微观结构对天然橡胶的性能影响研究

研究了各牌号天然橡胶结构,以研究微观结构对天然橡胶各性能的影响.本文采用红外光谱(FTIR)、X射线衍射(XRD)、核磁共振(nmR)、热重分析(TG)等多种手段对泰国产1号烟片、马来西亚产3号烟片、马来西亚产1号烟片和印度尼西亚1号标准胶等四种牌号天然橡胶的微观结构进行了表征,并对各牌号天然橡胶硫化胶进行了一系列测试...     

Crystallization of 2‐methyl‐1,3‐propanediol substituted poly(ethylene terephthalate). I. Thermal behavior and isothermal crystallization

Differential scanning calorimetry (DSC) was used to evaluate the thermal behavior and isothermal crystallization kinetics of poly(ethylene terephthalate) (PET) copolymers containing 2‐methyl‐1,3‐propanediol as a comonomer unit. The addition of comonomer reduces the melting temperature and decreases the range between the glass transition and melting point. The rate of crystallization is also decreased with the addition of this comonomer. In this case it appears that the more flexible glycol group does not significantly increase crystallization rates by promoting chain folding during crystallization, as has been suggested for some other glycol‐modified PET copolyesters. The melting behavior following isothermal crystallization was examined using a Hoffman–Weeks approach, showing very good linearity for all copolymers tested, and predicted an equilibrium melting temperature (T_m⁰) of 280.0°C for PET homopolymer, in agreement with literature values. The remaining copolymers showed a marked decrease in T_m⁰ with increasing copolymer composition. The results of this study support the claim that these comonomers are excluded from the polymer crystal during growth. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2592–2603, 2006     

Nucleation Effect of Layered Metal Phosphonate on Crystallization of Bacterial Poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyhexanoate)]

The nucleating effect of zinc phenylphosphonate (PPZn) was investigated on the as‐bacterially synthesized poly(3‐hydroxybutyrate) [P(3HB)] and poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyhexanoate)]s [P(3HB‐co‐3HHx)s] in order to improve their crystallization rate. PPZn is found an efficient nucleating agent on the crystallization of P(3HB) and P(3HB‐co‐3HHx) with low 3HHx unit content. The nucleation mechanism is proposed to be epitaxial nucleation. Both the comonomer‐unit composition and its distribution of P(3HB‐co‐3HHx)s were found exhibiting significant effect on the nucleating effect of PPZn. It is found that PPZn is more efficient on nucleating the crystallization of P(3HB‐co‐3HHx) with a broader comonomer‐unit compositional distribution than that with a narrower distribution.

     

Secondary crystallization and premelting endo‐ and exotherms in oriented polymers

Crystallization in polyamide 6 (nylon 6) fibers during annealing was studied in detail by following the changes that occurred in the neighborhood of crystalline relaxation temperatures, by using wide‐ and small‐angle X‐ray scattering and differential scanning calorimetry (DSC). Two distinct crystallization regimes were observed depending on whether annealing was carried out below or above onset of crystalline relaxation at ～190°C. In fibers annealed below 190°C, minor melting peaks were followed by exothermic transitions. These were attributed to ～1.5% (by weight) of microcrystals formed during annealing that melt and recrystallize during the DSC scan. These microcrystals are nucleated from unoriented amorphous chains between the lamellar stack within a fibril, and are shown to account for the observed increase in the crystalline orientation and decrease in permeability. Fibers annealed above 190°C did not show the exotherm and had significantly fewer microcrystals. The crystallization in this regime was attributed to the growth of existing lamellae, as evidenced by the increase in crystallite size, crystalline density, crystalline orientation, lamellar spacing, and lamellar intensity. The changes at annealing temperatures >190°C are accompanied by increased dyeability, indicative of more open amorphous regions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 447–454, 2006     

Influence of alkyl chain length on the gelation mechanism of thermoreversible gels of regioregular poly(3‐alkyl thiophenes) in xylene

The gelation rates of poly(3‐alkyl thiophenes) (P3AT) are strongly dependent on the pendent alkyl chain length. Poly(3‐hexyl thiophene (P3HT) gels at higher isothermal temperatures than that of poly(3‐dodecyl thiophene), (P3DDT). Gelation rate has been expressed as a combination of a temperature dependent function f(T) and a concentration dependent function (φⁿ); φ being the reduced overlapping concentration of P3AT. From the slope of double logarithmic plot of gelation rate and φ, n values are calculated to be 0.52 and 0.60 for P3HT and P3DDT, respectively. These values are close to the value of percolation exponent β (0.45) for three‐dimensional lattice; so both the gels may approximately obey three dimensional percolation model. The f(T) of gelation rate consists of two steps (i) coil‐to‐rod transformation followed by (ii) fibrillar crystallization. The coil‐to‐rod transition is accompanied by a red shift in the π–π* transition band in UV–vis spectra. Flory and Weaver theory is used to understand the coil‐to‐rod transformation process. The theory of fibrillar crystallization extended to dilute solution has been employed to understand the crystallization process. The results clearly indicate that the activation energy of conformational change (ΔF) is higher for P3DDT than that of P3HT. But the free energy change for the formation of critical size nucleus (Δ G) is lower for P3DDT than that of P3HT. A comparison of ΔF and Δ G values indicate conformational ordering is the rate‐determining step for P3AT with dodecyl substituent whereas crystallization is the rate‐determining step for P3AT with hexyl substituent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2528–2537, 2007     

Crystallization behavior and morphology of polylactic acid (PLA) with aromatic sulfonate derivative

This article provides a detailed investigation of crystallization behavior and morphology of polylactic acid (PLA) in the presence of a nucleating agent: potassium salt of 5‐dimethyl sulfoisothalate, an aromatic sulfonate derivative (Lak‐301). Isothermal crystallization kinetics of PLA melt mixed with Lak at concentrations of 0.25–1 wt % was investigated at a range of crystallization temperature, 140–150 °C. To gain further insight on the effect of Lak, nonisothermal differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), polarized optical microscope (POM), heat deflection temperature (HDT), and rheology were also performed. At 0.25 wt % Lak, crystallinity of PLA increased from 10% to 45%, and in 1 wt % Lak, maximum crystallinity of 50% was achieved. With 1 wt % Lak, crystallization half time reduced to 1.8 min from 61 min for neat PLA at 140 °C. The isothermal crystallization kinetics was analyzed using Avrami model. Values of the Avrami exponent for PLA with Lak were mainly in the range of 3 indicating a three dimensional crystal growth is favored. Crystallization rate was found to increase with increase in Lak content. Observation from POM confirmed that the presence of Lak in the PLA matrix significantly increased the nucleation density. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43673.     

Effects of the catalyst system on the crystallization of polypropylene*

In search of a better understanding of catalyst effects on final product qualities of polypropylene, an attempt was made to establish a correlation between catalyst type, polymer chain structure of homopolymers, crystallization behavior, as well as final morphology and mechanical properties. Conventional Ziegler–Natta catalyst systems as well as novel metallocene catalysts were investigated, and influences of molar mass distribution and chain regularity were investigated as separate factors. Metallocene-based isotactic polypropylene shows some special effects regarding the nucleation density and the correlation between stereoregularity and mechanics that do not fit into the general picture for Ziegler–Natta catalyst based products. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2507–2515, 1999     

间苯二甲酸和邻菲罗啉与Cd（Ⅱ）配位聚合物的合成、表征及晶体结构

在水热条件下,过渡金属离子Cd2＋与间苯二甲酸和1,10-菲罗啉配体反应制得配位聚合物[Cd（m-bdc）（phen）]n（m-bdc=间苯二甲酸根,phen=1,10-菲罗啉）。通过X射线单晶衍射、元素分析、红外、热重分析及荧光对其结构、组成和性质进行了表征。X射线单晶衍射结果表明该配合物为一维链状结构,间苯二甲酸的羧基氧原子分别采用双齿桥联和单齿桥联2种配位方式将相邻的2个Cd2＋连接起来。热重（TG）曲线表明,该配合物的热分解过程均为2个阶段。结合Achar微分法和Coats-Redfern积分法,对其不同阶段的热分解反应动力学参数E、lnA进行了计算。     

Study on the structure of nylon 6 films iodinated before forming. II. Investigation of the crystallization behavior through thermal analysis

Two kinds of amorphous nylon 6 films iodinated before forming from the powders iodinated with 0.2N and 1.0N I₂/KI aqueous solutions were prepared by a melt‐press, and isothermally treated at 20 to 80°C for 1 day to 20 days. Thermal analyses were performed to investigate mainly the crystallization behavior on the treatment. The DSC thermograms for the treated films exhibit three temperature‐groups of endothermic peaks at 60 ～ 70°C, 105 ～ 120°C, and higher than 150°C, which may be associated with the melting of the complex crystal, the relaxed γ‐crystal, and the relaxed α‐crystal, respectively. The film containing less I₂/KI and treated at the higher temperature exhibits the peaks associated with the more stable type of crystal. The peak temperature generally increases with the treating temperature and time. On the occasion of there being two peaks associated with the γ‐crystal and the α‐crystals, ΔH for the α‐crystal increases while that for the γ‐crystal decreases with increasing the treating time. The TG curves indicate two temperature‐zones of weight loss by the volatilization of I₂ from I₅^? and the decompositions of I₃^? and nylon 6. With increasing treating temperature, the % weight loss by the volatilization of I₂ decreases, and consequently the temperature of the weight loss by the decomposition of nylon 6 increases. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1062–1069, 2004     

Thermotropic liquid crystalline polyphenylphosphates containing aryl ester mesogens

A series of main‐chain liquid crystalline polyphosphate esters with varying center core in a triad ester mesogen were prepared. The phosphorus is incorporated in the middle of the spacer unit. All the monomers and polymers were characterized by spectral and thermal techniques. Thermogravimetric analysis shows that these polymers were stable up to 295–340°C. The char yields of the polymer were in range of 11–31%. Differential scanning calorimetry (DSC) thermal analysis confirms the mesophase formation of the polymers. Some of the polymers exhibited micro‐grainy textures with low glass transition. The DSC and microscopic analysis reveal that the polymer containing central unit which increases the aspect ratio shows liquid crystalline properties, whereas the unit that decreases the aspect ratio failed to show the mesophase formation. Energy minimized structures for the mesogenic units reveal that the polymers containing phenyl, pyridazine, diphenyl ester, and biphenyl unit shows high aspect ratio compared to nonmesogenic phenolphthalein, bisphenol‐A, and bisphenol‐S units. It revealed that increasing the length of the mesogen and incorporating heteroatoms in the aromatic moiety increased the mesophase stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3924–3930, 2007     

Characterization of polyhydroxybutyrate biosynthesized from crude glycerol waste using mixed microbial consortia

This study focused on the characterization of polyhydroxybutyrate (PHB) produced from crude glycerol (CG) using mixed microbial consortia (MMC). PHB recovered from two biomass drying treatments (65°C oven drying and lyophilization) was characterized comparatively along with a commercially sourced PHB (PHB‐C). Characterization results showed that oven‐drying method caused PHB partial hydrolysis, as indicated by its lower molecular weight (M_w) (PHB‐O, 144,000 g mol^?1), which further affected its physical and chemical properties. Lyophilization helped alleviate PHB hydrolysis during drying process, leading to PHB (PHB‐L) of higher M_w (309,000 g mol^?1) and material properties comparable with commercial PHB. Furthermore, crystallization and morphological studies showed that PHB‐L featured faster crystallization rates and smaller spherulites as compared with PHB‐C, probably due to its lower M_w. In general, the results from this study suggested that CG‐MMC‐derived PHB‐L possessed material properties comparable with those of pure substrate/culture produced PHB. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

低分子量PVA对PVA共混体系熔融结晶行为的影响

通过熔融挤出制备了低分子量PVA(PVA0599)改性PVA(PVA1799)共混材料,采用差示扫描量热法(DSC)、X射线衍射(XRD)和偏光显微镜(PLM)研究了PVA0599对PVA共混体系熔融结晶行为的影响,结果表明:低分子量PVA的加入降低了共混材料的熔点和结晶度,且随低分子量PVA含量的增加,共混材料的结晶速率先增加后减小,当加入20%的PVA0599时,结晶速率达最大。共混材料的球晶尺寸随低分子量PVA含量增加逐渐减小,低分子量PVA在一定程度上降低了PVA的结晶能力,抑制了其结晶。     

Molecular fractionation in melt-crystallized polyethylene: 1. Differential scanning calorimetry

This is the first paper in a series in which molecular fractionation (segregation) in melt-crystallized polyethylene (PE) has been studied by differential scanning calorimetry (d.s.c.). A number of PE's (both high- and medium-density materials) have been given a variety of thermal treatments, including isothermal crystallization from the melt and annealing. The melting of the samples as registered by d.s.c. has been extensively analysed and information regarding the crystallization, particularly in relation to molecular fractionation, is presented.     

高分子甲醛吸收剂对聚甲醛的热稳定性能与结构的影响研究

采用差式扫描量热仪、热重分析仪及偏光显微镜研究高分子甲醛吸收剂共聚酰胺(COPA)和密胺树脂(MF)对聚甲醛(POM)的热稳定性能与结构的影响。结果表明,两种高分子甲醛吸收剂都能起到结晶成核剂的作用。同时,COPA对POM的热稳定性效果要优于MF,但会提高POM的黄色指数,而MF会降低POM的黄色指数。