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Thermal Properties and Three-Phase Structure of cis-1,4-Polybutadiene~!2009-11-20~!2009-12-15~!2010-04-20~! 顺式-1,4-聚丁二烯的热性质及三相结构
Pub Date : 2010-05-04 DOI: 10.2174/1874343901004010015
M. L. Lorenzo
The thermal properties of cis-1,4-polybutadiene (cis-PBD) were investigated in dependence of content of cis units and of linearity of the main chain. cis-PBD grades containing a fraction of cis-segments ranging from 93 to 98 %, and with linear or branched chains, were analyzed. Upon isothermal crystallization from the melt at -26 °C for 1 h, followed by cooling to below the glass transition temperature, cis-PBD develops a three-phase structure, where the mobile amorphous phase is equal to 0.41, independently of chain structure, crystallinity ranges from 0.23 to 0.28, and the rigid amorphous fraction varies from 0.31 to 0.35. Up to three main endotherms can be evidenced by calorimetry at slow heating rate, depending on chain regularity. The multiple melting behavior was discussed on the basis of the three-phase structure, as well as of crystallization kinetics.
研究了顺式-1,4-聚丁二烯(cis- pbd)的热性能与顺式单元含量和主链线性的关系。分析了含有93 - 98%顺式片段的顺式pbd等级,以及线性链或支链。熔体在-26℃下等温结晶1 h,冷却至玻璃化转变温度以下,顺式pbd形成三相结构,其中流动非晶相为0.41,与链结构无关,结晶度为0.23 ~ 0.28,刚性非晶部分为0.31 ~ 0.35。在慢加热速率下,根据链的规律性,量热法可以证明多达三个主要的恒温体。在三相结构和结晶动力学的基础上讨论了多重熔融行为。
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引用次数: 1
Polyolefin-Clay Nanocomposites from Olefin Polymerization between Clay Layers 聚烯烃-粘土纳米复合材料
Pub Date : 2010-01-27 DOI: 10.2174/1874343901004010001
J. Qian, Cun-Yue Guo
This mini-review article addresses the development in synthesizing polyolefin/clay nanocomposites by olefin polymerization under catalysis of clay intercalated precatalysts in recent years. The review comprises three parts which focus on mainly the synthetic route, structural characterization, and properties of polyolefin/clay nanocomposites, respec- tively. Moreover, outlook for future research and development trends is outlined.
本文综述了近年来在粘土插层预催化剂催化下烯烃聚合合成聚烯烃/粘土纳米复合材料的研究进展。本文主要介绍了聚烯烃/粘土纳米复合材料的合成路线、结构表征和性能。并对未来的研究发展趋势进行了展望。
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引用次数: 5
Viscosity, Relaxation and Stability of Natural Rubber 天然橡胶的粘度、松弛和稳定性
Pub Date : 2009-10-23 DOI: 10.2174/1874343900903010041
J. Maláč
Mooney viscosity and Mooney relaxation of unaged and oven aged SMR L natural rubber samples were stud- ied. The viscosity was characterized by ML (1+4) 100°C and the rate of stress relaxation by the exponent a in a power law M = k (t) a . With the increasing time of oven aging at 140°C the decrease of both viscosity and stress relaxation rate expo- nent were observed. Aging of raw natural rubber can therefore be studied by Mooney viscosity and Mooney relaxation tests and obtained results are sensitive enough to be used for characterization of raw natural rubber stability.
研究了未老化和烘箱老化SMR - L天然橡胶试样的穆尼粘度和穆尼弛豫。粘度表征为ML(1+4) 100°C,应力松弛率表征为幂律M = k (t) a的指数a。随着140℃高温时效时间的延长,黏度和应力松弛率均呈下降趋势。因此,可以通过穆尼粘度和穆尼松弛试验来研究天然生胶的老化,所得结果足够灵敏,可用于表征天然生胶的稳定性。
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引用次数: 10
Polymerization in Magnetic Field. XX. Thermal Behavior of the Copolymersof Styrene with 2, 3 Epoxypropyl Methacrylate Synthesized in theMagnetic Field Presence 磁场聚合。XX。苯乙烯与2,3环氧丙基甲基丙烯酸酯共聚物在磁场作用下的热行为
Pub Date : 2009-09-11 DOI: 10.2174/1874343900903010027
L. Nita, A. Chiriac, S. Cimmino, C. Silvestre, D. Duraccio, C. Vasile
The thermal behavior of polystyrene (PS) and of styrene copolymers with 2, 3 epoxypropyl methacrylate (GMA) synthesized in the presence of the magnetic field has been studied. The thermal behavior was investigated by thermogravimetry (TGA) and differential scanning calorimetry (DSC) techniques. The synthesized polymeric latexes were also characterized from the view point of the particle size distribution (70-200 nm) as well as of their stability by de- termining the zeta potential values. The decrease of zeta potential absolute value with the increase of GMA content or growth of the temperature it was observed. At the same time, the increase of zeta potential absolute value corresponds to latexes prepared in the MF presence. The presence of the magnetic field during syntheses increases the swelling capaci- ties, glass transition temperature and thermal stability of both homopolymers as well as of the synthesized copolymers. The behavior was attributed to a potential ordered structure induced by the magnetic field during syntheses upon macro- molecular chains.
研究了在磁场作用下合成的聚苯乙烯(PS)及其与2,3环氧甲基丙烯酸丙酯(GMA)共聚物的热行为。采用热重法(TGA)和差示扫描量热法(DSC)研究了其热行为。从粒径分布(70 ~ 200 nm)和zeta电位值的测定对合成的聚合物乳液进行了表征。zeta电位绝对值随GMA含量的增加或温度的升高而减小。同时,zeta电位绝对值的增加对应于在MF存在下制备的乳胶。合成过程中磁场的存在提高了均聚物和合成共聚物的溶胀能力、玻璃化转变温度和热稳定性。这种行为归因于在大分子链合成过程中磁场诱导的潜在有序结构。
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引用次数: 1
Polyamide 66 Polymorphic Single Polymer Composites 聚酰胺66多态单聚合物复合材料
Pub Date : 2009-09-07 DOI: 10.2174/1874343900903010037
M. Duhovic, P. Maitrot, S. Fakirov
Exploring the polymorphism phenomenon of polyamide 66 (PA 66) a single polymer composite (SPC) was prepared. The matrix was obtained via compression molding and quenching in ice water expecting to comprise the modi- fication with lower melting temperature (Tm). The reinforcement was commercial textile yarn of PA 66, characterized by a higher Tm. Layers of the yarn were sandwiched between matrix films and compression molded at 250 °C, i.e. 10 °C below Tm of the reinforcement. SEM observations revealed the layered structure of SPC as well as a good adhesion between the composite components due to surface premelting. The tensile testing showed, as compared with the matrix, an increase of the initial modulus by 28% and of the tensile strength by 160% when the reinforcing component of the SPC amounted to only 20 wt%. Optimization of the preparation conditions, including variation of the matrix/reinforcement ratio as well as trialing of other polyamides, is in progress.
研究了聚酰胺66 (pa66)的多态现象,制备了一种单聚合物复合材料(SPC)。通过压缩成型和在冰水中淬火得到基体,期望包含较低熔化温度(Tm)的改性。补强材料为具有较高Tm的PA 66商用纺织纱。纱线层被夹在基质薄膜之间,在250°C下压缩成型,即比增强材料的Tm低10°C。SEM观察表明,SPC具有层状结构,由于表面预熔,复合组分之间具有良好的附着力。拉伸试验表明,与基体相比,当SPC的增强成分仅为20%时,初始模量增加28%,抗拉强度增加160%。制备条件的优化,包括基质/增强比的变化以及其他聚酰胺的试验,正在进行中。
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引用次数: 26
Competitive Supramolecular Encapsulation of Amphiphilic HyperbranchedPolymers Made from A2 and BB’2 Type Monomers. 1. Polyadditionof 1-(2-aminoethyl)piperazine to Divinyl Sulfone 由A2和BB ' 2型单体制备的两亲性超支化聚合物的竞争性超分子包封。1-(2-氨基乙基)哌嗪与二乙烯基砜的聚合加成
Pub Date : 2009-04-16 DOI: 10.2174/1874343900903010012
Jiayan Wu, Cuihua Liu, Chao Gao
The competitive host-guest encapsulations of palmityl chloride-modified amphiphilic hyperbranched poly(amido-amine) (HPAMAM-PC) and poly(sulfone-amine) (HPSA-PC) to selected pairs of dyes are reported. Water- soluble and chloroform-insoluble dyes, such as methyl orange (MO), methyl blue (MB), rose bengal (RB), fluorescein so- dium (FSS), eosin Y (EY) and phloxine B (PB), can be transferred from aqueous phase into chloroform phase by the HPAMAM-PC and HPSA-PC. UV/Vis spectra were used to determine the loading capabilities (Cloads) of different dyes in the case of single-dye encapsulations (Exp I). Four pairs of dyes: (1) MO and RB, (2) MO and PB, (3) MO and EY, (4) MO and FSS, were chosen to perform comparative experiments to investigate the influence of competitive interactions on the Cloads of dye pairs. As a result, in the cases of one-step double-dye encapsulations (Exp II) and gradual double-dye en- capsulations (Exp III), we found three kinds of competitive relationships: (1) The Cload of MO decreased significantly in the presence of either RB or PB, compared with the Cload in the single-dye encapsulation, while the existence of MO did not affect the encapsulations to RB and PB greatly, (2) the Cloads of both dyes decreased if they were encapsulated simul- taneously by HPAMAM-PC or HPSA-PC (MO & EY), (3) FSS can hardly be encapsulated by the hyperbranched poly- mers with the existence of MO in the aqueous solution. 1 H NMR, FTIR and thermogravimetric analysis (TGA) were used to confirm the resulting competitive encapsulations. Relatively selective constant to MO (Rdye/MO) was defined to measure the competitive ability of each dye to MO quantitatively. The competitive abilities of RB, PB were larger than that of MO, while EY almost equal to MO and FSS lower than MO. The size of the dye molecules, electrostatic acid-base interactions between the dye molecules and the polymers, the interaction between different dyes were considered to be the main causes of the results.
报道了棕榈酰氯修饰的两亲性超支化聚氨基胺(HPAMAM-PC)和聚砜胺(HPSA-PC)在选定染料对上的竞争性主-客包封。甲基橙(MO)、甲基蓝(MB)、玫瑰红(RB)、荧光素钠(FSS)、伊红Y (EY)和苯氧辛B (PB)等水溶性和氯仿不溶性染料可通过HPAMAM-PC和HPSA-PC从水相转移到氯仿相。利用紫外/可见光谱测定了单染料包封情况下不同染料的负载能力(Cloads)(实验1)。选择四对染料:(1)MO和RB, (2) MO和PB, (3) MO和EY, (4) MO和FSS进行对比实验,研究竞争相互作用对染料对负载的影响。因此,在一步双染料胶囊化(实验II)和渐进式双染料胶囊化(实验III)的情况下,我们发现了三种竞争关系:(1)与单染料包封相比,在RB或PB的存在下,MO的包封量显著降低,而MO的存在对RB和PB的包封量影响不大;(2)两种染料同时被HPAMAM-PC或HPSA-PC (MO & EY)包封时,两种染料的包封量均有所降低;(3)水溶液中有MO存在时,超支化聚合物对FSS的包封效果较差。1h NMR, FTIR和热重分析(TGA)证实了所得到的竞争性封装。定义对MO的相对选择常数(Rdye/MO),定量衡量各染料对MO的竞争能力。RB、PB的竞争能力大于MO,而EY几乎与MO相当,FSS的竞争能力低于MO。染料分子的大小、染料分子与聚合物之间的静电酸碱相互作用、不同染料之间的相互作用是造成这一结果的主要原因。
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引用次数: 5
Nonisothermal Crystallization Behavior of In-Situ Formed Polyethylene/Montmorillonite (PE/MMT) Nanocomposites Through Ethylene Copolym-erization 乙烯共聚原位形成聚乙烯/蒙脱土纳米复合材料的非等温结晶行为
Pub Date : 2009-03-06 DOI: 10.2174/1874343900903010006
B. Shi, Cun-Yue Guo, Y. Ke, Mingge Zhang, You-liang Hu
PE/MMT nanocomposites containing different amount of MMT were measured for isothermal crystallization. The combination of Ozawa equation and Avrami equation was found applicable in explaining the crystallization behavior of the nanocomposites. In certain range of MMT loadings, MMT particles played the role of nucleating agents that pro- moted the crystallization rate of the polymer matrix, thus making the adjustment of the crystallinity of PE nanocomposites flexible and convenient.
采用等温结晶法测定了含不同量MMT的PE/MMT纳米复合材料的结晶性能。发现Ozawa方程和Avrami方程的组合可以很好地解释纳米复合材料的结晶行为。在一定的MMT负载范围内,MMT颗粒起到成核剂的作用,促进了聚合物基体的结晶速率,从而使PE纳米复合材料结晶度的调节变得灵活和方便。
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引用次数: 6
Proteolytic Degradation of Silk Fibroin Scaffold by Protease XXIII 蛋白酶水解丝素蛋白支架的研究
Pub Date : 2009-03-06 DOI: 10.2174/1874343900903010001
P. Srihanam, W. Simchuer
Two-dimensional silk scaffolds were directly spun on the glass plates by Bombyx mori (called locally Nang- Lai) silkworms and used as subject for proteolytic degradation study with protease XXIII. The silk scaffolds were incu- bated with enzyme solution at 37 °C up to 10 weeks. Those of the scaffold properties: surface morphology, secondary structure, mass loss, degradation ratios and particle sizes were investigated. Silk fibroin scaffolds slightly changed of their structure after exposure to the protease. They were also loose of mass greater than 20% at the end of enzyme incubation periods. Much degradation of the scaffolds was quickly during the 4 weeks and scattering of the particle sizes between 1 to 15 μm were found. The results suggested that protease XXIII is an enzyme which could be degraded of the silk fibroin. Therefore, it will be used this enzyme as model study or for preparing silk material for further applications.
利用家蚕直接在玻璃板上纺出二维丝支架,并利用蛋白酶XXIII进行蛋白水解降解研究。酶液37℃孵育10周。研究了支架的表面形貌、二级结构、质量损失、降解率和粒径等性能。蛋白酶作用后丝素蛋白支架结构发生轻微变化。在酶孵育期结束时,它们的质量也大于20%。在4周的时间内,支架的降解速度很快,颗粒大小在1 ~ 15 μm之间出现了散射。结果表明,蛋白酶XXIII是一种能够降解丝素蛋白的酶。因此,该酶可作为模型研究或用于制备蚕丝材料,进一步推广应用。
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引用次数: 9
The Growth Process of the Soluble Cross-Linked Macromolecule of PU 聚氨酯可溶交联大分子的生长过程
Pub Date : 2009-01-02 DOI: 10.2174/1874343900802010080
F. Li, P. Jiang, Boyue Wu, Rui-rui Sun, Jun Chen, Dongping Liu, L. Zhong, Yanfen Wang
TEM pictures that were taken at different polymerization times during the formation process of the in- tramolecularly cross-linked macromolecule (ICM) indicate that ICM growth undergoes three stages. At the first stage, monomers (i.e. prepolymers) react with each other to form small coils, called "dot molecules" (DM), which are shown as small black dots in TEM pictures. At the second phase, the reaction of functional groups on the surface of DMs produces globular intramolecularly cross-linked macromolecules which are called pre-ICMs. At the third stages, the globular pre- ICMs react with each other to form ICMs. As soon as DMs formed, they aggregate into molecular cluster. DMs are re- stricted within the molecular cluster. This state of aggregation is beneficial to reaction between DMs, since a higher fre- quency of collision can occur in the molecular cluster. In fact, the molecular cluster is the key polymerization site in the controllable cross-linking polymerization system.
分子内交联大分子(ICM)形成过程中不同聚合时间的TEM图像表明,ICM的生长经历了三个阶段。在第一阶段,单体(即预聚物)相互反应形成小线圈,称为“点分子”(DM),在TEM图片中显示为小黑点。在第二阶段,DMs表面官能团的反应产生球形分子内交联大分子,称为预icms。在第三阶段,球状的预icm相互反应形成icm。dm一旦形成,就会聚集成分子簇。DMs被限制在分子簇内。这种聚集状态有利于DMs之间的反应,因为在分子簇中可以发生更高频率的碰撞。实际上,分子簇是可控交联聚合体系中的关键聚合位点。
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引用次数: 0
Synthesis and Electrical Characterization of Self-Supported Conducting Polypyrrole-Poly(vinylidene fluoride) Composite Films 自支撑导电聚吡咯-聚偏氟乙烯复合薄膜的合成及电学特性
Pub Date : 2009-01-02 DOI: 10.2174/1874343900802010074
Manish Taunk, A. Kapil, S. Chand
We report the synthesis of polypyrrole composite films by chemical oxidation polymerization of pyrrole dif- fused inside poly(vinylidene fluoride) matrix and temperature dependant dc conductivity study of these composite films. Ammonium persulfate is used as an oxidizing agent and HCl as the dopant in aqueous medium. This technique produces highly conductive, flexible and free standing polymer composite films in semi-interpenetrating architecture. It is observed that conductivity of the composite films can be controlled by varying the dopant concentration. The variation of conduc- tivity with temperature indicates the semiconducting nature of these composite films. The temperature dependence of conductivity is explained in the light of two different models from which activation energy (Ea) and other hopping pa- rameters are determined. Experimental data fits well with variable range hopping model and three dimensional charge transport mechanism is shown to occur in these films.
本文报道了吡咯在聚偏氟乙烯基体内扩散的化学氧化聚合法制备了聚吡咯复合膜,并研究了复合膜的直流电导率随温度的变化规律。在水介质中以过硫酸铵为氧化剂,盐酸为掺杂剂。该技术可生产具有半互穿结构的高导电性、柔性和独立的聚合物复合薄膜。观察到复合膜的电导率可以通过改变掺杂剂浓度来控制。电导率随温度的变化表明复合薄膜具有半导体性质。用两种不同的模型解释了电导率的温度依赖性,由此确定了活化能(Ea)和其他跳变参数。实验数据与变程跳变模型吻合较好,证明了薄膜中存在三维电荷输运机制。
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引用次数: 13
期刊
The Open Macromolecules Journal
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