on Preformed Polymers. 2. Investigation of the Hydrosilation Route to Substituted Poly(silylenemethylenes)

Rushkin

Interrante

1996

Macromolecules

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A series of polymers of the type [Si(CH3)(C3H6R)CH2] n where R = C3H7, NEt2, carbazole, and OC2H4OC2H4OCH3 were prepared by hydrosilation of the appropriate terminal olefin with the [Si(H)(CH3)CH2] n (1) polymer using Karsted's catalyst. It was found that hydrosilation of these olefins with 1 proceeds with a relatively high (80−95%) conversion of the polymer SiH groups. NMR and DSC data on these polymers as well as their relative thermal and oxidative stabilities are reported. The phenol-substituted polymers, [Si(CH3)(C3H6C6H4OH)X] n (5), where X = O (5e) or CH2 (5f), were also prepared and their stability toward base hydrolysis was evaluated. It was found that the polycarbosilane 5f shows superior hydrolytic stability relative to the polysiloxane 5e.

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Section: Resultssupporting

confidence: 93%

Section: Resultssupporting

confidence: 79%

Synthesis of Poly(silylenemethylenes) through Reactions Carried Out on Preformed Polymers. 2. Investigation of the Hydrosilation Route to Substituted Poly(silylenemethylenes)

Rushkin

Interrante

1996

Macromolecules

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“…However, some of them are decomposed by oxidation, hydrolysis, and acid−base reactions. Silicon-containing polymers are exceptionally thermally and chemically stable. , Polyorganosiloxanes form a class of commercially important materials known as silicones. Poly(dimethylsiloxane) (PDMS) is the most common of the industrial silicone polymers.…”

Section: Introductionmentioning

confidence: 99%

Preparation and Characterization of Inclusion Complexes of Poly(dimethylsiloxane)s with Cyclodextrins

2001

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β-Cyclodextrin (β-CD) and γ-cyclodextrin (γ-CD) formed inclusion complexes with poly(dimethylsiloxane)s (PDMS) of various molecular weights to give crystalline compounds. However, α-cyclodextrin (α-CD) did not form complexes with PDMS of any molecular weight. The yields of the β-CD−PDMS inclusion complexes decreased with increasing molecular weight of PDMS. In contrast, the yields of the γ-CD−PDMS inclusion complexes increased with increasing molecular weight, reached a maximum at molecular weight of around 760, and gradually decreased at higher molecular weight. The chain-length selectivity is reversed between β-CD and γ-CD. The β-CD−PDMS inclusion complexes are stoichiometric 1:1 compounds when the molecular weights of PDMS are low. The γ-CD−PDMS inclusion complexes are stoichiometric 2:3 (cyclodextrin:monomer unit of PDMS) compounds. The complexes were isolated and characterized by 1H NMR, 13C CP/MAS NMR, and X-ray diffraction studies. The inclusion modes are discussed.

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“…Catalyst poisoning has been suggested as a possible cause of this problem . It is also well-known that electropositive and bulky groups attached to the silicon retard the hydrosilation process …”

Section: Introductionmentioning

confidence: 99%

Modification of a Hyperbranched Hydridopolycarbosilane as a Route to New Polycarbosilanes

et al. 1997

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A general method for introducing various side chains onto a highly branched polysilaethylene (HBPSE) backbone is described. This method starts with a commercial oligomer mixture which has a highly branched structure, consisting of [H3SiCH2], [SiH2CH2], [SiH(CH2)2], and [Si(CH2)3] subunits combined to give an overall "SiH2CH2" average formula. Several alkyl-, aryl-, and allyl-substituted HBPSEs were prepared by first converting the parent HBPSE into a highly reactive bromo-substituted derivative which was then treated with organolithium reagents (RLi, R ) C4H9, C6H13, C8H17, C6H5, C6H4N(Me)2) or Grignard reagents (RMgBr, R ) Et, allyl). The parent HBPSE and its derivatives were characterized by means of NMR and IR spectroscopy, as well as elemental analysis, DSC, GPC, and VPO. It was shown that the allyl-substituted HBPSE can be used as a synthetic platform for attaching functional side chains via the hydrosilation reaction.

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Silicones

Cited by 12 publications

References 107 publications

Synthesis of Poly(silylenemethylenes) through Reactions Carried Out on Preformed Polymers. 2. Investigation of the Hydrosilation Route to Substituted Poly(silylenemethylenes)

Synthesis of Poly(silylenemethylenes) through Reactions Carried Out on Preformed Polymers. 2. Investigation of the Hydrosilation Route to Substituted Poly(silylenemethylenes)

Preparation and Characterization of Inclusion Complexes of Poly(dimethylsiloxane)s with Cyclodextrins

Modification of a Hyperbranched Hydridopolycarbosilane as a Route to New Polycarbosilanes

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