- Environmentally benign synthesis of vinyl ester resin from biowaste glycerin
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We present here for the first time a novel environmentally benign protocol for the synthesis of vinyl ester resin (VER). Our synthetic strategy utilizes a commercial waste material, glycerin, from biodiesel manufacturing and converts it into a widely utilized resin. The VER was synthesized using bisphenol A (BPA) and glycidyl methacrylate (GMA) as precursors. GMA was synthesized via a multistep synthetic protocol using glycerin obtained from a biodiesel manufacturing waste stream. The structure of the intermediates was confirmed by 1H NMR, HPLC and FT-IR spectroscopy.
- Shah, Priyank N.,Kim, Namjoon,Huang, Zhuangrong,Jayamanna, Mahesh,Kokil, Akshay,Pine, Alex,Kaltsas, Jarmin,Jahngen, Edwin,Ryan, David K.,Yoon, Seongkyu,Kovar, Robert F.,Lee, Yongwoo
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Read Online
- Life Cycle Assessment for the Organocatalytic Synthesis of Glycerol Carbonate Methacrylate
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Bifunctional ammonium and phosphonium salts have been identified as potential organocatalysts for the synthesis of glycerol carbonate methacrylate (GCMA). Three of these catalysts showed high efficiency and allowed the conversion of glycidyl methacrylate with CO2 to the desired product in >99 % conversion and selectivity. Subsequently, immobilized analogues of selected catalysts were prepared and tested. A phenol-substituted phosphonium salt on a silica support proved to be a promising candidate in recycling experiments. The same catalyst was used in 12 consecutive runs, resulting in GCMA yields of up to 88 %. Furthermore, a life cycle assessment was conducted for the synthesis of GCMA starting from epichlorohydrin (EPH) and methacrylic acid (MAA). For the functional unit of 1 kg GCMA, 15 wt % was attributed to the incorporation of CO2, which led to a reduction of the global warming potential of 3 % for the overall process.
- Büttner, Hendrik,Kohrt, Christina,Wulf, Christoph,Sch?ffner, Benjamin,Groenke, Karsten,Hu, Yuya,Kruse, Daniela,Werner, Thomas
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Read Online
- Sustainable chemo-enzymatic synthesis of glycerol carbonate (meth)acrylate from glycidol and carbon dioxide enabled by ionic liquid technologies
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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
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p. 4191 - 4200
(2021/06/17)
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- (Methyl) acrylic acid ether hydroxyl alkane ester synthesis method
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The invention relates to the field of organic synthesis and discloses an (methyl) acrylic acid ether hydroxyl alkane ester synthesis method. The method includes steps: subjecting methyl acrylic acid and epoxy chloropropane to reaction to generate acrylic ester with an epoxy group; subjecting the epoxy group to positioning and ring opening to enable a hydroxyl at 2-site carbon and a sterically hindered ether bond at a 3 site; subjecting to reaction with a primary alcohol compound to generate a target product. The method has advantages that side reactions in a synthesizing process are less, polymer crystallinity can be changed, mechanical performances such as tensile strength of a polymer are enhanced, and the hydrophilic performance can be changed.
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Paragraph 0027
(2019/08/07)
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- From epoxide to cyclodithiocarbonate Telechelic polycyclooctene through chain-transfer ring-opening metathesis polymerization (ROMP): Precursors to non-isocyanate polyurethanes (NIPUS)
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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.
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- Production method of glycidyl methacrylate
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The invention relates to a production method of glycidyl methacrylate. The method comprises a reaction process and a post-treatment process. The reaction process is characterized in a one-step synthesis method. According to the reaction process, methacrylic acid and sodium carbonate are subjected to a neutralization reaction in excessive epichlorohydrin, such that sodium salt is prepared; without solid-liquid separation, system water content is removed with an azeotropic solvent; under the catalysis effect of a phase transfer catalyst, the glycidyl methacrylate is prepared. The post-treatment process comprises the following steps: a reaction finished liquid is washed; liquid separation is carried out, such that an organic phase is obtained; solvent recovery is carried out with a film evaporation device; and finished product distillation is carried out with a molecular distillation device. With the production method provided by the invention, production process and industrial equipment can be simplified, and operation is convenient. During the post-treatment process, phenomena of poor product polymerization rate and yield caused by high temperature, poor heat transfer effect, low distillation efficiency and the like of a conventional kettle distillation method can be avoided. With the method provided by the invention, product quality and yield can be effectively ensured. The obtained product has a purity higher than 98% and a yield of 85-90%.
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Paragraph 0015; 0016
(2016/11/14)
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- Glycidyl methacrylate or glycidyl acrylate manufacturing method
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The invention relates to a manufacturing method of glycidyl methacrylate or glycidyl acrylate. The invention provides glycidyl (meth)acrylate with low impurity content. The manufacturing method of glycidyl (meth)acrylate comprises a step of reacting epichlorohydrin and (meth)acrylic acid alkali metal salt or (meth)acrylic acid in the presence of catalyst and a step of washing the reaction liquid obtained through the reaction at the temperature ranging from minus 13 DEG C to 20 DEG C.
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Paragraph 0066-0068
(2017/04/07)
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- Manufacturing method of glycidyl methacrylate
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PROBLEM TO BE SOLVED: To provide a method for producing glycidyl methacrylate from an alkali metal salt of methacrylic acid and epichlorohydrin, which method suppresses generation of a polymer to improve productivity.SOLUTION: There is provided a method for producing glycidyl methacrylate from an alkali metal salt of methacrylic acid and epichlorohydrin, wherein the productivity can be improved by suppressing generation of a polymer and preventing the blockage trouble of pipes and the like by maintaining a concentration of a bisphenol-based polymerization inhibitor at 100 ppm or more.
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Paragraph 0039
(2018/02/10)
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- Preparation of glycidyl methacrylate
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PROBLEM TO BE SOLVED: To provide a method for producing glycidyl methacrylate from alkali metal salt of methacrylic acid and epichlorohydrin, in which the deterioration of interfacial properties during removal of the by-produced alkali metal hydrochloride by water washing is prevented.SOLUTION: In a process for obtaining an alkali metal salt of methacrylic acid from methacrylic acid and alkali metal carbonate, an alkali metal carbonate in which water-insoluble matter is removed beforehand, is used. By using an alkali metal carbonate in which water-insoluble matter has been removed, insoluble solids near the interface at the time of water-washing operation for removing the alkali metal hydrochloride which is by-produced during the reaction of alkali metal salt of methacrylic acid and epichlorohydrin to obtain glycidyl methacrylate, no longer occurs and a clear interface can be obtained, and the loss of the oil layer discharged together with the water layer can be suppressed.
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Paragraph 0028-0033
(2020/06/02)
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- PROCESS FOR PRODUCING GLYCIDYL (METH)ACRYLATE
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Provided is glycidyl(meth)acrylate which is reduced in the content of impurities including chlorine. This process comprises reacting epichlorohydrin with an alkali metal (meth)acrylate in the presence of a catalyst to produce glycidyl(meth)acrylate, the process including a step in which the reaction is conducted while making a Bronsted acid present in the reaction system in an amount of 0.0001-0.08 mol per mol of the alkali metal (meth)acrylate.
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Paragraph 0049-0052
(2015/11/18)
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- Improved process for preparing glycerol monomethacrylate
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The present invention refers to glycidyl methacrylate purity by mixing epoxy hydration under acid catalyst using glycerol monoesters by dog annular reaction 950,000 to 4,100,000. method relates to manufacturing. Heteropoly acid or as acid catalyst in of the present invention manufacturing method carried with sulfate ion heterogeneous system of complex metal oxides for selecting and using solid acid catalyst by shortened response time yield high purity and in glycerol monoesters 950,000 to 4,100,000. forming the, all reaction-catalyst was widths method are formed on the same level of wastewater treatment or calcium hydrate the insertion groove. (by machine translation)
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Paragraph 0025; 0026
(2016/12/07)
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- PROCESS FOR PREPARING GLYCIDYL ESTERS
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Process for preparing glycidyl esters, wherein carbonate esters of the formula I are reacted in the presence of a homogeneous catalyst with elimination of carbon dioxide to form glycidyl esters of the formula II where R in the above formulae is an organic radical having from 1 to 20 carbon atoms.
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Page/Page column 4
(2011/04/14)
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- MANUFACTURE OF AN EPOXYETHYL CARBOXYLATE OR GLYCIDYL CARBOXYLATE
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The invention relates to a process for the manufacture of an epoxyethyl carboxylate or glycidyl carboxylate, including reacting a vinyl carboxylate or an allyl carboxylate using an oxidant and a water-soluble manganese complex in an aqueous reaction medium, and the water-soluble manganese complex comprises an oxidation catalyst, characterized in that the water-soluble manganese complex is a mononuclear species of the general formula (I): [LMnX3]Y, or a binuclear species of the general formula (II): [LMn(μ-X)3MnL]Yn, wherein Mn is a manganese; L is a ligand and each L is independently a polydentate ligand, each X is independently a coordinating species and each μ-X is independently a bridging coordinating species, Y is a non-coordinating counter ion, and wherein the epoxidation is carried out at a pH in the range of from 1.0 to 7.0.
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Page/Page column 15-16
(2011/09/14)
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- Method of producing glycidyl methacrylate
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In the production of glycidyl methacrylate from an alkali metal salt of methacrylic acid and epichlorohydrin, at least one water-soluble polymerization inhibitor is added at an appropriate stage of the production. The addition of the water-soluble polymerization inhibitor prevents the formation of insoluble solid matters to increase the efficiency of phase separation in the washing operation for removing a by-produced salt and form a clear interface between the phases, thereby minimizing the recovery loss. In addition, the troubles such as clogging of pipe lines of production apparatus and equipment for waster water treatment can be avoided.
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Page/Page column 2; 3
(2008/06/13)
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- Separating material
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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.
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- Process for the conversion of aldehydes to esters
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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.
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Page/Page column 4
(2010/01/31)
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- Phosphonylated derivatives of aliphatic heterochain and acrylate erpolyms and applications thereof
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A variety of phosphonylated heterochain polymers are disclosed, including, most preferably, phosphonylated polymethyl methacrylate. For each polymeric composition the phosphorous atom of a phosphorous-containing functional group is covalently bonded to a carbon atom of the polymeric chain. The phosphorous atoms are present in an amount of at least about 0.1 percent by weight in each polymeric composition.
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- Radically polymerizable dental material
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The invention relates to a dental material with at least one polymerizable binder and at least one filler containing a redox-initiator system for the radical polymerization, which comprises an initiator and an activator. The material is characterized in that the filler contains a homogeneous mixture of a first part of the filler, which is mixed with the initiator, a second part of the filler, which is mixed with the activator, and a third part of the filler, which does not contain a component of the initiator system. The materials are particularly suitable as cements and filling materials.
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- Process for producing glycidyl ester of acrylic acid or methacrylic acid
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There is disclosed a process for producing a glycidyl ester of acrylic acid or methacrylic acid which comprises the steps of neutralizing acrylic acid or methacrylic acid with a carbonate or a bicarbonate of an alkali metal in an excess amount of epichlorohydrin while an oxygen-containing gas is blown into the liquid reaction system; subjecting water formed by the neutralization and epichlorohydrin to azeotropic distillation to discharge them outside the reaction system and to form an alkali metal salt of acrylic acid or methacrylic acid; adding a quaternary ammonium salt as a catalyst to the reaction system to react the alkali metal salt of the acid with the epichlorohydrin and thus synthesize the glycidyl ester of the acid; cooling the liquid reaction product while recovering part of the excess epichlorohydrin under reduced pressure; adding aqueous solution of an alkali hydroxide to the liquid reaction product to separate into aqueous layer and organic layer; adding a catalyst deactivator to the organic phase; and subsequently distilling the organic layer to separate the glycidyl ester of the acid while blowing an oxygen-containing gas into the organic layer. The above process makes it possible to efficiently produce a highly pure glycidyl ester of acrylic acid or methacrylic acid in high yield with minimized contents of impurities.
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- Process for producing glycidyl acrylate or glycidyl methacrylate
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There are disclosed a process for producing glycidyl acrylate or glycidyl methacrylate by the transesterification of glycidol and methyl methacrylate, etc. which process comprises carrying out the transesterification in the presence of a polymerization inhibitor by using, as a catalyst, a quaternary ammonium salt represented by the general formula (I) or a quaternary phosphonium salt represented by the general formula (II) wherein R1, R2, R3 and R4 are each an alkyl group having 1 to 20 carbon atoms, or the like, and X is a cyanide ion, cyanate ion or the like to complete the reaction; thereafter arresting the reaction by adding a catalyst deactivator represented by the general formula (III) wherein S is a sulfonic acid or a heteropolyacid and B is an alkali metal excluding potassium or an alkaline earth metal; and distilling away unreacted methyl methacrylate, etc. under reduced pressure and two similar modified processes. The processes can produce highly pure glycidyl methacrylate, etc. substantially free from a chlorine component and the processes can enhance the conversion of glycidol without lowering the purity and yield of the objective product.
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- Method of purifying crude glycidyl (meth)acrylate
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A method of purifying a crude glycidyl (meth)acrylate, by (1) subjecting a crude glycidyl (meth)acrylate containing epichlorohydrin and other chlorine compounds as impurities to a stripping treatment with a mixed gas containing oxygen gas in the presence of a quaternary ammonium salt, and then (2) distilling the treated product to obtain a purified glycidyl (meth)acrylate.
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- Synthesis of epoxy (meth)acrylic esters by selective epoxidation of unsaturated (meth)acrylic esters using the system H2O2-Na2WO4 under phase transfer catalysis
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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
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p. 5099 - 5110
(2007/10/02)
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- A Convenient Synthesis of Glycidyl Esters (2,3-Epoxypropyl Alkanoates)
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A novel method for synthesizing glycidyl esters (2,3-epoxypropyl alkanoates) 1 has been achieved by the sequence of the organotin phosphate catalyzed reaction of epichlorohydrin 2 with carboxylic acids and dehydrochlorination of the resulting mixture of ester chlorohydrins 3 + 4 followed by separation.
- Otera, Junzo,Matsuzaki, Shinjiro
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p. 1019 - 1020
(2007/10/02)
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- Method for producing glycidyl (metha)acrylate
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Glycidyl methacrylate or glycidyl acrylate is produced by reacting methyl methacrylate or methyl acrylate with glycide in the presence of a metal salt of a fatty acid.
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- Process for the production of glycidyl methacrylate
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Glycidyl methacrylate is produced by transesterifying methyl methacrylate with glycidol in the presence of a polymerization inhibitor and a transesterification catalyst in which the catalyst is a salt of formula MeX where Me is an alkali metal ion and X is a cyanide, cyanate or thiocyanate ion.
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- Hydroxylapatite ceramic
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A novel ceramic form of hydroxylapatite and a novel ceramic product comprising a mixture of the latter and whitlockite, the preparation of these ceramics and dental restorative compositions and dental and surgical prosthetic materials containing the same are disclosed. Also described is a novel and improved process for producing polycrystalline ceramic oxides.
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