Crystallization behavior of PCL in hybrid confined environment

Poly(epsilon -caprolactone) (PCL) and silica (SiO2) organic-inorganic hybrid materials have been synthesized by the sol-gel method. The crystallization behavior of PCL in silica networks has been investigated using differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The degree of PCL crystallinity in PCL/SiO2 hybrid networks reduces with increase of SiO2. PCL is in an amorphous state when the concentration of PCL is lower than 40wt% in the hybrid system. The melting point of PCL in the networks is lower than, but close to that of pure PCL. WAXD and SEM results show that the crystalline behavior of PCL in PCL/SiO2 hybrid system is strictly confined. (C) 2001 Elsevier Science Ltd. All rights reserved.

Studies on the nature of the macromolecular condensed state of "nascent" ultra high molar mass polyethylene

Ultra high molar mass polyethylene (UHPE) powder as polymerized in a slurry process has been studied, in its nascent state, after recrystallization on rapid cooling from the melt and after hot compression molding to a film, by DSC, effect of annealing the recrystallized specimen at 120 similar to 130 degreesC, morphology by polarizing optical microscopy and small angle X-ray scattering. Based on the experimental results obtained the macromolecular condensed state of the nascent UHPE powder is a rare case of a multi-chain condensed state of non-interpenetrating chains, involving interlaced extended chain crystalline layers and relaxed parallel chain amorphous layers. On melting, a nematic rubbery state of nanometer size domain resulted. The nematic-isotropic transition temperature was judged from literature data to be at least 220 degreesC, possibly higher than 300 degreesC, the exact temperature is however not sue because of chain degradation at such high temperatures. The recrystallization process from the melt is a crystallization from a nematic rubbery state. The drop of remelting peak temperature by 10 K of the specimen recrystallized from its melt as compared to the nascent state has its origin in the decrease both of the crystalline chain stem length and of the degree of crystallinity. The remelting peak temperature could be returned close to that of the nascent state by annealing at 120 similar to 130 degreesC.

Phase structure and transitions in a poly(methyloctadecylsilane) oligomer

A poly(methyloctadecylsilane) oligomer was synthesized by a typical Wurtz coupling reaction. Upon cooling, three transitions were observed at temperatures of 39.9, 37.5 and 33.9 degreesC at a rate of 2.5 degreesC/min in differential scanning calorimetry (DSC). The first transition, with enthalpy change of 0.47 kT/mol and supercooling of 0.2 degreesC, was characteristic of the conformational change in the Si-Si backbone into an all-trans conformation, which was detected by temperature-dependent Fourier transform infrared (FT-FR) spectroscopy. The second and the third transitions with large supercooling were identified as the formation of two-dimensional hexagonal crystal packing and three-dimensional two-chain orthorhombic crystal packing, respectively. The crystal structure was determined by the combination of WAXD and transmission electron microscopy (TEM) experiments. (C) 2000 Elsevier Science Ltd. All rights reserved.

碳酸乙烯酯(EC)增塑的(PEO)_(16)LiClO_4聚电解质电导率的研究

采用差示扫描量热法 (DSC)和交流阻抗方法对EC增塑的 (PEO) 16 LiClO4 聚电解质进行了研究。结果表明 (PEO) 16 LiClO4 /EC体系的玻璃化转变温度 (tg)及PEO的结晶度 (Xc)降低 ,电导率 (б)增加 ,且б与温度 (T)的关系符合Arrhenius行为。提出了离子导电聚电解质 /不锈钢 (SS)这种结构的界面双层结构和交流阻抗谱图的模拟等效电路

高磺化度芳香聚醚醚酮的合成与表征

用 3 ,3’-二磺酸钠基 -4 ,4 -二氟二苯酮合成了具有高磺化度的荷电聚醚醚酮 .用红外吸收光谱及 DSC对其进行了表征 .研究了共聚物的组成、热稳定性、溶解性、成膜性及磺化度对共聚物性能的影响

含亚环己基荷电聚醚醚酮的合成表征与性能

以 3,3′ 二磺酸钠基 4,4′ 二氟二苯酮和 4,4′ 二氟二苯酮与 4,4′ 亚环己基双酚进行亲核共缩聚 ,合成了磺化度从 0 4～ 2 0的一系列含亚环己基的荷电聚醚醚酮 .聚合物除保持了荷电聚醚醚酮良好的热稳定性和机械性能外 ,还具有良好的耐水性 .聚合物的DSC和广角X射线衍射数据表明 :上述磺化度聚合物均呈无定型聚集态结构 .比较了聚合物与双酚A系列荷电聚醚醚酮的性能差异 ,讨论了聚合物的溶解特点

聚β-羟基丁酸酯顺丁烯二酸酐接枝共聚物的研究

采用DSC、TGA、POM和WAXD等方法对聚 β 羟基丁酸酯 (PHB)及其接枝顺丁烯二酸酐共聚物 (PHB g MA)的结晶行为、热稳定性和生物降解特性进行了研究 .结果表明接枝产物的热稳定性明显优于PHB ,热分解温度提高了 2 0余度 ;结晶行为发生很大的变化 .结晶速率减小 ,结晶温度降低 ,冷结晶温度升高 ,球晶的织态结构也随着MA接枝量的变化发生明显变化 ,并且接枝MA促进了PHB的生物降解

成核剂对PHBV等温结晶行为的影响

用DSC方法测定了氮化硼及滑石粉成核剂对 (β 羟基丁酸酯 与 β 羟基戊酸酯 )共聚物 (简称PHBV)等温结晶行为的影响 .结果表明 ,Avrami方程指数n、成核机理、晶体生长方式基本上不受成核剂的影响 .少量的成核剂可使结晶成核自由能降低 ,结晶速率加大 ,其中氮化硼的效果最为显著

PA6/UHMWPE/HDPE-g-MAH共混物反应增容作用的研究

通过 DSC、SEM、Molau试验和力学性能测试 ,研究了 PA6/ UHMWPE共混过程中 HDPE- g- MAH对体系的增容作用、力学性能及结晶行为的影响。结果表明 ,共混体系为热力学不相容体系 ;在熔融共混过程中 ,PA6和 HDPE- g- MAH发生化学反应 ,生成的接枝共聚物对 PA6/ UHMWPE体系有增容作用 ,分散性和界面形态以及力学性能明显改善 ;共混体系中两相的结晶行为亦发生变化 ,尼龙组分的熔融热焓明显下降

有机/无机杂化体系中聚氧化乙烯的受限结晶

通过 sol- gel技术合成了聚氧化乙烯 ( PEO)和二氧化硅 ( Si O2 )的有机 -无机杂化材料 ,通过 DSC和WAXD方法测试了杂化样品中 PEO的结晶度、结晶结构和 ( 12 0 )晶面的微晶尺寸 ,说明了 PEO在该杂化体系中的受限结晶行为

官能化聚烯烃弹性体增韧PA1010体系Ⅱ.结晶行为的研究

用 WAXD、偏光显微镜 (PM)及 DSC研究了聚烯烃弹性体乙烯 - α-烯烃共聚物 (EOCP)对 PA10 10结晶行为的影响。WAXD结果显示纯弹性体 (EOCP)和接枝弹性体 (EOCP- g- MA)对 PA10 10的晶型均不产生影响。PM观察则表明共混体系中 EOCP与 PA10 10的相互作用很弱 ,在 PA10 10结晶过程中 ,大部分 EOCP被排除在球晶之外 ;而接枝 EOCP与 PA10 10存在较强的相互作用 ,大量的 EOCP- g- MA作为成核剂 ,使 PA10 10球晶向细晶化方向发展 ,而且随弹性体含量的增多而加强。DSC分析证实了接枝EOCP以异相成核剂的方式促进了 PA10 10的结晶 ,尤其是促进了 PA10 10的高温结晶

聚合物载体负载TiCl_4/i-Bu_3Al催化烯烃聚合

探讨了聚合物负载烯烃聚合催化剂的合成及用于聚合的研究 .研究了聚合物作为载体的催化行为 ,并通过 IR,DSC,元素分析和粘度法测定分子量等手段对催化剂及聚合物进行了表征 .包括合成聚合物负载的 Ti体系催化剂和用所合成的催化剂进行乙烯聚合 ,乙烯、丙烯与丁二烯共聚合的研究 .

茂金属催化剂Cp_2~tMCl_2(Cp~t=~tBuC_5H_4,M=Ti、Zr、Hf)聚合丁烯-1的研究

探讨了茂金属催化剂 Cpt2 MCl2 ( Cpt=t Bu C5 H4,M=Ti,Zr,Hf)的合成以及用于聚合丁烯 -1的研究 ,研究了几种不同的茂金属催化剂和不同聚合条件下的催化行为 ,并通过 IR、1 H NMR、EI-MS、DSC、粘度法测分子量和正庚烷抽提等测试手段对催化剂和聚合物进行了表征 .结果表明 ,叔丁基取代的茂金属催化剂催化丁烯 -1聚合具有较高的催化活性 ,叔丁基的引入提高了聚合物的等规度和分子量

含环己烯氮杂环结构的聚醚砜酮三元共聚物合成

用 1 -甲基 -4 ,5-二 ( 4-氯代苯甲酰基 )环己烯与 4 -( 4-羟基苯基 ) -2 ,3 -二氮杂萘 -1 -酮、4 ,4′-二氯二苯砜经亲核共缩聚反应 ,合成了含环己烯结构的杂环联苯型聚醚砜酮三元共聚物。用FT -IR、1H -NMR、DSC、X -射线衍射等方法对聚合物进行了表征 ,并研究了聚合物的溶解性能。结果表明 ,聚合物是一种具有较高的玻璃化转变温度的可溶性无规共聚物。聚合物含有不饱和双键结构 ,是一种反应性高分子。

Non-isothermal crystallization kinetics of the poly(3-alkylthiophenes)

According to the data obtained from Differential Scanning Calorimetry (DSC),the method of Jeziorny, BOPOXOBCKHH and a new approach proposed by our laboratry are applied to study the nonisothermal crystallization behavior of poly( 3-dodecylthiophene) (P3DDT) and poly(3-octadecylthiophene) (P3ODT),and Kissinger method is used to get the value of the crystallization activation energy. The effect of the different alkyl substitution on crystallization is also investigated. In comparison to the methods of Jeziorny and BOPOXOBCKHH in which it can be found that the deviation from the line occurs in the later stage of crystallization, the new approach appears applicable due to the better linear relation. The values of the crystallization activation energy of P3DDT and P3ODT are estimated as 184.78kJ/mol and 246.93kJ/mol, respectivley, which implies that it is easiser to crystallize P3DDT than P3ODT.