聚恶唑啉的合成及其共混物

综述了恶唑啉单体的合成及其聚合方法，并对其聚合物的化学改性及共混物作了概述。     

手性二噁唑啉吡啶铁和镍配合物的制备与表征

Tridentate bis(oxazolinylpyridine)(1) reacted with nickel chloride or ferrous chloride in anhydrous ethanol to form bis(oxazolinylpyridine) Nickel(Ⅱ) and Iron(Ⅱ) complexes. The stable solid complexes were characterized with IR， UV， MS， XPS and elemental analysis. No stable complexes were formed with bidentate bis(oxazoline)(2) ins- tead of bis(oxazolinylpyridine).     

异噁唑啉盐的合成及其应用

作为一类重要的有机合成中间体,异噁唑啉盐广泛地应用于具有生物活性化合物的制备.对异噁唑啉盐的结构、制备方法,及其作为多功能合成中间体,在N-甲基异噁唑烷、N-甲基氨基醇、N-甲基氨基多醇、α-氨基酸和β-氨基酸等重要化合物合成中的应用作了较详尽阐述,同时简单地介绍了新型N-取代异噁唑啉盐的合成及其应用.在对这些研究现状进行分析的基础上,对该研究领域下一步的发展方向进行了展望.     

PVC与端噁唑啉聚环氧丙烷的热共混接枝

本文研究聚氯乙烯(PVC)与端-2-噁唑啉聚环氧丙烷(活性聚醚)在加工过程中的接枝反应,通过溶剂萃取、IR、DSC、GPC和SEM分析方法证实接枝反应的发生,并发现无催化剂存在时,在PVC加工温度下亦能较快的发生接枝共聚反应。     

新型含异噁唑环1,3,4-噁二唑啉衍生物的合成

以N-羟基-4-甲氧基苯甲醛肟氯化物为原料,经两步反应制得3-对甲氧基苯基-5-甲基-异噁唑-4-甲酰肼(3);3依次经缩合和环合反应合成了一系列新型的2-芳基3-乙酰基-5-(3-对甲氧基苯基-5-甲基-异噁唑-4-基)-Δ4-1,3,4-噁二唑啉衍生物,其结构经~1H NMR,13C NMR,IR,MS(EI)和元素分析表征。     

聚环氧乙烷/聚乙基■唑啉共混体系结晶行为及相容性的研究

用偏光显微镜（ＰＬＭ）、ＤＳＣ、ＩＲ和ＷＡＸＤ等测试方法对聚环氧乙烷（ＰＥＯ）／聚乙基唑啉（ＰＥＯｘ）共混体系结晶行为及相容性进行了研究．结果表明，ＰＥＯ含量在３０％以上的共混体系中，几乎完全被球晶充满，非晶态ＰＥＯｘ作为微区分散在大球晶之间或之中；含量为２０％的共混体系照片上呈树枝状晶；含量低于１０％时则看不到结晶出现，体系形成单一的非晶相．对任何组成的共混物，均只出现单一的玻璃化转变温度（Ｔｇ），而且符合Ｆｏｘ方程揭示的规律；随ＰＥＯｘ组分含量的增加，共混体系的结晶度减小，熔点下降，并利用平衡熔点方程计算出ＰＥＯ与ＰＥＯｘ的相互作用能密度．非晶ＰＥＯ与ＰＥＯｘ热力学相容，其相容性是由于这两种分子间存在着特殊相互作用．ＰＥＯｘ的加入不会改变ＰＥＯ的晶胞参数．     

含氟1,3,4-噁唑啉和1,3,4-噁二唑类化合物的合成及其抗癌活性

对氟苯甲酰腙与乙酸酐或丙酸酐反应后再脱水环化制得2-苯基-3-乙酰基-5-对氟苯基-1,3,4-噁唑啉(3)或2-苯基-3-丙酰基-5-对氟苯基-1,3,4-噁唑啉(4).N-对氟苯甲酰基-N′-苯甲酰肼在POCl3存在下脱水环化制得2-苯基-5-对氟苯基-1,3,4-噁二唑(6).新化合物3,4和6的结构经1H NMR,IR,MS和元素分析表征.用MTT方法评价了其对HepG-2,A549-1和231-2癌细胞株的体外生长抑制活性.结果表明,3,4和6均具有潜在的体外抑制癌细胞生长活性,其中3的活性最强.     

一锅法合成噁唑啉金属配合物研究进展

一锅法合成金属配合物是近年来金属有机化学研究的一个热点之一。在对国内外噁唑啉金属配合物的合成及应用进行大量文献调研基础上,综述了本课题组近年来用腈类与手性氨基醇作用,在不同物质的量的金属盐如氯化锌、乙酸铜和氯化钴等金属氯化物或金属乙酸盐作用下,一锅法一步合成系列噁唑啉金属配合物及应用研究进展。同时,对该方法在其他噁唑啉金属配合物合成及应用领域提出展望。     

手性多噁唑啉的一步合成方法

尽管已报道了多种结构类型的手性单或双噁唑啉, 但手性多噁唑啉的合成及其应用的文献报道比较少. 本工作以多元羧酸为原料, 与手性2-氨基-1-丁醇经一步反应合成了8个手性多噁唑啉, 产率为89%～98%, 其结构经¹ H NMR谱、IR谱、MS谱和元素分析确证.     

聚乙二醇负载的二茂铁噁唑啉配体的合成及其应用

报道了聚乙二醇(MeO-PEG)负载的二茂铁噁唑啉衍生的手性N,P和N,S配体的合成. 所得负载N,P配体可以成功应用于银催化的[3+2]环加成反应, 最高取得了97%的对映选择性. 另外聚乙二醇负载二茂铁N,S配体可以成功应用于钯催化的烯丙基取代反应, 取得了90%的ee值. 值得注意是, 聚乙二醇负载形成的催化剂循环使用4次后其催化活性和选择性仍可基本保持.     

聚醚砜与含萘环的聚芳醚酮增容共混物的研究

以双酚S型含萘环的聚芳醚酮为增容剂,研究了对聚醚砜(PES)与对苯二酚型-1,4-萘环的聚芳醚酮(1,4-NA-PAEK)共混体系的相容性及力学性能.结果表明,双酚S型含萘环的聚芳醚酮可显著降低PES/NA-PAEK共混体系中NA-PAEK分散相尺寸,改善两组分间的相容性,并且增容剂的加入使共混体系形成了双连续的互锁结构,提高了共混物的力学性能.     

多组分聚合物体系中的相容和络合

在含可控特殊相互作用的多组分聚合物体系中，随着体系中的相互作用密度的增强，体系在本体中可经历由不相容到相容直至络合的不同物理状态。本文概述了相容、络合研究的进展，着重讨论了相容和络合的区别和联系，提出了含氢键相互作用的高分子共混体系中相容－络合转变存在的普遍性。     

Formation of Co-continuous Structures in Melt-Mixed Immiscible Polymer Blends

Abstract

Co-continuous structures can be regarded as the coexistence of at least two continuous structures within the same volume. Blends with co-continuous structures may combine the properties of both components in a favorable way, for example, mechanical moduli. This review article deals with the identification, characterization, and properties of co-continuous structures as well as with the development of co-continuous structures during the melt blending process. Co-continuous structures usually can be formed within a composition region about the phase inversion composition, which mainly depends on the viscosity ratio. On the other hand, co-continuous structures can be found independent of composition as intermediate stages during the initial state of morphology development and during phase inversion process in blends in which the component finally forming the dispersed phase forms the matrix in early mixing states. In addition, even at low volume fractions of one component, stable co-continuous morphologies can be created using suitable processing conditions, forming long elongated interconnected structures that do not break up because of the flow. The interfacial tension plays an important role for the stability; a lower interfacial tension leads to broader composition ranges of co-continuous structures. Another factor enhancing the formation and stability of co-continuous structure is melt yield stress of one or both components of blends. In addition, this article reviews the stability of co-continuous structures during further processing and the influence of compatibilization on the structure formation and stability. Subsequently, two models describing the co-continuous composition range are discussed.     

反应性杂化纳米粒子的合成及其对不相容共混物的增容研究

采用八环氧多面体低聚倍半硅氧烷(POSS(epoxy)8)和端羧基聚甲基丙烯酸甲酯(PMMA-COOH)的开环反应,运用Graft-onto的方法合成了一种反应性杂化纳米粒子:四环氧多面体低聚倍半硅氧烷-接枝-四聚甲基丙烯酸甲酯(POSS(epoxy)4-g-PMMA4).通过傅里叶红外光谱仪(FTIR),示差扫描量热仪(DSC),热失重分析仪(TGA),核磁共振波谱仪(1H-NMR)等对反应性杂化纳米粒子的结构进行了表征,结果表明成功合成了POSS(epoxy)4-g-PMMA4.并将上述合成的反应性杂化纳米粒子应用于聚偏氟乙烯/聚乳酸(PVDF/PLLA)不相容体系的增容,运用万能材料试验机、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对其增容原理和效果进行研究,结果表明POSS(epoxy)4-g-PMMA4可以作为PVDF/PLLA不相容体系的反应性增容剂.     

聚酰亚胺对高性能树脂共混体系界面的反应增强

研究了以5-降冰片烯-2,3-二羧酸单甲酯为端基的PMR型聚酰亚胺(POI)作为界面介质对部分相容的聚醚砜/聚苯硫醚(PES/PPS)、聚醚醚酮/聚醚砜(PEEK/PES)共混体系的界面性质、形态结构及结晶行为的影响.结果表明,POI可以有效地增强两相间的界面粘结,显著降低PPS/PES共混物中PPS分散区的尺寸,改善两组分间的相容性.在熔融共混过程中,POI从本体向界面扩散并同PPS,PES产生交联和/或接枝,POI同PPS的反应活性远高于PES,但POI与PES发生反应.POI是PPS结晶的有效成核剂.     

PTW对PA1010/PP共混物的增容作用

为了增加聚酰胺1010/聚丙烯(PA1010/PP)共混物的相容性,提高共混物的力学性能,采用一种新型的反应型增容剂乙烯-丙烯酸丁酯-甲基丙烯酸缩水甘油酯共聚物(PTW)进行增容,通过扫描电镜(SEM)、力学性能、傅里叶变换红外光谱(FTIR)和差示扫描量热(DSC)测试,研究了PTW对PA1010/PP共混物的增容作用.结果表明,随着PTW的加入,共混物的相区尺寸明显变小,当PA1010/PP/PTW质量比为70∶30∶7时,分散相尺寸细小而均匀,表明PTW有较好的增容作用.FTIR结果表明,PTW上的环氧基团和PA1010在熔融共混中发生了化学反应.DSC研究结果表明,PA1010的结晶温度随PTW的加入而降低,说明PTW对PA1010结晶有抑制作用.另外,PTW的加入使PP的结晶温度下降,当PTW质量分数为5%时出现2个结晶峰,即出现异相成核结晶和均相成核结晶,PP均相成核结晶的出现从另一个方面说明,在PA1010基体中分散相PP尺寸非常细小.当PTW质量分数为7%时共混物的力学性能最佳,干态冲击强度达到13.93kJ/m2,是未加增容剂时的2倍,拉伸和弯曲性能基本不变.PTW的增容机理在于其分子链中的甲基丙烯酸缩水甘油酯能与PA1010发生化学反应,而乙烯链段与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.     

超临界二氧化碳中的高分子合成

近年来,超临界二氧化碳（sc-CO2）在聚合反应中的应用受到了越来越多的关注。本文主要综述了以sc-CO2为反应介质的自由基聚合、阳离子聚合、过渡金属催化聚合、热致开环聚合、溶胶-凝胶聚合以及氧化耦合聚合的研究概况。一系列研究结果表明sc-CO2是非常有前途的反应溶剂,在高分子合成领域将会有更加广阔的应用前景。     

Synthesis of Stereocontrolled Degradable Polymer by Living Cascade Enyne Metathesis Polymerization

A stereocontrolled degradable polymer was synthesized via living cascade enyne metathesis polymerization. Highly stereodefined N,O-acetal-containing enyne monomers were prepared using the Pd-catalyzed hydroamination of alkoxyallenes and ring-closing metathesis. The resulting chiral polymer exhibited a narrow dispersity window. Block copolymers were prepared not only by sequentially adding nondegradable and degradable monomers but also by using enantiomerically different monomers to produce stereocontrolled blocks. Owing to the hydrolyzable N,O-acetal moiety in the backbone structure, the resulting polymer could degrade under acidic conditions generated using various acid concentrations to control the degradation. Additionally, the aza-Diels–Alder reaction modified the polymer without losing the stereochemistry.     

Solvent-Polymer Interaction. II. Measurements of Liquid Solvent Molecules Associating with Polymer Sites and of Their Transport Behavior in Polymer Membrane by Thermogravimetry,GLC, and Mass Spectrometry

The measurement of sorption and diffusion behavior of liquid ethanol and water solvent mixtures in polyurethane membrane were made simultaneously by thermogravimetry. The individual amounts of sorbed water and ethanol in the polymer membrane were estimated by thermogravimetry and differentiated by mass spectrometry. In addition, from a single dynamic thermogravimetric experiment the activation energy for solvent molecules desorbing from the polymer membrane was also determined. The thermodynamic activity of ethanol vapor in equilibrium with the ethanol-water-polyurethane system was determined by gas-liquid chromatography. The clustering functions, the mean numbers of solvent molecules in the clusters, and those associating with polymer sites were evaluated by applying simplified mathematical derivatives using the experimentally determined values of activity and volume fraction of solvent molecules. It was found that at lower ethanol concentration the tendency for ethanol molecules to cluster together is high. At higher ethanol activity, ethanol-polymer site interactions predominantly occurred.

Similar results were observed for ethanol-water molecules. However, water molecules in this particular system did not exhibit a self-associating tendency nor interact with the polymer sites. It was concluded that the Zimm-Lundberg clustering theory can be adequately applied to the interpretation of sorption and diffusion behavior of liquid ethanol-water mixtures in the polymer membrane.     

Small Molecule: Polymer Blends for N-type Organic Thin Film Transistors via Bar-coating in Air

Fabricating n-type organic thin film transistors(OTFTs)based on small molecules via solution processing under atmospheric conditions remains challenging.Blending small molecules with polymer is an effective strategy to improve the solution processibility and air stability of the resulted devices.In this study,polystyrene was chosen to blend with n-type small molecule DPP1012-4F to enhance the continuity of the semiconductor layer and maintain a favorable edge-on stacking of semiconductors.The introduction of high-boiling point 1-chloronaphthalene as a solvent additive in the blending system can reduce the grain boundary defects in the microscopic morphology.These changes in aggregation behavior are confirmed by X-ray diffraction,atomic force microscopy and polarized optical microscopy analyses.Via bar-coating of the semiconductor layers in air,the electron mobility of the resulted OTFTs under the optimal condition is 0.73 cm2·V–1·s–1,which is amongst the highest n-type small molecule-based OTFTs with active layers prepared in air up to now.These results show a great potential of the blending strategy in industrial roll-to-roll manufacture of high-mobility n-type OTFTs.