Short-range order in some polymer melts from X-ray diffraction

Wide-angle X-ray diffraction measurements were performed on polymer melts of isotactic and syndiotactic polypropylene (IPP and SPP), poly(ethylenepropylene) (PEP), polystyrene (PS), polyisobutylene (PIB), and polyethylene (PE), to study the dependence of the short-range structure of polymer liquids on chain architecture. Total structure functions, which comprise intra- and intermolecular contributions, were derived from the scattering data. The trivial Fourier components of the intramolecular structure (C(SINGLE BOND)>C ≃ 1.54 Å and C(SINGLE BOND)C(SINGLE BOND)C ≃ 2.55 Å) were subtracted from the total structure functions. The remaining functions contain only those intramolecular contributions dependent on the chain's conformational degrees of freedom, plus the intramolecular contributions. The structural differences between the polymers in momentum space are discerned only when the trivial components are subtracted. This subtraction also reduces the effects of truncation errors on Fourier transformation to real space. The short-range structure of PIB appears very different compared to all the others, which correlates with anomalies in a number of physical properties for this polymer. © 1996 John Wiley & Sons, Inc.     

The nonlinear strain measure of polyisobutylene melt in general biaxial flow and its comparison to the Doi-Edwards model

The nonlinear strain measure of a polyisobutylene (PIB) melt as determined by analysis of uniaxial, planar, ellipsoidal, and equibiaxial extensions is compared to the predictions of the molecular model of Doi and Edwards. It is found that the universal strain function of the Doi-Edwards model is unable to predict the nonlinear behavior of this polymer melt in general extensional flow. The qualitative agreement between predictions and experimental data for the strain dependence of shear stress and first normal stress difference in shear flow that was considered as powerful evidence for the correctness of the Doi-Edwards model seems to be accidental. The exaggerated strain dependence of the model suggests a need to reconsider the assumptions concerning the chain retraction process.Presented at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.Dedicated to Professor F.R. Schwarzl on the occasion of his 65th birthday     

Catalytic chain transfer polymerization of isobutylene: The role of nucleophilic impurities

Fast polymerization of isobutylene (IB) initiated by tert‐butyl chloride using ethylaluminum dichloride·bis(2‐chloroethyl) ether complex (T. Rajasekhar, J. Emert, R. Faust, Polym. Chem. 2017, 8, 2852) was drastically slowed down in the presence of impurities, such as propionic acid, acetone, methanol, and acetonitrile. The effect of impurities on the polymerization rate was neutralized by using two different approaches. First, addition of a small amount of iron trichloride (FeCl₃) scavenged the impurity and formed an insoluble · impurity complex in hexanes. The polymerization rate and exo‐olefin content were virtually identical to that obtained in the absence of impurities. Heterogeneous phase scavenger (FeCl₃) exhibited better performance than homogenous phase scavengers. In the second approach, conducting the polymerization in wet hexanes, the fast polymerization of IB was retained in the presence of impurities with a slight decrease in exo‐olefin content. ¹H NMR studies suggest that nucleophilic impurities are protonated in the presence of water, and thereby neutralized. Mechanistic studies suggest that the rate constant of activation (k_a), rate constant of propagation (k_p), and rate constant of β‐proton elimination (k_tr) are not affected by the presence of impurities. To account for the retardation of polymerization in the presence of impurities, delay of proton transfer to monomer in the chain transfer step is proposed. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3697–3704     

New Types of Telechelic Polyisobutylenes, 1

Summary: A new, simple, and effective synthetic method for the preparation of glucose‐terminated polyisobutylenes starting from the corresponding hydroxyl‐terminated polymers is reported. Detailed NMR and matrix‐assisted laser desorption/ionization mass spectrometric (MALDI‐TOF MS) investigations showed the exclusive presence of bis(glucopyranosyl) polyisobutylene. Dynamic light scattering (DLS) investigations of this polymer in solution in both tetrahydrofuran and water showed that microphase separation takes place by the formation of micelles and/or vesicles.

Representative structure of the glucose‐terminated polyisobutylenes synthesized here.     

13C-NMR Study of the Compounds Resulting from the Reaction of 5-Methylene-2-norbornene with Trifluoroacetic Acid

Isomerization of the adduct resulting from the protonation of 5-methylene-2-norbornene by trifluoroacetic acid was studied by ^UC-NMR spectroscopy. Relative rate constants were determined under various experimental conditions. The influence of temperature, solvent, and relative reactant concentrations was examined.     

环状光束通过透镜的聚焦特性研究

给出了环状光束在柱坐标系下的一种描述模型,并利用广义衍射积分理论,推导出环状光束经过近轴ABCD光学系统的传输公式.在此基础上,通过数值模拟方法定量分析了环状光束的聚焦光强分布以及焦面处的桶中功率.研究结果表明,环状光束的聚焦特性与光束阶数以及系统菲涅耳数有关;环状光束在实际焦面和几何焦面上的桶中功率均随着遮拦比的增大而降低,而随着系统菲涅耳数的增大而增大.在实际工作中,通过合理地选取系统菲涅耳数和光束遮拦比可以有效地控制环状光束聚焦后的光束质量.     

正支共焦非稳腔的自动准直调整实验研究

谐振腔的自动准直调整技术是实现高能激光器系统自动化的关键技术之一。在对正支共焦非稳腔自动准直调整方法的研究基础上,应用基于系统性能评价函数无模型最优化的随机并行梯度下降（SPGD）控制算法实现腔的自动准直调整。实验结果表明该方法可实现腔镜的闭环控制准直调整,其调腔共轴精度在一定程度上高于传统的人工调腔精度。     

Dimethyldioxirane as a new and effective oxidation agent for the epoxidation of α,ω‐di(isobutenyl)polyisobutylene: A convenient synthesis of α,ω‐di(2‐methyl‐3‐hydroxypropyl)‐polyisobutylene

The synthesis and characterization of α,ω‐di(2‐methyl‐2,3‐epoxypropyl)polyisobutylene are reported. The epoxidation of α,ω‐di(isobutenyl)polyisobutylene was achieved at room temperature with dimethyldioxirane, which proved to be a very effective reagent for epoxidation without the formation of byproducts. A very good agreement was found for the conversion determined by ¹H NMR and matrix‐assisted laser desorption/ionization mass spectrometry (MALDI HMS). The epoxy end groups were converted quantitatively into aldehyde termini with zinc bromide as a catalyst. The aldehyde groups were then reduced with LiAlH₄ into primary hydroxyl functions to obtain α,ω‐di(2‐methyl‐3‐hydroxylpropyl)polyisobutylene with high efficiency. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3974–3986, 2002     

INITIATION VIA HALOBORATION IN LIVING CATIONIC POLYMERIZATION. 6. A NOVEL METHOD FOR THE SYNTHESIS OF PRIMARY AMINE FUNCTIONAL POLYISOBUTYLENES

Polyisobutylene (PIB) benzyl amine was synthesized by reacting benzyl azide with the dichloroboron head group of PIB obtained by polymerization of isobutylene (IB) via haloboration-initia-tion with boron trichloride. The facile, one-pot reaction at room temperature resulted in quantitative conversion of the PIB dichloroboron head groups into benzyl amine functionality, determined by ¹H NMR spectroscopy and titration with per-chloric acid. The hydrogenation of the secondary amine was attempted with various hydrogenation catalysts, of which only palladium yielded primary amine functional PIB. Pt and PtO hydrogenated the benzene ring resulting in PIB cyclohexyl methylene amine. With Pd only about 80% of the chain ends carried the primary amine functional group, apparently due to a side reaction. The side reaction was studied by ¹H NMR spectroscopy using PIB benzyl amine prepared from deuterated IB. Although direct evidence was not obtained, the ¹H NMR spectrum of the debenzylated product indicates that elimination of the amine group from the α carbon and elimination of a methyl group from the β carbon take place simultaneously, presumably due to the crowded nature of the neopentyl-type structure. The primary amine functional PIB was converted into PIB acetyl amide and imide via acylation with acetyl chloride. The products were analyzed by IR, ¹H NMR, and ¹³C NMR spectroscopy.     

微小孔非傍轴衍射光束传输特性的研究

基于非傍轴标量光束横截面上光强的精确定义,对桶中功率和二阶矩定义的光束束宽、远场发散角和M2因子等进行了比较研究.以平面波的微小圆孔衍射光束为例,进行了详细的数值计算.结果表明,桶中功率定义的光束束宽、远场发散角和M2因子较二阶矩定义的小,两种定义的M2因子都随束腰趋于零而趋向于零,桶中功率定义的光束束宽的传播规律与双曲线存在一定偏差.