106-90-1Relevant articles and documents
From epoxide to cyclodithiocarbonate Telechelic polycyclooctene through chain-transfer ring-opening metathesis polymerization (ROMP): Precursors to non-isocyanate polyurethanes (NIPUS)
Vanbiervliet, Elise,Fouquay, Stéphane,Michaud, Guillaume,Simon, Frédéric,Carpentier, Jean-Fran?ois,Guillaume, Sophie M.
, p. 69 - 82 (2017)
Telechelic polycyclooctenes (PCOEs) have been successfully synthesized by ring-opening metathesis polymerization (ROMP)/cross-metathesis (CM) of cyclooctene (COE) using Grubbs' second-generation catalyst (G2) in the presence of epoxide-functionalized chain-transfer agents (CTAs). The monofunctional epoxide oxiran-2-ylmethyl acrylate CTA (1) afforded the isomerized α-(glycidyl alkenoate),ω-propenyl functional (IMF) PCOEs. The use of 1,4-benzoquinone (BZQ) as additive completely inhibited the C=C isomerization process, thereby leading selectively to α-(glycidyl alkenoate),ω-vinyl telechelic (MF) PCOE. On the other hand, difunctional epoxide CTAs, bis(oxiran-2-ylmethyl) fumarate (3), bis(oxiran-2-ylmethyl) maleate (4), bis(oxiran-2-ylmethyl) (E)-hex-3-enedioate (5), and (Z)-1,4-bis(oxiran-2-ylmethoxy)but-2-ene (6), selectively afforded the corresponding α,ω-di(glycidyl alkenoate) telechelic PCOEs (DF) along with minor amounts of cyclic nonfunctional (CNF) PCOE. In the presence of these difunctional symmetric CTAs, the mechanism is proposed to proceed through a tandem one-pot CM/ROMP/ring-closing metathesis (RCM) approach. CM was more effective with Z-than E-configurated CTAs (4 > 6 ? 3 ? 5), regardless of the presence of a methylene group in-between the C=C double bond and the glycidyl moiety. Subsequent dithiocarbonatation of the α,ω-diepoxide telechelic PCOEs upon reaction with CS2 in the presence of LiBr quantitatively afforded the first examples of bis(cyclodithiocarbonate) end-functional PCOEs. Ensuing aminolysis of the bis(cyclodithiocarbonate) telechelic PCOEs with the polyether (triethylene glycol) diamine JEFFAMINE EDR-148 quantitatively afforded, at room temperature without any added catalyst, the desired poly(mercaptothiourethane)s NIPUs, as evidenced from FTIR spectroscopy, TGA, and DSC analyses.
Sustainable chemo-enzymatic synthesis of glycerol carbonate (meth)acrylate from glycidol and carbon dioxide enabled by ionic liquid technologies
Donaire, Antonio,Garcia-Verdugo, Eduardo,Lozano, Pedro,Luis, Santiago V.,Nieto, Susana,Porcar, Raul,Villa, Rocio
, p. 4191 - 4200 (2021/06/17)
A sustainable chemo-enzymatic process for producing both glycerol carbonate acrylate (GCA) and glycerol carbonate methacrylate (GCMA), as useful monomers for the preparation of biodegradable plastic materials, has been carried out by taking advantage of ionic liquid (IL) technologies. The process consisted of two consecutive catalytic steps, which can be carried out by either sequential or one-pot experimental approaches. Glycidyl (meth)acrylate was firstly synthesized by enzymatic transesterification of (meth)acrylate vinyl ester with glycidol in Sponge Like Ionic Liquids (SLILs) as the reaction medium (100% yield after 6 h at 60 °C). SLILs not only provided a suitable reaction medium, but also allowed the simple isolation of the resulting glycidyl esters as an IL-free pure fraction through a straightforward cooling/centrifugation protocol. The second step consisted of the synthesis of GCA, or GCMA, as the outcome of the cycloaddition of CO2to the obtained glycidyl acrylate or glycidyl methacrylate, respectively, catalysed by a covalently attached 1-decyl-2-methylimidazolium moiety (Supported Ionic Liquid-Like Phase, SILLP) in a solvent-free system and under mild conditions (60 °C, 1-10 bar), leading to up to 100% yield after 6 h. The components of the reaction system (biocatalyst/SLIL/SILLP) can be fully recovered and reused for at least 6 cycles with unchanged catalytic performance.
Separating material
-
, (2008/06/13)
The present invention provides a separating material producable by a) providing a solid substrate, having amino-functional groups coupled to the substrate surface, b) covalently coupling of the amino-functional groups with a thermally labile radical initiator, c) contacting the substrate surface with a solution of polymerizable monomers under conditions, where thermally initiated graft copolymerization of the monomers takes place, to form a structure of adjacent functional polymer chains on the surface of the substrate. The present invention further provides a method for the production of a separating material by a) providing a solid substrate, having amino-functional groups coupled to the substrate surface, b) covalently coupling of the amino-functional groups with a thermally labile radical initiator, c) contacting the substrate surface with a solution of polymerizable monomers under conditions, where thermally initiated graft copolymerization of the monomers takes place, to form a structure of adjacent functional polymer chains on the surface of the substrate.
