旋转挤出加工制备高性能聚合物管

聚合物管主要用于流体压力输送,要求环向强度高,耐应力开裂性能好,使用寿命长。我们借鉴天然管竹子因竹纤维轴向排列使其轴向破裂易,横向破裂难的结构特点,提出形成偏离轴向的增强相结构可以显著提高聚合物管的性能,自行设计研制了新型的聚合物管旋转挤出装置,通过芯棒和口模独立可调的旋转运动与轴向速度可调的挤出/牵引运动的不同组合,形成与常规挤出不同的应力场,并通过管内外壁双冷技术调控聚合物管中温度场,从而在聚合物管中形成和定构不同层次的偏离轴向排列的增强相结构(如取向分子、串晶、原位成纤诱导形成串晶、外加纤维等),大幅度提高聚合物管的环向强度和耐应力开裂性能,如旋转挤出聚乙烯管形成偏离轴向串晶结构,使其环向拉伸强度和裂纹引发时间分别比常规挤出聚乙烯管提高78%和544%。我们还从理论上分析了旋转挤出中聚合物的流变行为,得到其流动速率数学表达式,阐明旋转挤出形成偏离轴向增强相结构的机理。旋转挤出加工为制备高性能聚合物管提供新设备、新技术、新理论。本文简要总结了我们通过旋转挤出制备高性能聚合物管的一些研究工作。     

芯棒与口模反向旋转挤出聚乙烯管结构与性能的研究

采用自行研制的新型旋转挤出装置,通过芯棒与口模同时反向旋转挤出制备聚乙烯(PE)管.结果表明,在口模与芯棒反向旋转挤出过程中,管道内外壁除受到轴向应力作用外,还受到芯棒和口模旋转所施加的环向应力,其合力方向不再是沿管道轴向而是与其有一定的角度.因此,分子链的取向方向和以此链为初级成核点形成的串晶偏离轴向,增强了管道抵抗...     

PVCH-PE-PVCH中PE片晶链轴在柱状微区中的取向

以柱状微相分离结构的聚乙烯基环己烷-聚乙烯-聚乙烯基环己烷(PVCH-PE-PVCH)三嵌段共聚物为研究对象,分别采用压延法和旋转涂膜法制得取向样品。利用偏振红外光谱法测定了PE柱状微区内结晶区中—CH2—基团的面内扭摆振动吸收峰的变化,以此来考察PE晶区折叠链片晶的链轴在柱状微相分离结构中的取向性。结果表明:在压延取向的样品中,由于外力的作用使得PE柱状微区沿着样品流动的方向取向,PE片晶的链轴也同样倾向于沿着平行于PE柱状微区的柱轴方向排列。退火使得PE片晶沿着链轴取向方向的取向程度升高。在由旋转涂膜制得的取向薄膜样品中,PE柱状微区垂直于基板排列,而PE片晶链轴则更倾向于沿着垂直于PE柱状微区的柱轴方向取向。     

受限于纳米碳管中的乙醇分子的结构和扩散的分子模拟研究

利用分子模拟研究了常温常压下受限于(8,8) (管径1.081 nm)和(15,15) (管径 2.035 nm)单壁纳米碳管中的乙醇分子. 对受限分子的径向密度分布和氢键等静态性质以及扩散性质进行了分析. 结果显示在管内乙醇分子的平均氢键数目和主体相一致. 乙醇分子在(8,8)碳管内具有高度有序的结构, 而在(15,15)碳管内由于空间的增大导致结构有序度的降低, 其中分子取向已呈随机分布. 进一步对扩散系数的分析发现, 在管内乙醇分子的轴向扩散系数低于主体相, 特别在(8,8)碳管内乙醇分子几乎丧失了轴向扩散能力.     

成型方式对不同木塑复合体系的性能影响研究

以木粉为填充材料,以PE(聚乙烯)、PP(聚丙烯)为塑料基体,分别采用混炼-模压工艺和挤出-注塑工艺制备木塑复合材料,对比研究不同复合材料的力学性能、热性能以及流变性。结果表明,混炼-模压工艺制备的PE基复合材料综合性能较优,而挤出-注塑工艺制备的PP基复合材料综合性能较优,且在PE塑料系列中,HDPE(高密度聚乙烯)基复合材料综合力学性能最好,LLDPE(线性低密度聚乙烯)基复合材料的冲击韧性最好,但其综合力学性能较差。     

多孔基体负载的碳纳米管复合膜制备及其气体渗透性能

采用改进的浮动催化法在多孔Al2O3基体上制备了垂直取向的碳纳米管阵列, 并用旋转喷涂法将聚苯乙烯填充于碳纳米管的空隙, 进一步将其制备成复合碳纳米管膜, 研究了H2和CO2单组分在碳纳米管复合膜中的渗透性能, 实验结果表明, H2/CO2的理想分离系数随着复合膜中碳管管径的减小而增大, 在管径较小的复合膜中, 气体渗透分离系数高于努森扩散限制, 达到6.25, 具有一定的分离效果. 两种气体在复合膜中的渗透率随着渗透温度的增加而减小.     

速凝成晶-粘结法制备稀土磁致伸缩材料TbDyFe的研究

采用速凝成晶技术,制备了具有<112>和<110>择优取向的Tb0.27Dy0.73Fe1.95速凝片.研究发现,速凝片的择优取向和显微组织与冷却速度密切相关.随着冷却速度的增加,其择优取向从<112>向<110>变化,显微组织由枝状晶向胞枝晶转变.研究了由速凝片制备的稀土粘结磁致伸缩样品的性能.结果表明,当粉末粒度≤(100～150)μm时材料性能较好,具有<112择优取向的样品性能高于<110>择优取向的样品,磁场取向成型有利于材料性能的改善.获得了性能良好的粘结磁致伸缩材料,在238.8 kA·m-1时磁致伸缩系数达到740×10-6.     

聚乙烯在氧化铝模板中的结晶与取向行为

用多孔阳极氧化铝(AAO)模板制备了直径为200nm的聚乙烯(PE)纳米纤维,并用傅立叶变换红外光谱(FTIR)、偏光显微镜(PLM)和X-射线衍射(XRD)方法研究了PE在二维圆柱状受限条件下的结晶与取向行为.FTIR研究表明,由于模板的限制作用,PE纳米纤维的结晶度低于本体.同时,PE纳米纤维晶体的b轴平行于模板孔洞的方向取向,而a轴垂直于孔洞的方向取向.XRD结果进一步证明,在纳米孔洞中PE晶体的b轴平行于纳米孔洞方向.PLM结果表明,在结晶过程中,晶体主要是在模板与本体的界面处成核,然后晶体呈发散状向本体和纳米纤维中竞争生长.由于PE晶体的b轴是其生长速率最快的方向,在本体中形成典型的环带球晶形貌;而在二维圆柱受限条件下,只有沿孔洞方向生长的晶体才能增长,而其它生长方向则受到抑制,造成PE晶体的b轴沿孔洞方向优先取向.     

聚对苯二甲酸乙二酯的结晶与取向

为了了解PET球晶的拉伸性能与球晶结构的关系以及无定形PET的取向和结晶,我们采取了两条不同的路线来制备样品:(1)先用溶液浇铸成膜的办法制备具有正球晶、负球晶或非常球晶的薄膜,然后进行单轴拉伸。电子显微图象及电子衍射证明,球晶的拉伸性能与C轴和球晶半径方向的夹角有关,夹角愈大拉伸愈困难;(2)先制备无定形的薄膜,然后在玻璃化温度附近进行单轴拉伸以获得C轴取向,再在215℃退火,使之结晶。电子衍射图证明,这样制备的样品具有高度的C轴取向。DSC结果表明,结晶的完善程度远比球晶的为高。     

流变光学方法研究结晶高聚物的形变机理(摘要)

用光学方法研究结晶高聚物的形变和流动过程称为流变光学(Rheo-opties)。通常研究结构用的光学方法与动态力学试验装置相结合,还可观察其动态形变过程中相应的结构变化。 X射线衍射法可以测定高聚物形变过程中晶粒的取向。我们发现:聚乙烯随拉伸程度的增长昌区的取向程度也增加,但晶区的取向滞后于非晶区的取向且随晶区取向的增加其非晶区的取向逐渐松弛。因此,     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.