顺-1,4-聚丁二烯的本体结晶和溶液结晶

以稀土催化剂聚合得到的聚丁二烯(Ln-PB)的顺式含量接近99%,支化度小,分子具有较高的规整性。本工作用电镜,线膨胀仪、体膨胀仪、DSC、GPC、X-光衍射等实验方法在较宽的分子量范围和结晶温度范围下对Ln-PB的本体结晶和溶液结晶行为进行了研究。     

两嵌段共聚物PB-PDMS中PDMS的结晶行为与共聚物形态结构的关系

聚二甲基硅氧烷(PDMS)的结晶熔融温度(T_m)约为-43℃,远高于其玻璃化转变温度(T_g)(-124℃),为扩大其低温使用范围,需要破坏其链结构规整性以抑制结晶发生。但是我们发现在前人工作中,含PDMS段的嵌段共聚物,即使不破坏PDMS段的链结构规整性,其动态力学谱上有时也观测不到PDMS的结晶峰。遗憾的是这些作者末曾对这一不寻常现象给予足够的重视。无疑,搞清共聚物中PDMS不寻常结晶行为同共聚物形态结构的关系,对提高含有PDMS段的嵌段型热塑性弹性体的低温使用范围将有指导意义。本文报导PB-PDMS中的结晶行为与共聚物形态结构的关系。     

顺丁橡胶的聚集态结构及其拉伸行为

用电子显微镜及光学显微镜研究了高顺式1,4-聚丁二烯橡胶的聚集态结构及其对力学性能的影响。观察了样品的低温结晶、室温下的溶胶和凝胶结构,及其拉伸和松弛过程。证明在室温下,无定形结构的顺丁橡胶内部并不是均匀的,而是具有一定规整度的区域所组成。其基本单元为链结(nodule),链球(Aggre-gation of nodules),及胶团(cluster of gel)。结构单元及其连接均与分子量及凝胶含量有关。这些结构因素均通过超分子结构而影响拉伸及松弛行为。     

稀土丁二烯-异戊二烯无规共聚物低温转变的研究

本文研究了稀土丁二烯-异戊二烯无规共聚物的低温转变性能。实验证明,这类聚合物的玻璃化转变温度、结晶速率和最大主级结晶值都随共聚比的变化而变化,当丁/异戊重量组成比为84/16时,系不完全结晶橡胶。从丁二烯-异成戊二烯共聚物(不同共聚比)的最大结晶速率温度(Tc_max)用外推法可求得稀土顺丁橡胶的最大结晶速率温度为-72℃,这在文献上尚未见报导。稀土顺丁橡胶的玻璃化温度(T_g)为-113℃,其Tc_max(°K)/T_g(°K)=0.796,而天然橡胶的Tc_max(°K)/T_g(°K)=0.814,两者具有与0.80相近的值。     

高顺式-1,4-立构规整丁戊橡胶的合成与性能研究

采用非茂PNP型稀土钇催化剂1催化丁二烯和异戊二烯无规共聚合,制备出了异戊二烯摩尔含量为11%～53%,高顺式-1,4-立构规整的丁戊橡胶。通过~1H NMR、~(13)C NMR和GPC对所得共聚合的微观结构、立构规整性以及分子量及其分布进行了表征分析。采用密炼、开炼两步法将该系列丁戊橡胶与炭黑、各种助剂进行混炼和硫化成型。通过拉伸、阿克隆磨耗和动态热机械分析等实验,研究了异戊二烯含量、分子量大小等因素对丁戊橡胶硫化胶拉伸强度、撕裂强度、磨耗性能及其玻璃化转变温度和结晶性能的影响规律。     

X-射线衍射法研究稀土催化丁二烯异戊二烯共聚物低温下的结晶

本工作用WAXD法对以环烷酸稀土盐为主的催化剂合成的丁二烯和异戊二烯共聚物(Ln-PBI)在低温下的结晶行为进行了研究。Ln-PBI室温下为非晶态,在低温下,异戊二烯含量(重量)>20%时不能生成结晶;含量(重量)<20%时,可观察到结晶的生成。并且结晶度随结晶温度的下降而增加,晶格常数则逐渐减小。Ln-PBI基本上保持了Ln-PB单斜晶系的结晶结构,其晶区由Ln-PB链段所贡献。     

X-射线衍射法研究稀土顺-1,4-聚丁二烯低温结晶动力学

本文用广角X-射线衍射法(WAXD)研究了稀土催化聚合顺-1,4-聚丁二烯(Ln-PB)低温下分子量和温度对结晶过程的影响.随着分子量的改变,结晶速度在M_η=8×10~5左右有一极小值;在M_η=29×10~5左右有一极大值.最大结晶速度发生在T_(c,max)=-60～-70℃之间.最大平衡结晶度值,在M_η大于10~6以上与分子量无关,而最大平衡结晶度值所对应的温度与M_η呈线性关系.随着温度上升,晶胞参数略有增大.Ln-PB主级结晶属于非均相成核,以原纤状和盘状混合生长.     

SO_4~(2-)/ZrO_2-TiO_2固体超强酸的制备

用低温陈化和添加稀土添加剂 (硝酸镧 )的方法制备了 SO2 - 4/Zr O2 -Ti O2 固体超强酸 ,用 IR和 XRD对样品进行了表征 .并通过在 3 5℃条件下催化正丁烷异构化反应和流动指示剂法考察了 Zr和 Ti的摩尔比以及稀土添加剂对样品的酸性和催化活性的影响 . IR和 XRD谱图显示 ,该条件下制备的样品具有较多的超强酸位 ,其晶体为 Ti O2 的锐钛矿晶相结构     

稀土聚乙烯的形态结构及性能

本文研究了用稀土催化剂聚合得到的聚乙烯(稀土聚乙烯)的结构及性能。发现初生聚乙烯粉末具有条状形态结构,其支化度、结晶度及晶粒尺寸均与低压聚乙烯相似,但其熔点和特性粘数较高。用各种物理方法初步证明,稀土聚乙烯熔点较高的原因可能与其具有伸展链结晶结构有关。     

分子结构对1,2-聚丁二烯橡胶性能的影响

本文研究了分子链结构、分子量及其分布对钼催化聚合1,2-聚丁二烯(1,2-PB)的加工工艺性能及硫化胶性能的影响.实验发现,1,2-PB的加工工艺行为随分子量降低和分子量分布加宽而得以改善,其抗湿滑性能随分子链中1,2-结构含量增加而提高,而1,2-结构的空间规整性—间同含量的增加则导致1,2-PB应变诱导结晶、降低硫化胶的弹性和增加生热值。     

Light scattering studies of mixtures and fractions of linear polyethylene

Previous work on the small-angle light scattering of polyethylene films, to determine the supermolecular structure, has been continued. One of the main efforts has been the study of a binary mixture whose low molecular weight component forms well defined spherulites and whose high molecular weight component yields a poorly defined rod-like morphology. The addition of the high molecular weight fraction causes a progressive deterioration of the initial spherulitic morphology; a relatively small amount of the high molecular weight species causes a major decrease in the spherulitic size. However, there are no indications of any spherulitic structures when the weight fraction of the high molecular weight species is 0.5 or greater. The isothermal crystallization of a fraction M = 6.6 × 10⁵ was also studied. Spherulites were formed at low crystallization temperatures while at the higher crystallization temperatures the morphology became nondistinct. Preliminary studies with solvents indicate that high molecular fractions, which do not form spherulites when crystallized in the pure state, do so when crystallized from highly swollen solutions.     

Isothermal crystallization kinetics of poly(ethylene terephthalate)s of different molecular weights

The isothermal crystallization kinetics and morphology of poly(ethylene terephthalate) (PET) polymers of different molecular weights have been studied by means of differential scanning calorimetry and transmission microscopy (TM). The kinetic parameters of Avrami exponent n, the rate constant k, half time t _1/2, rate at 50 % crystallinity, τ _1/2 for crystallization of different PETs were evaluated from double logarithmic plots of log {?ln[1 ? X(t)]} versus log t, where X(t) is extent of crystallinity at a given crystallization temperature. The crystallization rate of polymers with high molecular weight found to be lower than that of polymers with low molecular weight, at the same crystallization temperature. It was found that the nucleation mechanism and growth dimension of polymers with low molecular weight are different from those of polymers with high molecular weight. The results of TM and isothermal crystallization kinetics showed a consistent trend for the crystallization of all PET polymers studied, comprising a primary stage and a secondary stage. The activation energy in the PET polymers of low molecular weight was found to be lower than that of polymers with high molecular weight.     

Morphology and modulus–temperature behavior of semicrystalline poly(ethylene terephthalate) (PET)

The influence of the thermal history on the morphology and mechanical behavior of PET was studied. The degree of crystallinity (density measurements) and the morphological structure (electron microscopy and small-angle x-ray diffraction) depend on the crystallization temperature. The viscoelastic parameters obtained from the modulus–temperature curves are mainly determined by the morphology of the samples. The glass-transition temperature, T_i, is a function of the crystallinity and the crystallization temperature. It is maximum for a crystallinity between 0.34 and 0.39 for a sample crystallized isothermally between 120 and 150°C. This dependence on crystallization conditions is ascribed to the conformation of the amorphous chain segments between the crystalline lamellae as well as the concentration and the molecular weight of the polymer material rejected during isothermal crystallization. Both factors are supposed to be temperature-dependent. The value of the rubbery modulus is a function of both the volume concentration of the crystalline lamellae and the structure of the interlamellar amorphous regions (chain folds, tie molecules, chain ends, and segregated low molecular weight material). Annealing above the crystallization temperature of isothermally crystallized samples has a marked influence on their morphology and mechanical behavior. The morphological structure and the viscoelastic properties of annealed PET samples are completely different from those obtained with samples isothermally crystallized at the same temperature.     

SAPO-5分子筛的晶化过程研究

采用X射线衍射、 X射线荧光光谱、 扫描电子显微镜和固体核磁共振波谱等方法对SAPO-5分子筛的晶化过程进行了研究. 结果表明, SAPO-5分子筛的生成遵循液相晶化机理. 在晶化前期首先生成一种具有较为规整形貌的无定形磷酸铝(记为Am), 晶化温度大于200 ℃后开始出现SAPO-5, 同时无定形物质Am的量也明显增加, 随后Am逐渐溶解并贡献于SAPO-5的生长; 硅原子在晶化初期直接参与晶化进入SAPO-5分子筛骨架, 随着晶化时间延长, 分子筛晶体中硅含量逐渐增加; SAPO-5骨架仅能容纳少量的Si(4Al)物种, 在样品含有较低硅含量时骨架中即出现硅岛. XPS分析进一步揭示SAPO-5分子筛存在表面富硅现象, 硅在晶体中从核到壳含量递增. 研究结果也表明, 分子筛的拓扑结构和硅源选择影响晶体表面富硅程度.     

CHAIN ENTANGLEMENT AND CRYSTALLIZATION OF cis-1, 4-POLYBUTADIENE

The morphological structure and mechanism of nucleation and growth of Ln-PB and Ni-PBwith different molecular weight were investigated by transmission electron microscopy. The crys-tallization of low molecular weight fraction is primarily from predetermined nuclei, crystallizationfor the high molecular weight fraction is primarily from sporadic nuclei. Two types morphologyof spherulite with different lamellar entanglement have been observed. The entanglement of highermolecular weight fractions are found to be of significance in the morphology and rate of crystallizationof polymer.     

稀土顺1,4聚丁二烯的分子缠结与结晶

本文用电镜研究了经过分级得到的不同分子量及不同分子量分布的稀土顺1,4 聚丁二烯(Ln-PB)及镍顺1,4 聚丁二烯(Ni-PB)的低温结晶形态、结晶成核及生长机理。发现低分子量 PB以预现成核为主,而高分子量PB以大分子的缠结为中心的散现成核为主,得到两种不同片层缠结形态的PB球晶。其结晶形态及速率主要受高分子量中的大分子缠结影响。     

茂金属聚乙烯的非等温结晶行为及其动力学研究

为探索分子量和支链含量对聚乙烯非等温结晶过程的影响,选用3组样品:(1)不同分子量的无支链线形聚乙烯;(2)低分子量的支链含量不同的试样;(3)高分子量的支链含量不同的试样.用DSC研究了这3组样品的非等温结晶动力学.结果表明:(1)与支链含量相比,分子量大小对结晶的影响是次要的,但高分子量样品的结晶度比低分子量样品低;(2)支链对聚乙烯的非等温结晶有重要影响,在支化聚乙烯中起决定作用;(3)无论是高分子量试样还是低分子量试样,支化含量增加,聚乙烯的结晶温度、结晶度、结晶动力学以及晶体的熔点等显著降低.     

MORPHOLOGY AND MECHANICAL PROPERTIES OF POLY(ETHYLENEOCTENE) COPOLYMERS OBTAINED BY DYNAMIC PACKING INJECTION MOLDING*

The morphology and mechanical properties of poly(ethylene-octene)copolymers(POE)obtained by dynamic packing injection molding were investigated by mechanical tests,differential scanning calorimetry(DSC),fourier transform infrared spectroscopy(FT-IR)and scanning electron microscopy(SEM).The mechanical tests found that only POE with low octene content and high molecular weight show apparent response for external shear field.Further investigation has been done by DSC,FT-IR,and SEM in order to make clear the reason of that phenomenon.Finally,the hypothetical mechanism of POE microstructure formation under shear field has been proposed.For POE with low octene content and high molecular weight,orientation degree and mechanical properties both increase substantially under shear field.For POE with low octene content and low molecular weight,orientation degree and crystallinity increase under shear field,but it is not dramatically benefit for the mechanical properties.For POE with high octene content and high molecular weight,the shear field has little effect on the morphology and mechanical properties.     

La cristallisation du polydioxolanne

Crystallization kinetics have been studied for two samples of polydioxolan (molecular weights 10.000 and 30.000). The crystallization was followed at temperatures between 0 and 21°C in a DSC calorimeter. The results obey Avrami's equation. The Avrami exponent was found to be two indicating a spontaneous and probably heterogeneous mode of nucleation. Over the temperature range studied, the crystallization lead to the growth of two-dimensional spherulites.The morphology of polydioxolan samples was studied by optical microscopy and small-angle light scattering. Samples crystallized in liquid nitrogen are made of small spherulites of the order of 5 μm. Samples crystallized between 0 and 21°C are made of large spherulites, of the order of 1 mm. Samples crystallized at 25 and 35°C show large and “abnormal” spherulites, made of two optical phases corresponding to the centre and the perimeter.No difference was seen between the morphologies of the two samples studied. In both cases, the time of half-crystallization was the same when plotted as a function of the degree of supercooling. Equilibrium melting points of 79 and 85°C were found for the low and high molecular weight samples, respectively.     

Inter and intra-molecular branching distribution of tailored LLDPEs inferred by melting and crystallization behavior of narrow fractions

Here we report the melting and isothermal crystallization behavior of two sets of fractions obtained from a film-grade metallocene catalyzed ethylene-1-hexene resin with enhanced mechanical properties. One set of fractions was obtained by molecular weight fractionation, the second set was obtained fractionating by content of 1-hexene. The melting behavior, crystallization kinetics and supermolecular morphology of the fractions are analyzed in reference to the behavior of model systems with uniform inter-chain branching content and a random intra-chain distribution. While melting and crystallization kinetics of molecular weight fractions conforms to the bivariate (molecular weight-comonomer content) distribution of the original copolymer, the behavior of 1-hexene compositional fractions indicate a blockier branching distribution in the highly branched high molar mass fractions. Major differences with model random copolymers are also observed in the supermolecular morphology of the latter fractions.