- From epoxide to cyclodithiocarbonate Telechelic polycyclooctene through chain-transfer ring-opening metathesis polymerization (ROMP): Precursors to non-isocyanate polyurethanes (NIPUS)
-
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.
- Vanbiervliet, Elise,Fouquay, Stéphane,Michaud, Guillaume,Simon, Frédéric,Carpentier, Jean-Fran?ois,Guillaume, Sophie M.
-
-
Read Online
- Hydrosilylation of allyl glycidyl ether with triethoxysilane
-
Hydrosilylation of allyl glycidyl ether with triethoxysilane in presence of Speier's catalyst leads to triethoxy(3-glycidoxypropyl)silane and triethoxy(2-glycidoxy-1-methylethyl)silane and is accompanied by isomerization of allyl glycidyl ether and cleavage of the oxirane ring and the ether bond. An effect of admixtures in allyl glycidyl ether on the process is revealed. Some other hydrosilylation catalysts and additives to Speier's catalyst are studied.
- Chernyshev,Belyakova,Knyazeva,Khromykh
-
-
Read Online
- Sustainable chemo-enzymatic synthesis of glycerol carbonate (meth)acrylate from glycidol and carbon dioxide enabled by ionic liquid technologies
-
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.
- Donaire, Antonio,Garcia-Verdugo, Eduardo,Lozano, Pedro,Luis, Santiago V.,Nieto, Susana,Porcar, Raul,Villa, Rocio
-
p. 4191 - 4200
(2021/06/17)
-
- (Meth) acrylate having glucoskeleton methylfluorene
-
PROBLEM TO BE SOLVED: To provide (meth)acrylate having a fluorene skeleton that has high refractive index and high heat resistance and reduces the stress of a cured product. SOLUTION: This (meth)acrylate having the fluorene skeleton is represented by formula (1). In formula (1), ring Z is a benzene ring or a condensed polycyclic aromatic hydrocarbon ring, R1is a halogen atom, alkyl group, or cyano group, R2is an alkylene group, R3is a hydrogen atom or a methyl group, R4is a hydrocarbon group, k is an integer of 0 to 4, m is 0 or an integer of 1 or larger, n is 0 or an integer of 1 or larger, and p is an integer of 1 or larger. Here, when ring Z is a benzene ring, n is an integer of 1 or larger, and at least one R4is an aryl group. COPYRIGHT: (C)2013,JPOandINPIT
- -
-
Paragraph 0064; 0065
(2016/12/12)
-
- Separating material
-
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.
- -
-
-
- Process for the conversion of aldehydes to esters
-
A process for the conversion of aldehydes to esters, specifically acrolein or methacrolein to methyl acrylate or methyl methacrylate, respectively. Essentially in the absence of water, an aldehyde is contacted with an oxidizing agent to form an intermediate and then the intermediate is contacted with a diol or an alcohol to form an ester or diester. Preferably, the oxidizing agent is also a chlorinating agent. Specifically, acrolein or methacrolein is contacted with an oxidizing/chlorinating agent, such as t-butyl hypochlorite, and the chlorinated compound is contacted with an alcohol, such as methanol, to form methyl acrylate or methyl methacrylate, respectively. Generally, the order of addition is for the oxidizing agent to be added to the aldehyde, specifically for t-butyl hypochlorite to be added to acrolein or methacrolein, and for the diol or alcohol to be added to the intermediate, specifically for the methanol to be added to the reaction product of acrolein or methacrolein and t-butyl hypochlorite. The process of the present invention can be carried out in the absence or in the presence of solvent. Generally, better methyl acrylate or methyl methacrylate yields are obtained at lower reaction temperatures.
- -
-
Page/Page column 3-4
(2010/01/31)
-
- Synthesis of epoxy (meth)acrylic esters by selective epoxidation of unsaturated (meth)acrylic esters using the system H2O2-Na2WO4 under phase transfer catalysis
-
Selective epoxidation of unsaturated (meth)acrylic esters by various classical epoxidizing agents was investigated. It is shown that high selectivity and good yields are obtained by using the system H2O2 (20%) - Na2WO4 under phase transfer catalysis. Under these conditions, the rigorous control of the temperature and of the initial pH allows to prevent polymerization during these selective epoxidations. It is shown that the selectivity of the epoxidation depends upon the difference of nucleophilicity of the two double bonds.
- Fort,Olszewski-Ortar,Caubere
-
p. 5099 - 5110
(2007/10/02)
-