Studies on the thermotropic liquid crystalline polymer. XII. Synthesis and properties of crosslinkable thermotropic liquid crystalline homo- and copoly(ether-ester)s

A series of crosslinkable thermotropic liquid crystalline poly(ether-ester)s and copoly(ether-ester)s was prepared. All of the polymers were crosslinked by thermal treatment or photo-irradiation upon heating. The thermal stability and thermal crosslinking reaction of these polymers were investigated. These polymers also could be crosslinked by copolymerization with vinyl monomers, such as styrene or methyl methacrylate. The crosslinked polymers exhibited thermotropic liquid crystalline behavior after softening by heating. The phase behavior of linear polymers and crosslinked polymers was studied by differential scanning calorimetry (DSC) and an optical polarizing microscope equipped with a heating stage. © 1995 John Wiley & Sons, Inc.     

Enthalpic determinations of aliphatic ester-solvent systems with correlations

Calorimetric measurements were carried out on ester-solvent systems where the esters were H(CH₂)_xCOO(CH₂)_yH, with x and y varying from 1 to 5, and the solvents were n-hexane and 1,2-dichloroethane. Calculation of the enthalpies of cavity formation enabled the enthalpies of interaction to be determined. Both enthalpies correlated with number of carbon atoms N, equal to x+y in the esters, giving for 1,2-dichloroethane

磷酰氨基酸的酯交换反应研究

本文利用^3^1P NMR , 对比研究了磷酰化组氨酸与其它磷酰化氨基酸和一级醇的磷上酯交换的反应速度,实验表明磷酰化组氨酸的反应速度最快. 由此提出了以下机理:由于咪唑环的参与,磷可以形成六配位过渡态,从而加快了反应速度.     

Preparation and characterization of octadecyl acrylate monoliths for capillary electrochromatography by photochemical,thermal, and chemical initiation†

Monolithic stationary phases based on octadecyl acrylate for CEC using different initiating systems (UV irradiation, thermal, and chemical initiation) in the presence of lauroyl peroxide as initiator were synthesized. For each initiation mode, the influence of the porogenic solvent composition on both the morphological and electrochromatographic properties of the resulting monoliths was investigated. Under optimal conditions, excellent efficiencies for the photochemically and chemically polymerized monoliths (minimum plate heights of 6.9–10.7 and 6.5–12.6 μm, respectively) were achieved. Thermally initiated columns gave lower efficiency values, permeabilities, and longer analysis times compared to these initiating systems. The produced monolithic stationary phases were evaluated in terms of reproducibility and gave RSD values below 9.2, 10.6, and 9.8% for UV, thermally, and chemically initiated columns, respectively.     

Thiol‐ene photopolymerization for efficient curing of vinyl esters

Monomers for radical photopolymerization based on vinyl esters (VEs) have recently been identified as suitable alternatives to (meth)acrylates on account of their low irritancy and cytotoxicity. The drawback of most VEs with abstractable hydrogens is their relatively low reactivity compared with (meth)acrylates. Within this article, we proved by photo‐differential scanning calorimetry measurements and real‐time Fourier transform infrared spectroscopy that the thiol‐ene concept is able to improve the photoreactivity of these VEs to a large extent to a level between those of acrylates and methacrylates. Other VEs have now a reactivity of at least the level of similar acrylates. Mechanical properties as determined by Dynamic Mechanical Analysis and Charpy impact tests showed significant toughening of these materials. Furthermore, we were able to confirm low toxicity of all components by osteoblast cell culture experiments. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis of Derivatives of Chlorin P6 Trimethyl Ester

The Vilsmeier reaction of nickel(II) chlorin P₆ trimethyl ester with 3-dimethyl-aminoacrolein yielded nickel(II) chlorin P₆ 20-(2-formylvinyl) trimethyl ester and nickel(II) chlorin P₆ 3-(1-hydroxyethyl)-3-devinyl-20-(2-formylvinyl) trimethyl ester. Also, the outgrowths of nickel(II) chlorin P₆ 20-(2-formyl) trimethyl ester and nickel(II) chlorin P₆ 3-(2-formylvinyl)-3-devinyl-20-(2-formyl) trimethyl ester were obtained by Vilsmeier reaction with dimethylformamide. By treating the derivatives of nickel(II) 20-(2-formyl)-chlorin and nickel(II) 3-(2-formylvinyl)-20-(2-formyl)-chlorin with trifluoracetic acid, the removal of the central nickel(II) ion was accomplished. The derivatives of 20-(2-formyl)-chlorin and 3-(2-formylvinyl)-20-(2-formyl)-chlorin demonstrated considerable bathochromic shift of the major absorption band in the red region of the optical spectrum.     

Oxidation of Poly(dimethylbutadiene) Popcorn Polymer

Poly(dimethylbutadiene) popcorn polymer oxidizes readily in the presence of oxygen at room temperature. Quantitative data are presented for the production of the major volatile product, 2,5-hexanedione, as well as for the secondary products: water, acetic acid, and acetaldehyde. Three reaction mechanisms formerly proposed for polyisoprene oxidation are considered for their applicability to poly(dimethylbutadiene) popcorn oxidation. Of these, one that assumes the formation of a Bevilacquatype peroxyalkoxy radical followed by hydrogen abstraction to form an alcohol group, double bond migration, formation of a peroxide radical adjacent to the alcohol, then elimination of a hydroxy radical and scission, can explain the experimental data.     

Cl3CCONH2/PPh3: A Versatile Reagent for Synthesis of Esters

Cl₃CCONH₂/PPh₃ was a versatile reagent to convert carboxylic acids into their corresponding acid chlorides. This intermediate was clearly confirmed by spectroscopic methods (IR, ¹H, ¹³C NMR). This one-pot reaction of in situ acid chloride generated with various alcohols successfully furnished the corresponding esters in moderate to excellent yields.     

Green Enzymatic Synthesis of L-Ascorbyl Fatty Acid Ester: An Antioxidant

In green chemistry, biocatalysis using microwaves is a very attractive tool for various regioselective syntheses. L-Ascorbyl fatty acid esters were synthesized by an immobilized lipase from Bulkholderia multivorans using microwaves, with a dynamically enhanced rate of reaction and appreciable yield of around 80%. Microwave radiation had no effect on enzymic inactivation, however, synergism between microwaves and biocatalyst was observed.     

酶促水解法拆分布洛芬乙酯的工艺研究

以布洛芬乙酯为反应底物,探索了酶促水解法拆分布洛芬的工艺。以曲拉通X-100为表面活性剂,利用南极假丝酵母脂肪酶B（CAL-B）催化拆分外消旋布洛芬乙酯,并对表面活性剂含量、有机溶剂种类和添加量、酶量、缓冲溶液pH、温度及时间等反应条件进行了优化;得到的最佳反应条件为：在pH为9.0的缓冲溶液中,添加80 mg曲拉通X-100、50 μL二氯甲烷和15 mg CAL-B,于30℃下反应48 h;在该条件下,S-布洛芬乙酯的剩余率（C）为65%,布洛芬乙酯的对映体过量值（ees）为94%。