- Preparation supported heteropoly (acid)/polyaniline catalysts and catalytic synthesis of tributyl citrate
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A series of polyaniline supported heteropoly acids were prepared through a simple method at room temperature. The obtained heterogeneous catalysts were comprehensively characterized by powder FTIR spectroscopy, UV-vis spectra, NH3 temperature programmed desorption (TPD) and scanning electron microscopy (SEM). The influence of various process parameters such as heteropoly loading (10 to 25 wt%), catalyst amount (3-5%), molar ratio of n-butanol to citric acid (3 to 5), and reaction time (3.5-12 h) have been investigated over heteropoly/polyaniline catalysts with the aim to maximize citric acid conversion and tributyl citrate selectivity. The different catalytic tests has shown that the catalyst exhibits high conversion and selectivity by using the as-prepared heteropoly/polyaniline catalysts for esterification under appropriate conditions. The present method of using 20% heteropoly/polyaniline catalyst for the synthesis of tributyl citrate would be environmentally benign in the reusability of catalyst.
- Wang, Limin,Ding, Bin,Zhang, Miao
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Read Online
- CITRATE-BASED PLASTICIZER COMPOSITION AND RESIN COMPOSITION COMPRISING SAME
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The present invention relates to a plasticizer composition, including a lower alkyl-based citrate and a higher alkyl-based citrate at the same time, as citrate, wherein the ratio of a hybrid type to a non-hybrid type and the ratio of the lower alkyl groups to the higher alkyl groups are controlled so that effects are achieved. When applying the plasticizer composition to a resin, stress resistance and mechanical properties can be maintained at an equal or higher level, the migration and volatile loss properties and the plasticization efficiency can be balanced, and the light resistance and heat resistance can be remarkably improved.
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Paragraph 0106; 0117-0119
(2021/10/20)
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- PLASTICIZER COMPOSITION AND RESIN COMPOSITION INCLUDING THE SAME
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Provided is a plasticizer composition including: a cyclohexane-1,2-diester-based substance of the following Chemical Formula 1; and a citrate-based substance of the following Chemical Formula 2: wherein in Chemical Formula 1 and Chemical Formula 2: R1 and R2 each independently are a C8 to C10 alkyl group; and R3 to R5 each independently are a C5 to C10 alkyl group.
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Paragraph 0119-0120; 0122
(2021/07/31)
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- Novel cyclohexylimide ionic liquid and method for catalyzing synthesis of butyl citrate and bisphenol F
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The invention provides a novel cyclohexylimide ionic liquid and a method for catalyzing synthesis of butyl citrate and bisphenol F, and can solve the technical problem that the reaction yield needs tobe further improved when the traditional cyclohexylimide ionic liquid catalyzes synthesis of butyl citrate and bisphenol F. The novel cyclohexylimide ionic liquid is characterized by being prepared by the following method: S1, mixing and dissolving 1, 3-propane sultone and toluene, cooling the solution, adding Mn (OAc) 2 and reduced hexylimide, heating to 65 DEG C, and reacting for 12 hours; s2,filtering the reaction solution obtained in the step S1 to obtain a white precipitate, rinsing, and drying to obtain a white intermediate; s3, dissolving the intermediate in water, stirring, dropwiseadding concentrated sulfuric acid, heating to 80 DEG C, and reacting for 16 hours to obtain yellow transparent liquid, and S4, removing water from the transparent liquid by rotary evaporation, rinsing, washing and drying to obtain the novel cyclohexylimide ionic liquid.
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Paragraph 0008; 0013-0019
(2021/03/31)
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- Citrate plasticizer
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The invention discloses a citrate plasticizer and a preparation method thereof, and the preparation method of citrate comprises the following steps: firstly, citric acid and alcohol react to prepare citric acid triester, and then dianhydride acylation is carried out to prepare carboxyl-containing citric acid triester. After chlorination, the carboxyl-containing citric acid triester and the tris(2-ethoxyl) isocyanurate are subjected to esterification reaction to prepare triester citrate containing the isocyanurate. According to the present invention, the preparation method has characteristics of simple operation, wide raw material source and mild reaction condition, and meets the industrial production, the prepared triester citrate containing isocyanurate has a good plasticizing effect and excellent thermal stability, low-temperature flexibility, solvent extraction resistance, migration resistance and flame retardance, and can be widely applied to plastic rubber plasticizers.
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Paragraph 0027-0029
(2021/05/15)
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- Citrate plasticizer and preparation method thereof
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The invention discloses a citrate plasticizer and a preparation method thereof. The preparation method comprises the following steps: firstly, carrying out reaction on citric acid and alcohol to prepare citric acid triester; acylating dianhydride to prepare carboxyl-containing triester citrate; carrying out acylating chlorination on the carboxyl-containing triester citrate, and then carrying out esterification reaction on the carboxyl-containing triester citrate and tri(2-hydroxyethyl) isocyanurate to prepare triester citrate containing isocyanurate; and finally, esterifying with fatty acyl chloride to obtain the modified citrate plasticizer. The preparation method is simple to operate, wide in raw material source and mild in reaction condition, and meets industrial production. The prepared triester citrate containing isocyanurate has a good plasticizing effect and excellent thermal stability, low-temperature flexibility, solvent extraction resistance, migration resistance and flame retardance, and can be widely applied to plastic rubber plasticizers.
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Paragraph 0029; 0030
(2021/05/29)
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- Method for catalytically synthesizing tributyl citrate
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The invention discloses a method for catalytic synthesis of tributyl citrate. According to the method, citric acid monohydrate and butanol are used as raw materials and reaction is carried out for 6-7hours under the condition of acid catalysis to obtain tributyl citrate. Citric acid and n-butyl alcohol are used as initial raw materials, sulfonic acid resin is used as a catalyst, catalytic efficiency is high, operation is easy, reaction conditions are mild, product selectivity and yield are high, and the method has wide industrial application prospects.
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Paragraph 0009; 0021-0026
(2020/01/14)
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- Robust acidic pseudo-ionic liquid catalyst with self-separation ability for esterification and acetalization
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The novel acidic pseudo-ionic liquid catalyst with self-separation ability has been synthesized through the quaternization of triphenylphosphine and the acidification with silicotungstic acid. The pseudo-IL showed high activities for the esterification with average conversions over 90%. The pseudo-IL showed even higher activities for acetalization than traditional sulfuric acid. The homogeneous catalytic process benefited the mass transfer efficiency. The pseudo-IL separated from the reaction mixture automatically after reactions, which was superior to other IL catalysts. The high catalytic activities, easy reusability and high stability were the key properties of the novel catalyst, which hold great potential for green chemical processes.
- Shi, Yingxia,Liang, Xuezheng
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p. 1413 - 1421
(2019/05/04)
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- Micro-flow nanocatalysis: synergic effect of TfOH@SPIONs and micro-flow technology as an efficient and robust catalytic system for the synthesis of plasticizers
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The combination of continuous flow technology with immobilizing of only 0.13?mol% of triflic acid (TfOH) on silica-encapsulated superparamagnetic iron oxide nanoparticles (SPIONs) under solvent-free conditions successfully provided a powerful, efficient, and eco-friendly route for the synthesis of plasticizers. The turnover frequency value in micro-flow conditions varied in the range of 948.7 to 7384.6 h?1 compared to 403.8 to 3099 h?1 for in-flask. This technique works efficiently, encouraging future applications of micro-flow nano-catalysis in green chemistry.
- Tashi, Maryam,Shafiee, Behnaz,Sakamaki, Yoshie,Hu, Ji-Yun,Heidrick, Zachary,Khosropour, Ahmad R.,Beyzavi, M. Hassan
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p. 37835 - 37840
(2018/11/26)
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- Synthetic method for auxiliary for 3D printing flexible material
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The invention designs a synthetic method for a tribenzyl citrate auxiliary for a 3D printing flexible material. The preparing method includes the steps that monohydric alcohol, benzyl alcohol and citric acid are used as main raw materials, a catalyst and a water carrying agent are used, and the product tribenzyl citrate is prepared through two steps of reaction including acid alcohol esterification and ester exchange, neutralizing, washing, reduced pressure distillation and purification. the product is the auxiliary for the 3D printing flexible material.
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Paragraph 0017; 0018
(2017/02/17)
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- AN AUTO-CATALYZED PROCESS FOR THE SYNTHESIS OF TRIBUTYL CITRATE (TBC)
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The present invention discloses a novel eco-friendly, cost effective, autocatalytic process for the synthesis of tributyl citrate (TBC) with high yields and purity. The process comprises the steps of a) adding citric acid solution in butanol to reactor followed by heating at temperature in the range of 100°C to 150°C; b) removing the sample of step (a) from reactor as initial sample and collecting the vapours of butanol and water in a separator via condenser; and c) recycling the upper layer of butanol of step (b) to column followed by removal of water periodically to afford tributyl citrate having purity in the range of 95 to 99.9%.
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Page/Page column 9
(2017/08/04)
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- Synthetic method of tributyl citrate
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The invention discloses a synthetic method of tributyl citrate. Sodium citrate, n-Butyl chloride and potassium iodide are heated to 30 to 75 DEG C to react for 3 to 5 hours in the solvent of N, N-dimethylacetamide to obtain a crude product tributyl citrate. The crude product is washed by water, decompressed, distilled and dried to obtain the tributyl citrate.
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Paragraph 0017
(2016/10/20)
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- A method of synthesizing tributyl citrate
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The invention discloses a method for synthesizing tributyl citrate. The method comprises the following steps: I, preparing a choline chloride acidic ionic liquid; II, performing esterification reaction; III, filtering the reaction system after reaction, thereby obtaining solid choline chloride and a liquid phase product; and IV, performing atmospheric distillation on the liquid phase product, washing residues generated after atmospheric distillation by using an alkali solution, adding activated carbon to decolor, filtering to remove the activated carbon, performing reduced pressure distillation on residues generated after filtration, and collecting fraction of 197-200 DEG C, thereby obtaining tributyl citrate. According to the method, choline chloride and citric acid are adopted to synthesize the acidic ionic liquid, the synthesized acidic ionic liquid is both a raw material and a catalyst, the acidic ionic liquid has esterification reaction with n-butyl alcohol to synthesize n-butyl alcohol, the efficiency of the esterification reaction is improved, the conversion rate can be greater than 90%, the choline chloride after esterification can be recycled and utilized, and the cost is low.
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Paragraph 0044-0048; 0052
(2017/04/07)
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- A composite solid acid for catalytic synthesis of acetyl tributyl citrate process
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A technology for synthesizing ATBC (acetyl tributyl citrate) under catalysis of composite solid acid comprises steps as follows: citri acid anhydrous and n-butyl alcohol are added to a reactor, a catalyst is added, the mixture reacts for 3-6 hours at the temperature of 120 DEG C-160 DEG C, and TBC (tributyl citrate) is synthesized and dealcoholized; acetic anhydride is added to dealcoholized TBC and reacts for 1-2 hours at the temperature of 60 DEG C-100 DEG C, the catalyst is obtained through filtering after a reaction liquid is cooled, water is added to filtrate, acetic anhydride is hydrolyzed, acetic acid is recovered through deacidification, and an ATBC finished product is prepared through aftertreatment. Defects of a complicated technology, long production period, high product loss, numerous three wastes, environmental pollution and the like of an existing preparation method of ATBC are overcome; the catalyst is simple to prepare and easy to separate and recover and can be recycled without treatment.
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Paragraph 0027; 0028
(2017/01/02)
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- Plasticizer tributyl citrate production process
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The present invention discloses a plasticizer tributyl citrate production process, which comprises: (1) mixing citric acid monohydrate and n-butanol, adding p-toluenesulfonic acid and active carbon, introducing nitrogen gas, and carrying out an esterification reaction to obtain an esterified product; (2) carrying out dealcoholization on the esterified product to achieve a flash point of more than or equal to 162 DEG C; (3) dissolving and recovering the p-toluenesulfonic acid in the esterified product after the dealcoholization with water, and adding the separated water phase to the next batch production step (1) so as to be applied; (4) adding an alkali liquid to the oil phase, neutralizing, removing the water phase, and carrying out water washing on the oil phase to achieve a neutral state; (5) adding active carbon to the esterified product being subjected to the water washing, and carrying out dealcoholization again to achieve a flash point of more than or equal to 180 DEG C so as to obtain a crude ester; and (6) filtering the crude ester to obtain the industrial product tributyl citrate. According to the present invention, the conversion rate of the esterification reaction is up to 99.0%, the tributyl citrate yield can achieve more than or equal to 98%, and the unit consumption and the cost are reduced; and the catalyst has the good p-toluenesulfonic acid catalysis effect, the recovery rate after the completion of the esterification achieves more than or equal to 75%, the catalyst can be reused, the sewage emission can be reduced, and the COD and the BOD in the wastewater can be reduced.
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Paragraph 0010
(2017/06/20)
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- The carbon material functionalized with NH2+ and SO3H groups catalyzed esterification with high activity and selectivity
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A novel carbon-based solid acid was conveniently prepared by heating a mixture of d-glucose, p-toluenesulfonic acid and diphenylammonium tosylate. Its structure was measured by XRD, FT-IR, XPS, 13C MAS NMR and EA to illustrate that the carbon material has been functionalized with NH2+ and SO3H groups and has a strong "hydrophobic effect". It can be used to catalyze the esterification reaction of carboxylic acids with equimolar amounts of sterically demanding and acid-sensitive alcohols with high reactivity (yield up to 90%) and selectivity (up to 95%) in heptane at 80 °C. It could be easily recovered and reused more than ten times without loss of activity.
- Zhan, Shaoqi,Tao, Xiaochun,Cai, Liangzhen,Liu, Xiaohui,Liu, Taoping
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supporting information
p. 4649 - 4653
(2015/02/19)
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- Sulfonated graphene as highly efficient and reusable acid carbocatalyst for the synthesis of ester plasticizers
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Plasticizers are well known for their effectiveness in producing flexible plastics. The automotive, plastic and pharmaceutical industries, essential to a healthy economy, rely heavily on plasticizers to produce everything from construction materials to medical devices, cosmetics, children toys, food wraps, adhesives, paints, and 'wonder drugs'. Although H2SO4 is commonly used as commodity catalyst for plasticizer synthesis it is energy-inefficient, non-recyclable, and requires tedious separation from the homogeneous reaction mixture resulting in abundant non-recyclable acid waste. In this study, for the first time, we report an efficient synthesis of ester plasticizers (>90% yields) using sulfonated graphene (GSO3H) as an energy-efficient, water tolerant, reusable and highly active solid acid carbocatalyst. The hydrothermal sulfonation of reduced graphene oxide with fuming H2SO4 at 120°C for 3 days afforded GSO3H with remarkable acid activity as demonstrated by 31P magic-angle spinning (MAS) NMR spectroscopy. The superior catalytic performance of GSO3H over traditional homogeneous acids, Amberlyst-15, and acidic ionic liquids has been attributed to the presence of highly acidic and stable sulfonic acid groups within the two dimensional graphene domain, which synergistically work for high mass transfer in the reaction. Furthermore, the preliminary experimental results indicate that GSO3H is quite effective as a catalyst in the esterification of oleic and salicylic acid and thus may pave the way for its broad industrial applications in the near future.
- Garg, Bhaskar,Bisht, Tanuja,Ling, Yong-Chien
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p. 57297 - 57307
(2015/02/02)
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- COMPOSITIONS CONTAINING TETRAHYDROFURFURYL AND/OR ALKYL-SUBSTITUTED TETRAHYDROFURFURYL ESTERS OF CITRIC ACID
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Compositions containing tetrahydrofurfuryl and/or alkyl-substituted tetrahydrofurfuryl esters of citric acid are provided. These esters of citric acid can be formed from renewable materials and can be used, for example, as plasticizers for various polymeric materials. The tetrahydrofurfuryl and/or alkyl-substituted tetrahydrofurfuryl esters of citric acid typically have a low odor, have good compatibility with a variety of polymeric materials, and can be used at temperatures often encountered during hot melt processing of polymeric materials.
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Page/Page column 19-21
(2013/10/21)
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- Reductive coupling of aldehydes by H2S in aqueous solutions, a C-C bond forming reaction of prebiotic interest
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We report here a novel reductive coupling reaction of conjugated, non- or poorly enolizable aldehydes induced by H2S and operative in aqueous solutions under prebiotically relevant conditions. This reaction leads from retinal to β-carotene, and from benzylic aldehydes to the corresponding diarylethylenes. This novel reaction also opens a new potentially prebiotic pathway leading from glyoxylic acid to various compounds that are involved in the reductive tricarboxylic acid cycle. This C-C bond forming reaction of prebiotic interest might have been operative, notably, in the sulfide-rich environments of hydrothermal vents, which have been postulated as possible sites for the first steps of organic chemical evolution.
- Kajjout, Mohammed,Hebting, Yanek,Albrecht, Pierre,Adam, Pierre
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experimental part
p. 714 - 726
(2012/07/14)
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- A novel Bronsted acidic heteropolyanion-based polymeric hybrid catalyst for esterification
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A new SO3H-functionalized HPA-based acidic polymeric hybrid was prepared by coupling task-specifically designed SO3H-functionalized polymeric ionic liquid with Keggin-structured heteropolyanion, and characterized by 1H NMR, FT-IR, TG, XRD, BET, Hammett indicator, melting point, and elemental analysis. Its catalytic performance for esterification of alcohols with carboxylic acids was studied under solvent-free conditions. The results demonstrate that the polymeric hybrid is a highly active and selective solid catalyst for various esterifications, and can be easily recovered and steadily reused.
- Leng, Yan,Jiang, Pingping,Wang, Jun
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experimental part
p. 41 - 44
(2012/10/07)
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- Short communication: Synthesis of tributyl citrate using SO 42-/Zr-MCM-41 as catalyst
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Zirconium-containing mesoporous molecular sieve SO4 2-/Zr-MCM-41 was synthesized for catalyst in synthesis of tributyl citrate. The structure was characterized by XRD, N2 Ad/De isotherms and FT-IR. The results indicated that the solid acids show good catalytic performance and are reusable. Under optimum conditions and using SO 42-/Zr-MCM-41 as catalyst, the conversion of citric acid was 95%. After easy separation of the products from the solid acid catalyst, it could be reused three times and gave a conversion of citric acid not less than 92%. The structure of tributyl citrate was characterized by FT-IR and 1H-NMR.
- Zheng, Zhifeng,Xu, Junming,Jiang, Jianchun,Lu, Yanju,Huang, Yuanbo
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experimental part
p. 147 - 150
(2012/05/20)
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- Heteropolyanion-based ionic liquids: Reaction-induced self-separation catalysts for esterification
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(Figure Presented) It comes out in the wash: In the esterification of citric acid with n-butanol, heteropolyanion-based ionic liquid (IL) catalysts show high catalytic activity, self-separation, and easy reuse. The good solubility in reactants, nonmiscibility with ester product, and high melting point of the IL catalysts enable the reaction-induced switching from homogeneous (b in the picture) to heterogeneous (c) with subsequent precipitation of the catalyst (d).
- Leng, Yan,Wang, Jun,Zhu, Dunru,Ren, Xiaoqian,Ge, Hanqing,Shen, Lei
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experimental part
p. 168 - 171
(2009/04/18)
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- Process for reactive esterification distillation
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A process for producing organic acid di- or tri-esters, particularly citric acid tri-esters, with the available acid groups esterified using countercurrent reactive distillation using acid catalysts in a structured packing is described. In the reactive distillation an organic acid di- or triester is formed by chemical reaction and purified to its final state within the single column. Organic acid di- or tri-esters are produced at relatively low cost, with less waste production in by-products of the reaction, and in a less complicated manner than prior processes. Organic acid di- and tri-esters have uses as solvents, as plasticizers and in conversion products.
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Page/Page column 21-22
(2008/06/13)
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- Bulky diarylammonium arenesulfonates as mild and extremely active dehydrative ester condensation catalysts
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More environmentally benign alternatives to current chemical processes, especially large-scale, fundamental reactions like ester condensations, are highly desirable for many reactions. Bulky diarylammonium pentafluorobenzenesulfonates and tosylates serve as extremely active dehydration catalysts for the ester condensation reaction of carboxylic acids with equimolar amounts of sterically demanding alcohols and acid-sensitive alcohols. Typically, the esterification reaction is performed in heptane by heating at 80°C in the presence of 1 mol% of the catalyst without removing water. Esterification with primary alcohols proceeds without solvents even at room temperature. Furthermore, 4-(N-mesitylamino)polystyrene resin-bound pentafluorobenzenesulfonate can be recycled more than 10 times without a loss of activity.
- Sakakura, Akira,Nakagawa, Shoko,Ishihara, Kazuaki
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p. 422 - 433
(2007/10/03)
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- ESTER COMPOUND, PLASTICIZER FOR BIODEGRADABLE ALIPHATIC POLYESTER RESIN, AND BIODEGRADABLE RESIN COMPOSITION
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An ester compound represented by formula (1)R1OOC―(CH2)m―COOR2???( 1 ) wherein R1 and R2 are different from each other and each represents a group of formula (2)―(R3O)nR4???( 2 ) wherein R3 is a C1-6 alkylene group; R4 is a C1-10 straight- or branched-chain alkyl group, a C6-12 aryl group, C7-15 arylalkyl group or a C7-15 alkylaryl group; m is an integer from 0 to 8, and n is an integer from 0 to 6. This compound is suitable as a plasticizer for biodegradable aliphatic polyester resins.
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- Hair growth composition containing citric acid esters
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Triesters of citric acid are used for inducing, maintaining or increasing hair growth. Compositions for topical application to mammalian hair or scalp comprise an effective amount of from 1% to 99% by weight of an ester of citric acid having the structure (1): where, R1, R2 and R3 each independently represent a branched or unbranched alkyl, alkenyl, aryl, alkylaryl or arylalkyl group, each said group having from 1 to 18 carbon atoms, R4 represents -H, or a branched or unbranched saturated or unsaturated acyl, alkyl, aryl, alkylaryl or aylalkyl group having from 1 to 18 carbon atoms, in the presence of a cosmetically acceptable vehicle for the citric acid ester and in the absence of solid absorbent for the ester;, said effective amount of said ester being sufficient to increase hair growth in the rat, when said composition is applied topically thereto over a period of no more than three months, by at least 10% more than that obtainable using a control composition from which the said ester has been omitted, in accordance with the Rat Hair Growth Test.
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