一组线型聚苯乙烯和星形支化聚苯乙烯的凝胶色谱与热场流分级方法的比较

本文应用热场流分级方法,在两种不同的场强下(△T=30℃、△T=50℃),测试了一系列窄分布聚苯乙烯标样和星形支化聚苯乙烯的淋出体积V_r和分子量M的依赖关系。星形支化物的臂数不同,但臂的分子量相同,上述样品进行了GPC测试,实验表明,由TFFF得到的支化的与线型聚苯乙烯在V_r～M关系上的差别大于GPC的结果,表明链结构对扩散系数的影响大于对分子体积的影响。     

SILICA-SUPPORTED NICKEL AND ZIRCONIUM CATALYSTS FOR BRANCHED POLYETHYLENE*

8-Aminoquinoline nickel dichloride and bis(cyclopentadienyl)zirconium dichloride (Cp_2ZrCl_2) were supportedsimultaneously on silica to produce branched polyethylene successfully by combined polymerization. The supportedpolymerization results showed that the molecular weight of polyethylene increased while the molecular weight distributionbecame wider and the molecular chains of oligomers remaning in the final solution became shorter as compared to theoligomers obtained in polymerization processes with pure 8-aminoquinoline nickel dichloride catalysis, as well as theCp_2ZrCl_2 and nickel combination system. With decreasing amount of Ni catalyst in the supported catalyst, the molecular chains of oligomers in the resulting solution became shorter, while α-olefin selectivity increased.     

星形聚苯乙烯的动态力学性能

星形聚合物是近年发展的新材料。本工作用扭辫分析(TBA)方法研究了以二乙烯基苯微凝胶为核的星形聚苯乙烯的动态力学性能。这方面的工作尚未见报导。     

13－臂星形文化聚苯乙烯的某些溶液性质

本文对合成的四个不同分子量的１３－臂星形聚苯乙烯试样，用ＧＰＣ－粘度计联用装置对之进行了测定，用良溶液剂中的粘度数据，通过一定的线性外推，得到它们在θ条件下的ｇθ因子（＝＜η＞ｂ，θ／＜η＞ｌ，θ）。良溶剂中的ｇ’因子（＝＜η＞ｂ／＜η＞ｌ）和ｇθ因子之间存在的差异以及ｇθ因子与ｇθ因子（＝Ｓｂ＾２，θ／Ｓｌ＾２，θ）间关系式ｇθ’＝ｇθ＾ｅ中ε的选值问题进行了详细的实验验证和讨论，并与前文＜７＞     

CROSSLINKING AND COMPATIBILIZATION IN BLENDS OF POLYSTYRENE AND POLYETHYLENE

This paper investigated the influences of butadiene rubber (BR) and dicumylperoxide (DCP) on thermal and rheological behaviour, morphology and mechanical proper-ties of PS/LLDPE/SBS blend. Addition of DCP alone was found to decrease the mechanicalproperties of PS/LLDPE/SBS blend due to the decomposition of PS. When BR was addedtogether with DCP, it is found that the co-crosslinking of BR, SBS and PE takes place,and the decomposition of PS is reduced simultaneously because of the consumption of thefree radicals in the crosslinking process. Synergism was thus realised which resulted in theimprovement of the ductility of blend.     

ASPHERICITY AND PROLATENESS OF LINEAR AND CIRCULAR MACROMOLECULES

The shape asymmetry of gaussian models of linear and circular macromolecules hasbeen numerically invesigated in terms of asphericity and prolateness parameters. Theseparameters are found to decrease with increasing length for the macromolecule eitherconfined to a plane or in three dimensions. The effect of dimensionality on theseparameters is visible only for low dimensions and is generally weak. As dimensionality goesto infinity, it is found that asphericity and prolateness for both chains and rings approachslowly yet descendingly values of corresponding asphericity and prolateness factors, withthe exception of the chain which shows a minimum value of asphericity when theembedding space has a dimensionality of four.     

PREPARATION OF Au/SULFONATED POLYSTYRENE CATALYSTS FOR LOW-TEMPERATURE CO OXIDATION*

Supported An catalysts for low-temperature CO oxidation were prepared by solvated motal atom impregnation(SMAI) and conventional impregnation (CI). X-ray photoelectron spectroscopy (XPS) investigations indicated that theelemental gold in all the samples was in the metallic state. XRD measurements showed that the mean diameters of Auparticles prepared by SMAI were smaller than those prepared by CI with the same gold content. Catalytic tests showed thatthe SMAI catalyst had higher CO oxidation activity than the CI catalyst with the same compositions. Both SMAI and CIcatalysts exhibited high activity in low temperature CO oxidation. Full CO conversion was obtained at 323--383K.     

THERMAL ACTIVATION OF IMMOBILIZED PAPAIN

Papain (Papainase, EC 3.4.22.2) was immobilized on porous silica beadsby cross linking with glutaraldehyde. The thermal activation of this immobilized papainin aqueous system was found at a temperature range from 50 to 90℃. The higher thetemperature, the more active the immobilized papain will possess. At the same time,the durability of the immobilized papain on heating was greatly improved. The effect ofadditives and salts on the activity of the immobilized papain were also studied. The resultsshowed that the additives and some of the salts studied could markedly enhance the activityof the immobilized papain at elevated temperature.     

THERMAL ANALYSIS OF ACRYLIC FIBERS

This is a comprehensive survey of our work during the past thirteen years on the thermal analysis of acrylic fiber, including some recent, unpublished results.     

SOLUTION CRYSTALLIZATION OF METALLOCENE SHORT CHAIN BRANCHED POLYETHYLENE:MORPHOLOGY AND MECHANISM*

Solution crystallization of metallocene short chain branched polyethylene (SCBPE) was carried out and very nicesingle crystals were obtained. Compared with single crystals grown from linear polyethylene, SCBPE single crystals are dirtydue to intermolecular heterogeneity The crystal morphology changes with crystallization temperatures. Lozenge, truncatedlozenge, hexagonal, rounded and elongated crystal morphologies have been found at much lower crystallization temperaturethan in linear polyethylene. The electron diffraction shows there is a possibility that the single crystals may have hexagonalpacking in a crystallization temperature range. The lateral habits of single crystal are discussed based on roughening theories.     

MISCIBILITY, THERMAL STABILITY AND RETENTION OF PVP FOR CROSSLINKED PVA/PVP BLENDS

The thermal behavior, miscibility, crystallite conformation and thermal stability ofcrosslinked(CL-) PVA/PVP blends were studied by DSC and TG methods, respectively. DSCresults showed that in the blend, the crystallinity,T_m and T_c of PVA were obviously lower thanthose of pure PVA; the crystal growth changed from three dimensional to two dimensional andonly a single T_g was detected. These facts demonstrated that this crystalline and amorphousblend have good miscibility. TG curves showed that providing the quantity of K_2S_2O_8 added ismore than 3 wt%,in the blends PVA will form a stable CL-network, whose thermal degradationtemperature was near to that of PVP. But crosslinking reaction will not take place for PVP. Theprocesses of thermal degradation of CL-blends are based on combining both the thermaldegradation of PVP and that of PVA crosslinked with corresponding quantity of K_2S_2O_8 CL-agent, respectively. The UV measurements showed that 75 wt% of PVP may be remained in CL-blend hydrogelscrosslinked by adding (3--5 wt% )K_2S_2O_8. This is mainly due to the stable CL-network formed and the good compatibility and properentanglement between the composites in the CL-blends.     

THERMAL ANALYSIS OF POLYPROPYLENE-b-POLYETHYLENE DIBLOCK COPOLYMERS AND CORRESPONDING BLENDS

Difference in thermal behavior of presumed polypropylene-b-polyethylene block copolymers(PP-PE) and corresponding PP+PE blends was studied. Different views in the literature were unified in our observation that faster cooling rate yielded only one exothermal peak for the blends, while slower cooling rates revealed both PP and PE exothermal peaks. Further details on when a single or double exothermal peaks would appear are discussed. Melting and crystallization temperatures for both PP and PE in blends were found to be a few degrees higher than for PP and PE in block copolymers. Thus, thermal analysis can be used to identify PP-PE block copolymers. These phenomena and the lower △H_f-values of PP and PE in block copolymers than the △H_f-values of pure homo-PP and -PE (for PE even more so) are explained in terms of restricted block movement due to covalent bond between blocks and of crystallization processes in block copolymers. The presence of block structure in the PP-PE samples studied is inferred.     

THE SYNTHESIS OF MACROPOROUS CROSSLINKED POLYSTYRENE AMIDOPHOSPHONIC ACID

A series of macromolecular copolymers of styrene and divinyl-benzene were prepared in the presence of iso-octanol or 2-ethyl butyl alcohol. The factors which affected the physical structures of the copolymer were discussed. The macroporous amido-phosphonic acid resin was obtained after the acetylation, phosphonylation and amination of the crosslinked polystyrene. The factors which affected each reaction were studied and the change of physical structures of the copolymer were discussed.     

SYNTHESES OF POLYSTYRENE RESINS CONTAINING POLYETHER OLIGOMERS AND THEIR EXTRACTION FOR GOLD (Ⅲ)*

Three polystyrene resins containing polyether oligomers as extractants were synthesized andtheir extraction properties were studied. Gold (III) ion could be extracted rapidly by the resins(T_(1/2),相似文献   

SYNTHESIS AND THERMAL PROPERTIES OF A NEW CHOLIC ACIDCONTAINING COPOLYMER

A new copolymer was synthesized by free radical polymerization in solution from methyl 3α-methylacryloyl-7α, 12α-dihydroxy-5β-cholan-24-oate (MACAME) and maleic anhydride (MAN). The copolymer was characterized by FT-IR and functional group analysis. The reactivity ratios of the two monomers were estimated [r_1 = 11.6 (MACAME), r_2 = 0.01(MAN)] by conducting a series of copolymerizations with a variety of monomer feed compositions and analyzing thecopolymer composition. Thermogravimetric and differential scanning calorimetric analyses of the samples indicate that thecopolymer possesses good thermal stability. The temperature at which the copolymer samples experienced a 10% weight loss(T_(WL)) is over 287℃, and the T_g ranged from 174 to 185℃ for the copolymers.     

RADIATION CROSSLINKING OF BRANCHED POLY (VINYL ACETATE)

In the present work, radiation crosslinking of different branched poly (vinyl acetate) have beemstudied and the validity of the relationship between sol fraction and radiation dose: R(S+S~(1/2)=1/U_(1qo)+p′_o/q_oR~βto branched poly(vinyl acetate) have been assured.     

CRYSTALLIZATION AND MECHANICAL PROPERTIES OF BLENDS OF METALLOCENE SHORT CHAIN BRANCHED POLYETHYLENE WITH CONVENTIONAL POLYOLEFINS

Metallocene-catalyzed short chain branched polyethylene (SCBPE) was blended with LDPE, HDPE, PS, EPDM and iPP in the weight proportions of 80 and 20. The crystallization and mechanical properties of these blends were studied by PLM, DSC and DMA. It has been observed in PLM that SCBPE/LDPE, SCBPE/HDPE and SCBPE/EPDM can form band spherulites whose band width and size are both smaller than that of the pure SCBPE. Tiny crystallites are observed in the completely immiscible SCBPE/PS blend. The crystallites in SCBPE/iPP are very small and only irregular spherulites are seen. The crystallization kinetics and mechanical properties of SCBPE are greatly affected by the second polyolefin, but in a different way, depending on the phase behavior and the modulus of the second components. SCBPE may be phase miscible in the melt with HDPE, LDPE and EPDM and co-crystallize together with HDPE or LDPE during cooling. A big change of crystal morphology and crystallization kinetics is seen in SCBPE/iPP blend compared with pure SCBPE and the lowest tanδ is also seen for this system. DMA results show that the tensile modulus of the blends has nothing to do with phase behavior, but only depends on the modulus of the second component.     

CHARACTERIZATION OF COMPOSITIONAL HETEROGENEITY OF SEGMENTED COPOLYMERS BY GPC TECHNIQUE

The GPC technique wth two detectors has been used to study the heterogeneity in compositionthard segment content) of a series of polyethylene terephthalate/polycaprolactone segmented copoly-mers. Improvement in data treatment has been made to avoid the difficulty resulted from the lake oflow molecular weight hard segment homopolymers. Results show that for each sample the moleculesof larger coil size in CHCI_3 usually have higher hard segment content. A parameter, the averagedeviation of hard segment content, has been proposed to characterize the heterogeneity in compositionof the samples. It is found that the heterogeneity of the samples increases with increasing theiraverage hard segment content.     

梳形支化聚苯乙烯模型化合物的合成及表征

本文用阴离子聚合的聚苯乙烯进行氯甲基化,再将此带有活泼氯的甲基化聚苯乙烯作为主链与活性聚苯乙烯阴离子偶合接枝,制备了12个具有等长度支链沿主链无规分布的、结构明确的梳形聚苯乙烯模型化合物,并用GPC—粘度计联用装置对之进行了表征.     

SYNTHESIS AND THERMAL PROPERTIES OF POLYBENZOXAZOLE FROM SOLUBLE PRECURSOR WITH HYDROXY-SUBSTITUTED POLYENAMINONITRILE

Aromatic polybenzoxazole (PBO) precursor, hydroxy-substituted polyenaminonitrile, was prepared by direct polycondensation of 1,4-bis(l-chloro-2,2-dicyanovinyl)benzene (CCB) and 4,6-diaminoresorcinol dihydrochloride (DAR) using pyridine and N,N-dimethylacetamide as condensing agent and solvent. The precursor has good solubility in polar aprotic solvent which is due to the strong dipolar nature of the main chain. The soluble precursor was subjected to thermal cyclization in an inert atmosphere to convert it into the corresponding PBO, which has its 5% weight loss temperature at 540℃ The fully cyclized PBO were characterized by FT-IR and TGA. The introduction of 10% mol 1,3,5-benzenetricarboxylic chloride (BTC) into the main chain not only has little effect on the solubility of PBO precursor but also raises its 5% weight loss temperature to 552℃ and char yield at 700℃ for the cyclized PBO with BTC.