An Improved Model for Polyether Production from 1,3‐Propanediol

A dynamic mathematical model is developed for production of Cerenol polyether from 1,3‐propanediol in a batch reactor system. The model accounts for polycondensation reactions and side reactions in the liquid phase and for mass transfer of volatile species to the vapor. Parameters are estimated using measured liquid‐phase concentrations of monomer, oligomers, water, and end groups as well as the mass and composition of condensate collected from the overhead condenser system. The proposed model uses novel probability factors to keep the model equations relatively simple while accounting for the complex influence of superacid catalyst on reaction rates. The model is a significant advance over previous Cerenol models because it better accounts for mass‐transfer rates and for the dynamic behavior of the condenser. In addition, the proposed model accounts for the inhibitory influence of water on polycondensation kinetics due to hydration of hydroxyl ends. The model equations and parameter estimates provide a substantial improvement in fit to the data, especially for long reaction times and high catalyst levels, resulting in a 97% reduction in the value of the weighted least squared objective function compared to equations and parameters from a previous model.     

一种考虑聚醚醚酮（PEEK）不同力学状态的本构模型

聚醚醚酮（简称PEEK）以其优良的性能而广泛应用于高端机械、 核工程和航空等科技领域.为了描述其在应变、应变率和温度3种因素作用下的力学行为,依据PEEK在不同温度下呈现的3种力学状态,在著名的JC(Johnson Cook)本构模型的基础上,提出了针对高分子不同力学状态的分段JC本构模型.与传统JC模型及文献中改进JC模型相比,提出的分段JC模型能够更精确地表征PEEK在中高温下的力学行为,为PEEK在复合材料中的应用和分析奠定了理论基础.     

Synthesis and structural characterization of a yttrium coordination polymer formed by bridging of an acyclic polyether

The amide-type acyclic polyether, 1,2-ethylenedioxy-bis(N-pyridin-2-ylmethyl-benzamide) (L) was synthesized and characterized by EA, IR and ¹H NMR spectroscopy. The reaction of yttrium nitrate with L produced a rare chain structural coordination polymer {[Y(NO₃)₃L(H₂O)]?·?(H₂O)} _n (1) by use of the flexible ligand L as the building blocks. The structure of 1 was determined by X-ray crystallography and thermal analysis. In 1, L, as a bidentate bridging spacer, binds two neighboring Y atoms to form a one-dimensional chain polymer. The chain polymer was further connected into the three-dimensional network by hydrogen bonding interactions.     

Complete C-labeling pattern of yessotoxin a marine ladder-frame polyether

Biosynthesis of a marine ladder-frame polyether yessotoxin (YTX) produced by the dinofalgellate Protoceratium reticulatum was investigated. The ¹³C-labeling experiments indicated that the carbons in YTX were derived from acetates, a methyl of methionine and glycolate, and six-membered ring tetrads (rings A-D and H-K) were constructed from repetition of C3 units (m-m-c), which consisted of a methyl of acetate and acetate.     

Glycidyl Tosylate: Polymerization of a “Non‐Polymerizable” Monomer permits Universal Post‐Functionalization of Polyethers

Glycidyl tosylate appears to be a non‐polymerizable epoxide when nucleophilic initiators are used because of the excellent leaving group properties of the tosylate. However, using the monomer‐activated mechanism, this unusual monomer can be copolymerized with ethylene oxide (EO) and propylene oxide (PO), respectively, yielding copolymers with 7–25 % incorporated tosylate‐moieties. The microstructure of the copolymers was investigated via in situ ¹H NMR spectroscopy, and the reactivity ratios of the copolymerizations have been determined. Quantitative nucleophilic substitution of the tosylate‐moiety is demonstrated for several examples. This new structure provides access to a library of functionalized polyethers that cannot be synthesized by conventional oxyanionic polymerization.     

新型的承载双金属氰化物络合催化剂

用双金属氰化物(DMC)络合催化剂可制得相对分子质量高、相对分子质量分布窄和不饱和度低的聚醚多元醇。为提高DMC催化剂的利用率,降低催化剂和聚醚的生产成本,国外开发了承载的DMC催化剂。它不仅可简化聚醚的后处理工艺,而且使聚醚的连续化大规模生产得以实现,因此代表了DMC催化剂的一个重要发展方向。     

4,4＇-二苯氧基二苯砜、4,4＇-二苯氧基二苯酮、对苯二甲酰氯三元共聚物的合成

聚醚酮醚酮酮;4;4＇-二苯氧基二苯砜、4;4＇-二苯氧基二苯酮、对苯二甲酰氯三元共聚物的合成;聚醚砜醚酮酮;低温溶液浓缩聚     

~1H-NMR对部分酯化聚醚端羟基分析及分子量测定

通过测量部分酯化聚醚和全酯化聚醚的酯氢~1H-NMR吸收峰面积的积分比率计算端羟基比例,且用酯氢测定聚醚分子量。     

Aggregation behavior of block polyethers with branched structure at air/water surface

The block polyethers with various branch structure, such as TEPA[(PO)₃₆(EO)₁₀₀]₇, TEPA[(PO)₃₆(EO)₁₀₀(PO)₃₆]₇, and TEPA[(PO)₃₆(EO)₁₀₀(PO)₅₆]₇ were synthesized. Moreover, the aggregation behavior was investigated via the measurements of equilibrium surface tension, dynamic surface tension, and surface dilational viscoelasticity, in order to probe the effect of the block structure on the property of the branched block polyethers. The surface tension results show that the efficiency and effectiveness of the block polyethers to lower surface tension increase with the increase of the PO group numbers. The maximum surface excess concentration (Γ_max) values and the minimum occupied area per molecule at the air/water interface (A_min) values of the branched block polyethers obtained from Gibbs adsorption equations increase and decrease with the increases of the PO group numbers, respectively. The dynamic parameters n and t^* representing the diffusion speed of the polyether molecules from bulky solution to the subsurface and from the subsurface to the air/water surface are obtained according to the equation proposed by Rosen. The results show that the n values firstly increase and then decrease and t^* values decrease with the increase of the polyether concentrations. The results of surface dilational viscoelasticity show that the dilational modulus of TEPA[(PO)₃₆(EO)₁₀₀(PO)₅₆]₇ is the largest among the three block copolymers at the low concentration (<1 mg L⁻¹) but that of TEPA[(PO)₃₆(EO)₁₀₀]₇ is the largest at the high concentration (>1 mg L⁻¹).