PP/HDPE 共混物及其纳米复合材料超临界流体微孔发泡

通过间歇法制备了聚丙烯(PP)/高密度聚乙烯(HDPE)共混物及其纳米复合材料的微孔塑料.用扫描电镜对发泡样品的泡孔结构进行表征,研究了纳米粒子的类型和含量对泡孔结构的影响.结果表明:在PP中加入25%的HDPE可改善泡孔结构;在 PP/HDPE 共混物中加入纳米粒子可使泡孔的直径减小、密度增加、泡孔分布更均匀;泡孔直径随着纳米粒子含量的增加会出现先减小后增加的趋势.     

显微镜图像分析研究聚丙烯/尼龙1010共混物相结构及其性能

用扫描电子显微镜图像分析研究了聚丙烯/聚酰胺1010共混物及其部分相容体系的相形态结构,计算了表征相结构和尺寸的结构参数,如分散相的平均直径、平均弦长和分散相的质心相关距等.并分别讨论了聚丙烯/聚酰胺1010共混物及其部分相容体系的相形态以及其结构参数与共混物组成的关系.测定了聚合物及其共混物体系的力学性能,讨论了共混物组成与力学性能的关系.聚丙烯/聚酰胺1010共混物的拉伸模量与组成的关系较为复杂,但其部分相容体系的拉伸模量与组成呈线性关系.聚丙烯/聚酰胺1010及其共混物体系的屈服强度与共混物组成均呈线性关系.表征相结构的两相平均弦长比(l-1/-l2)与组成以及共混物体系力学性能与组成的关系,二者相似.同时讨论了体系力学性能随相尺寸等的变化规律.     

低含量聚乳酸对微孔发泡聚丁二酸丁二醇酯泡孔结构的改善

通过挤出制备了可生物降解聚丁二酸丁二醇酯(PBS)和3种聚乳酸(PLA)含量(7 wt%、15 wt%和20 wt%)的PBS/PLA共混物样品,采用超临界二氧化碳作为物理发泡剂对样品进行间歇发泡,研究发泡样品的泡孔结构,并分析其形成机理.在120oC发泡温度(Tf)下,借助PLA对PBS熔体黏弹性尤其是熔体强度的改善,获得了分布较均匀、形状较规则、直径较小(平均值约10μm)的微孔;共混物发泡样品的直径分布明显变窄,且符合高斯分布,这归因于细小的PLA相较均匀地分布于PBS基体中.进一步地,研究Tf对PBS和PLA含量为15 wt%的PBS/PLA共混物发泡样品泡孔结构的影响.结果表明,加入15 wt%的PLA使PBS的Tf下限从115oC降低至110oC,并显著改善了较高Tf(120和125oC)下制备的发泡样品内泡孔结构的均匀性.     

利用水的相变热调控聚丙烯发泡材料的泡孔结构

为了控制发泡体内部泡孔结构,以制备聚丙烯(PP)泡沫为例,提出在CO2作为发泡剂进行物理发泡过程中,以水为助发泡剂,利用其发泡过程中汽化吸热,原位冷却发泡体内部.将PP与聚乙二醇(PEG)熔融共混制备共混物(PP/PEG),PEG的存在赋予了共混物吸水的能力.采用红外线成像仪测试发泡体表层和芯部温度,利用扫描电子显微镜表征了泡孔结构.结果表明,与纯PP发泡体相比,在同样发泡条件下,PP/PEG共混物发泡体内部温度明显降低,内部与表层泡孔结构相近,且发泡倍率提高.进一步分析讨论了PP/PEG共混物发泡体内部温度明显降低的机理.这种方法适用于不同聚合物体系和不同发泡工艺,如:模压、挤出、釜式发泡工艺.     

发泡聚乳酸/热塑性聚氨酯/二氧化硅纳米复合材料的泡孔结构

以超临界二氧化碳作为物理发泡剂,通过快速降压法制备聚乳酸(PLA)/热塑性聚氨酯(TPU)/二氧化硅(SiO2)纳米复合材料发泡样品。发泡样品的泡孔结构使用扫面电子显微镜进行观察。在低频区,SiO2增加PLA/TPU共混物的储能模量和复数黏度。SiO2的加入使PLA/TPU共混物发泡样品的泡孔直径减小、泡孔密度增大。SiO2对PLA/TPU共混物发泡样品泡孔结构的改善归因于SiO2的异相成核作用和对共混物流变性能的改善作用。     

PP/POE共混物的P-V-T属性及压力对结晶温度的影响

采用PVT膨胀仪研究了PP/POE共混物的P-V-T属性, 利用Tait方程预测其比容和热膨胀系数(α), 研究了压力对结晶温度(Tc)的影响. 结果表明, Tait状态方程可用来预测部分相容的、半结晶PP/POE共混物的PVT行为. PP结晶前后的比容变化比POE的大得多, 随着POE含量的增加, PP/POE共混物结晶前后比容的变化均逐渐减小. PP在熔融状态下的α比固体状态的大, 而POE正好相反. PP/POE共混物的α随温度和压力的变化与其组成密切相关. 随着压力的增高, PP, POE及其PP/POE共混物的结晶温度均呈线性增高的趋势.     

相容剂对PP/POE共混体系脆韧转变行为的影响

采用熔融挤出法制备了不同相容剂含量的PP/POE共混体系,测试了不同体系的脆韧转变温度、热性能和力学性能.结果表明,乙烯-丙烯多嵌段共聚物相容剂的加入降低了PP/POE共混物的脆韧转变温度,提高了共混物的韧性.AFM和STEM照片显示相容剂的加入减小了橡胶分散相的临界粒子间距,PP和POE在两相界面结合处相互扩散或渗透,实现了POE弹性体在PP树脂中合适的尺度分布以及良好的形态分散.当相容剂含量达到10％时,POE分散相尺寸细小均匀,分散相粒子粒径为0.54μm,粒子间距为0.1 μm,PP结晶链段更多地插入到弹性体内部,弹性体POE分散相形成明显的“硬核-软壳”结构.DSC曲线中结晶峰和熔融峰的变化说明适量的相容剂对于材料结晶度的提高具有一定的促进作用.力学性能测试结果可以看出相容剂的加入在提高材料韧性,降低其脆韧转变温度的同时也保持了材料的刚性性能.     

注压成型纳米结构PP/POE共混物表面的液滴低温冲击行为

以制备的阳极氧化不锈钢模板为模具嵌件, 采用注射压缩成型(ICM)工艺快速成型表面具有纳米丝结构的柔性聚丙烯/乙烯-辛烯共聚物(PP/POE, PP与POE质量比为3∶1)共混物复制物和准刚性PP复制物, 研究常温液滴冲击?10 ℃复制物表面的动态行为. 结果表明, 致密的纳米丝使复制物表面呈现超疏水、 极低黏附的润湿状态. 在低冲击速度范围内, 共混物复制物表面上液滴的接触时间比PP复制物上的短, 可归因于液滴铺展阶段柔性纳米丝储存的弹性势能在回缩阶段转换为液滴的动能; 在高冲击速度范围内, 共混物复制物基板和纳米丝储存的弹性势能被转换为液滴的动能, 进一步缩短了液滴的接触时间. 此结果表明, 共混物复制物的柔性和表面超疏水性使其具有优异的防冻黏性能. 共混物复制物表面上水滴(50 μL)的结冰时间得到明显延长、 冰黏附强度明显降低. 研究结果表明, 可采用ICM快速成型具有优异防冻黏和防冰性能的柔性超疏水高分子材料表面.     

含原位聚合物核壳粒子聚丙烯共混物的流变学研究

制备了含原位聚合物核壳粒子的聚丙烯/乙丙橡胶/高密度聚乙烯(PP/EPR/HDPE)共混物,并通过动态流变方法对其熔体结构稳定性进行了研究.动态时间扫描结果表明,PP/EPR/HDPE共混物具有较好的热稳定性.动态频率扫描结果表明,当EPR含量较低时,共混物中聚合物核壳粒子分散相的存在导致体系的长时松弛行为更加显著.当熔体结构在大应变下遭到破坏后,含核壳粒子分散相的共混物具有比普通PP/EPR共混物更快的结构回复速率,且结构回复速率随着核壳粒子的尺寸增大而加快.通过增大普通PP/EPR体系的EPR含量使其橡胶粒子尺寸与三元共混物中原位聚合物核壳粒子尺寸接近时,两者呈现类似的流变行为,这表明PP/EPR/HDPE体系的熔体结构稳定性源于核壳粒子结构导致的分散相尺寸增大的作用.     

POE-g-PMAH反应性增容PA1010/PP共混物的性能研究

乙烯-辛烯共聚物-g-聚马来酸酐(POE-g-PMAH)作为反应性增容剂,采用熔体共混的方法制备了PA1010/PP共混物,通过扫描电镜(SEM)、力学性能、傅立叶变换红外光谱(FTIR)和示差扫描量热(DSC)测试,研究了POE-g-PMAH对PA1010/PP共混物的增容作用.结果表明,POE-g-PMAH的加入可以减小共混物的相区尺寸,当PA1010/PP/POE-g-PMAH=70/30/15时,分散相尺寸小而均匀;FTIR结果表明接枝在POE上的马来酸酐基团和PA1010在熔融共混期间发生了化学反应;DSC研究结果表明共混体系中PA1010和PP的结晶温度和结晶度随POE-g-PMAH的加入而降低,表明POE-g-PMAH的增容作用对PA1010和PP的结晶有抑制作用.力学性能测试结果表明随着POE-g-PMAH的增加,共混物的冲击强度逐渐增加,当POE-g-PMAH含量增加到15%时,干态冲击强度达到21.13 kJ/m2,是不加增容剂的3.1倍,而拉伸和弯曲强度可以保持较高水平.POE-g-PMAH的增容机理在于其支链中的马来酸酐能与PA1010中的胺基(NH2—)发生化学反应,而主链POE与PP有较好的亲和性,从而降低界面张力,减少相区尺寸,大幅度提高力学性能.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.