• Title/Summary/Keyword: Hydrosilation

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Synthesis and Photopolymerization of Vinyl Ether and Epoxy-Functionalized Silicones

  • Pyun, Sang-Yong;Kim, Whan-Gi
    • Macromolecular Research
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    • v.11 no.3
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    • pp.202-205
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    • 2003
  • The reactive precursors, vinyl ethers, and epoxy-silicones, were synthesized. The vinyl ether monomers were prepared from primary alcohol and ethyl vinyl ether with mercury (II) acetate. The epoxy-functionalized silicones have been achieved by the controlled, rhodium-catalyzed, chemoselective hydrosilation of vinyl ether with siloxanes or silane. It was shown that the hydrosilation proceeds exclusively at the vinyl ether group of alkenyl vinyl ether without participation at the alkenyl group. The photoinduced cationic polymerization of these monomers was studied and found to be all highly reactive.

Temperature-dependent studies on catalytic hydrosilation of polyalkylsiloxane using NMR

  • Sul, Hyewon;Lee, Tae Hee;Lim, Eunsoo;Rho, Yecheol;Kim, Chong-Hyeak;Kim, Jeongkwon
    • Analytical Science and Technology
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    • v.30 no.4
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    • pp.213-219
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    • 2017
  • Polyalkylsiloxane has been spotlighted in pressure-sensitive adhesive (PSA) application due to excellent physical properties and good biocompatibility. Thermal behaviour of polyalkylsiloxane mixtures, such as thermal stability and heat flow, were studied using TG-DTA during catalytic hydrosilation. To understand reaction kinetics of cross-linking, catalytic hydrosilation of polyalkylsiloxane was monitored using variable temperature nuclear magnetic resonance (VT-NMR) as increased temperature. The formation of cross-linking bond $Si-CH_2-CH_2-Si$ was directly observed using distortionless enhanced by polarization transfer (DEPT) technique. Successfully polyalkylsiloxane PSA samples exhibited excellent adhesion properties by cross-linking reaction.

Synthesis and Characterization of A Carbosilane Dendrimer Containing Allylic End Groups

  • 김정균;박은미;강은주
    • Bulletin of the Korean Chemical Society
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    • v.17 no.7
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    • pp.592-595
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    • 1996
  • A silane dendrimer with 48 allylic end groups has been synthesized in excellent yield, via repetitive alkenylation-hydrosilation cycles. Starting with hexaallylethylenedisilane ((CH2=CHCH2)3SiCH2)2 as the core molecule (G0), a succession of alternate platinum catalyzed hydrosilation (Pt/C, 10% platinum content on active carbon) of all allyl groups with methyldichlorosilane and the allylation of all SiCl2 groups with allylmagnesium bromide in THF provided 3rd generation (G3) as carbosilane dendrimer. All the generations of dendrimer have been characterized by 1H and 13C NMR spectroscopy as well as elemental analysis.

Preparation of Carbosilane Dendrimers Based on Siloxane Tetramer: Silane Arborols $(VII)^1$

  • 김정균;안경미
    • Bulletin of the Korean Chemical Society
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    • v.18 no.2
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    • pp.164-170
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    • 1997
  • Via hydrosilation-alkenylation approach using hydrosilanes (HSiMeCl2 and HSiCl3) and allylmagnesium bromide with siloxane tetramer (MeCH2=CHSiO)4 as core molecule, noble carbosilane dendrimers with 12, 24, 48 and 96 allylic end groups have been prepared. The reaction path of the repetitive alkenylation and hydrosilation was monitored by means of NMR spectroscopic measurements. Every step for the formation of dendrimer provided almost quantitative yields as pure dendrimers. Based on the observation of UV spectroscopic measurements of Gn (n=1-4) molecules containing allylic end groups, the maximal molal absorption coefficients (εmax) at λmax and the number of double bonds proved an exponentially increased correlation.

Synthesis of Dendritic Carbosilanes by the Use of Hyperbranched Polymers (Hyperbranched Polymer를 이용한 나뭇가지꼴 카보실란 거대분자의 합성)

  • Kim, Chung Kyun;Kang, Sung Kyung;Park, Eun Mi
    • Journal of the Korean Chemical Society
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    • v.43 no.4
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    • pp.393-400
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    • 1999
  • Dendritic carbosilanes based on hyperbranched polycarbosilanes as core molecule have been prepared The core molecules were obtained by the use of hydrosilation of $HSiMe_{3-n}$$(CH_2CH=CH_2)_n$(n=2; $AB_2$,3;$AB_3$type). The hyperbranched core $AB_2\;and\; AB_3$ type polymers were generated to higher molecular dendritic carbosilanes Gn+1 by the use of hydrosilation and alkenylation sequence. The Gn+2P generations were not obtained as unified molecules by the use of hydrosilation with $HSiMeCl_2$. Gn and Gn+1 type polymers were produced to polysilol by the reaction of 9-BBN and alkali medium oxidation of hydroborated compounds. The degree for reaction has been controlled by the NMR spectroscopy.

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Photopolymerization of Methyl methacrylate with Phenylsilane

  • 홍란영;우희권;함희숙
    • Bulletin of the Korean Chemical Society
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    • v.16 no.4
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    • pp.360-363
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    • 1995
  • The photopolymerization of methyl methacrylate(MMA) with phenylsilane wasperformed. The molecular weights of the poly(MMA) containing SiH moieties were increased with augment of molar ratio of PhSiH3 over MMA by cross-linking via hydrosilation at the expense of isolated yield. Phenylsilane apparently influenced on the photopolymerization as a chain transfer agent and solvent.

Preparation and Termination of Carbosilane Dendrimer Based on Siloxane Tetramer (실옥산테트라머를 이용한 나뭇가지꼴 실란거대분자의 제조와 정지반응)

  • Kim, Chung Kyun;Park, Eun Mi
    • Journal of the Korean Chemical Society
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    • v.42 no.3
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    • pp.277-284
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    • 1998
  • Dendritic macromolecules of the first to fourth generation were synthesized, using alkenylation and hydrosilation cycles with allylmagnesium bromide and dichloromethylsilane as building blocks and siloxane tetramer $(Me(CH_2=CH)SiO)_4$, as core molecule. By the reaction of the dichloromethylsilyl-capped generation (G4P) with p-bromophenol, p-phenylphenol and lithium phenyethynylide, dendrimers with specific functions (G4P-BP (Mw: 16,300), G4P-PP (16,121), and CAP-PA (11,764)) have been produced. Analysis of new dendrimers by NMR, UV and MALD1 mass spectrometry suggests that they are pure and unified.

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Polymerization and Application of Contact Lens Materials (콘택트렌즈 재료의 합성과 응용에 관한 연구)

  • Song, Kyung-Sek;Lee, Jong-Heon;Sung, A-Young
    • Journal of Korean Ophthalmic Optics Society
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    • v.8 no.2
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    • pp.129-134
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    • 2003
  • A wide variety of unsaturated vinyl derivatives can be induced to undergo free-radical chain polymerization. The capability to carry out a thermodynamically feasible polymerization relies on its kinetic feasibility on whether the proceeds at a reasonable rate under a given set of reaction conditions. Initiator or promoter is often required to achieve the kinetic feasibility. Only a few unsaturated monomers including methyl methacrylate(MMA) are known to absorb light between 250 and 500 nm which is the most convenient wavelength range. Also, the polysilanes with unusual optical and electronic properties have been used as ceramic precursors, deep UV photoresists, photoconductors. The hydrosilation has been used to make many interesting types of silicon containing polymers such as copolymer, dendrimers. Bulk polymerization of monomers with different molar radio of hydrosilanes(9:1 through 1:9) were performed. A quartz test tube charged with monomer and hydrosilane was degassed and irradiated with 250 nm UV for 6 hours. The polymer was taken in toluene, precipitated in hexane, filtered off, and dried. It was found that the initiators appeared to competitively and concurrently function as both chain initiation and transfer agents in the polymerization of vinyl monomers.

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