用DSC研究稀土顺式聚丁二烯的低温结晶与熔融行为

采用示差扫描量热仪研究了稀土顺式聚丁二烯(PB)等温过程的结晶及其熔融行为。结果表明,在等温结晶的后期存在晶型完善的过程,而且随着等温结晶温度的提高,结晶速率均下降。PB的熔融总是在比等温结晶温度高约2℃处开始,而且在10℃/min的升温速率下,DSC曲线不仅显示出很宽的熔融温度范围,而且在低温处还出现了小肩峰,说明等温结晶后体系中具有在该升温速率下不同稳定性的晶体。

等规聚丙烯DSC熔融双峰的成因

论述了多种产生熔融双峰的情况及原因 ,对最近研究等规聚丙烯 DSC熔融双峰的进展进行了评述。最后 ,介绍了笔者在这一领域的最新研究成果

High resolution solid-state NMR and DSC study of poly(ethylene glycol) silicate hybrid materials via sol-gel process

Hybrid materials incorporating poly(ethylene glycol) (PEG) with tetraethoxysilane (TEOS) via a sol-gel process were studied for a wide range of compositions of PEG by DSC and high resolution solid-state C-13- and Si-29-NMR spectroscopy. The results indicate that the microstructure of the hybrid materials and the crystallization behavior of PEG in hybrids strongly depend on the relative content of PEG. With an increasing content of PEG, the microstructure of hybrid materials changes a lot, from intimate mixing to macrophase separation. It is found that the glass transition temperatures (T-g) (around 373 K) of PEG homogeneously embedded in a silica network are much higher than that (about 223 K) of pure PEG and also much higher in melting temperatures T-m (around 323 K) than PEG crystallites in heterogeneous hybrids. Meanwhile, the lower the PEG content, the more perfect the silica network, and the higher the T-g of PEG embedded in hybrids. An extended-chain structure of PEG was supposed to be responsible for the unusually high T-g of PEG. Homogeneous PEG-TEOS hybrids on a molecular level can be obtained provided that the PEG. content in the hybrids is less than 30% by weight. (C) 1998 John Wiley & Sons, Inc.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone) .1. DSC characterization of curing reaction

The curing reaction process of epoxy-terminated poly(phenylene ether ketone) (E-PEK) with 4,4'-diaminodiphenyl sulfone (DDS) and hexahydrophthalic acid anhydride (Nadic) as curing agents was investigated using isothermal differential scanning calorimetry (IDSC) and nonisothermal differential scanning calorimetry (DDSC) techniques. It was found that the curing reactions of E-PEK/DDS and E-PEK/Nadic are nth-order reactions but not autoaccelerating. The experimental results revealed that the curing reaction kinetics parameters measured from IDSC and DDSC are not equivalent. This means that, in the curing reaction kinetics model for our E-PEK system, both isothermal and nonisothermal reaction kinetics parameters are needed to describe isothermal and nonisothermal curing processes, The isothermal and nonisothermal curing processes were successfully simulated using this model. A new extrapolation method was suggested. On the basis of this method the maximum extent of the curing reaction (A(ult)) that is able to reach a certain temperature can be predicted. The A(ult) for the E-PEK system estimated by the new method agrees well with the results obtained from another procedure reported in the literature. (C) 1997 John Wiley & Sons, Inc.

PHASE-BEHAVIOR IN MIXTURES OF A HOMOPOLYMER AND A BLOCK-COPOLYMER .1. FTIR AND DSC STUDIES

Miscibility in blends of three styrene-butadiene-styrene and one styrene-isoprene-styrene triblock copolymers containing 28%, 30%, 48%, and 14% by weight of polystyrene, respectively, with poly(vinyl methyl ether) (PVME) were investigated by FTIR spectroscopy and differential scanning calorimetry (DSC). It was found from the optical clarity and the glass transition temperature behavior that the blends show miscibility for each kind of triblock copolymers below a certain concentration of PVME. The concentration range to show miscibility becomes wider as the polystyrene content and molecular weight of PS segment in the triblock copolymers increase. From the FTIR results, the relative peak intensity of the 1100 cm-1 region due to COCH3 band of PVME and peak position of 698 cm-1 region due to phenyl ring are sensitive to the miscibility of SBS(SIS)/PVME blends. The results show that the miscibility in SBS(SIS)/PVME blends is greatly affected by the composition of the copolymers and the polystyrene content in the triblock copolymers. Molecular weights of polystyrene segments have also affected the miscibility of the blends. (C) 1995 John Wiley & Sons, Inc.

DSC AND C-13 NMR-STUDIES OF ETHYLENE-PROPENE COPOLYMERS PREPARED BY A HIGHLY-ACTIVE AND STEREOSPECIFIC CATALYST

Ethylene-propene copolymers (EPR) were synthesized at different feed compositions using a highly active and isospecific MgCl2-supported Ti-based catalyst. The thermal behavior of EPR was studied by differential scanning calorimetry, the heterogeneity by f

A HIGH-RESOLUTION SOLID-STATE NMR AND DSC STUDY OF MISCIBILITY AND CRYSTALLIZATION BEHAVIOR OF POLY(VINYL ALCOHOL)/POLY(N-VINYL-2-PYRROLIDONE) BLENDS

Blends of crystallizable poly(vinyl alcohol) (PVA) with poly(N-vinyl-2-pyrrolidone) (PVPy) were studied by C-13 cross-polarization/magic angle spinning (CP/MAS) n.m.r. and d.s.c. The C-13 CP/MAS spectra show that the blends were miscible on a molecular level over the whole composition range studied, and that the intramolecular hydrogen bonds of PVA were broken and intermolecular hydrogen bonds between PVA and PVPy formed when the two polymers were mixed. The results of a spin-lattice relaxation study indicate that blending of the two polymers reduced the average intermolecular distance and molecular motion of each component, even in the miscible amorphous phase, and that addition of PVPy into PVA has a definite effect on the crystallinity of PVA in the blends over the whole composition range, yet there is still detectable crystallinity even when the PVPy content is as high as 80 wt%. These results are consistent with those obtained from d.s.c. studies.

苯乙烯-丁二烯-苯乙烯/聚乙烯基甲基醚共混体系相容性的FT-IR及DSC研究

嵌段高聚物、均聚物共混体系相容性是近年来研究的热点。本工作以光学显微镜、DSC、FT-IR为手段,研究了三嵌段高聚物苯乙烯-丁二烯-苯乙烯(SBS);SBS-48、SBS-30,SBS-28与聚乙烯基甲基醚共混体系的相容性。DSC结果表明,随SBS中PS含量的升高,体系相容性变好,PS段分子量增大,也有助于体系相容。FT-IR结果表明PVME中COCH_3在1100cm~(-1)附近呈现的双峰的相对强度对体系的相容性十分敏感,而由于苯环C—H振动产生的698cm~(-1)峰位却不象PS/PVME体系那样随相容性的改变而有显著的改变。总而言之,嵌段高聚物SBS/均聚物PVME共混体系中,体系的相容性依赖于嵌段高聚物在体系中的组份含量及嵌段高聚物中PS的重量百分含量,PS段分子量的大小对体系相容性也有影响。

n—C_(12)H_(25)NH_3Br固态相性质的DSC和拉曼光谱研究

用差示扫描量热(DSC)和拉曼光谱方法考察了n-C_(12)H_(25)NH_3Br(DoAB)的固相性质,确定了DoAB固-固结构相变的温度及其焓变,通过6种状态下所对应的拉曼光谱讨论了相变过程中分子构象的变化。

化学法镁钛系高效载体催化剂多活性中心的DSC证据

用高效载体钛催化剂进行乙丙共聚物的合成,已有大量报道,但从聚合产物热分析出发对其催化活性中心的性质进行探讨,报道尚少。我们用化学反应法制备的高效载体钛催化剂进行乙丙共聚反应,所得产物进行热分析结果表明,共聚产物具有很宽的链段序列分布,呈现出吸热双峰模式,与催化体系及其聚合过程ESR分析,共聚物溶剂萃取及其~(13)C-NMR分析结果一起,有力地支持催化体系多活性中心的结论。

DSC法对溶剂在膜中状态的研究

本文用DSC对溶剂在PVA热交联膜、PVA/NaOH膜PVA/MBA膜及PVA/P(AmCoAANa)共混膜中状态进行研究,在溶胀状态下,水存在三种状态即自由水中间水及键合水,水/乙醇溶液则存在自由态及其它状态,在渗透气化状态下,对于PVA/P(AmCoAANa)共混膜,当料液为水时,则有自由态水存在。另外结合测定渗透气化状态下膜中溶剂含量初步探讨了渗透气化机理。

几种缩聚耐热聚合物单体纯度的差示扫描量热(DSC)测定

利用差示扫描量热法测定了缩聚单体的纯度。对于一种新型聚芳醚砜的单体4,4′—二氯二苯砜的纯度在99.0和99.9mol%时,所得缩聚物的比浓粘度分别可达0.36和0.62。提出了适用于缩聚单体纯度DSC测定法的试验程序。采用封闭坩埚,该法可用于升温时有少量升华(或挥发)的单体的纯度测定。