Determination of the molecular characteristics of commercial polyethylenes with different architectures and the relation with the melt flow index

The molecular weight distribution curves of several commercial polyethylene samples were evaluated by high‐temperature gel permeation chromatography with two detectors (a refractive‐index detector and a viscometer) to determine the molecular sizes and architectures (branching). The polymer samples included high‐ and low‐density polyethylenes with different molecular weight distributions (wide, medium, unimodal, and bimodal) from nine producers. The results were tested against the melt flow index and zero‐shear melt viscosity to find correlations. The data for high‐density polyethylene correlated well with the molecular weight, whereas the data for low‐density polyethylene did not correlate. However, when the weight‐average molecular weight was corrected by the branching parameter and a factor form, all the polyethylene samples fit a single equation. These results indicate that the melt flow index is dependent not only on the molecular weight but also on the molecular shape, including branching. The relation accounted for samples of different resin producers, molecular weights (65,000–638,000), and polydispersities (2.9–20). The use of the branching parameter for the correction of the molecular weight allowed the correlation of these parameters despite differences in the technologies, molecular weights, and molecular architectures. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1572–1578, 2007     

Melting Properties of Syndiotactic Polystyrenes and Effect of Hydrogen on Molecular Weight Distribution

Summary: The melting properties of syndiotactic polystyrenes are significantly affected by the structural molecular properties of the polymers. The most important influences on the melting behavior are stereoregularity, molecular weight and molecular weight distribution of the polymers. The melting temperature is increased by an enhanced syndiotacticity at sufficiently high molecular weights and at narrow molecular weight distributions. The degree of syndiotacticity obtained primarily depends on the kind and structure of the cyclopentadienyl ligand of the transition metal catalyst, whereas the effect of the other ancillary ligands on stereoregularity is negligible at the same cyclopentadienyl ligand. At narrow molecular weight distributions with below 2.8 and at constant stereoregularities, the molecular weight has a remarkable effect on the melting behavior at weight‐average molecular weights lower than about 80 000 g · mol^?1, resulting in a significant decrease of the melting temperature until below 230 °C. The presence of hydrogen during polymerization leads to a significant shift to lower molecular weights at comparably small amounts of hydrogen, but results in the occurrence of an additional peak in the molecular weight distribution at larger hydrogen concentrations giving evidence for the formation of a second active polymerization site producing lower molecular weight polymers. At constant stereoregularity, the broadening of the molecular weight distribution leads to decreased melting temperatures and to improved flow properties of the syndiotactic polystyrenes with increasing shear rates at moderate molecular weight distributions.

Detailed molecular weight distributions of syndiotactic polystyrenes in dependence on the hydrogen concentration.     

Controlled rheology of polypropylene: Modeling of molecular weight distributions

A mathematical model for the controlled degradation of polypropylene is presented in this article. A previous model of this process was extended to predict the whole molecular weight distribution of the modified resin. Probability generating functions were applied to transform the infinite set of mass balance equations of both polymer and radicals. The integration of the transformed set of equations yielded the probability generating function transforms. These transforms were then inverted with two different inversion algorithms, recovering the molecular weight distributions of the polymer. The model predictions were compared with our experimental data and other information taken from the literature. Good agreement was obtained. The approach presented here is also useful for other polymerization and postpolymerization processes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1676–1685, 2003     

Effect of microorganisms during the initial coagulum maturation of Hevea natural rubber

The involvement of microorganisms in the initial stage of maturation of natural rubber coagula was assessed with five latex treatments that varied in the initial quantity of microorganisms; the treatments ranged from latex added with an antimicrobial agent (3.4 × 10⁴ CFU/mL) to strongly inoculated latex (2.4 × 10⁷ CFU/mL). After 0–6 days of maturation, the obtained rubber was characterized with respect to its physical and structural properties. The Wallace plasticity (P₀) and plasticity retention index (PRI) remained constant during maturation with the antibiotic‐added treatment. PRI decreased with the maturation time, and the rate was proportional to the initial microorganism concentration. P₀ of all inoculated rubber increased for the first 2 days of maturation and decreased after 6 days of maturation. With respect to structural parameters, a higher initial microorganism content corresponded to a higher gel content and a lower weight‐average molar mass after maturation, drying, and storage. The inoculated rubber showed a stable value for the number‐average molar mass (M_n), in contrast to the noninoculated samples, for which an increase in M_n during maturation was observed. The quantity of microorganisms significantly affected the physical properties and structure of the processed dry rubber. The mechanisms occurring during the initial stage of maturation are complex, and microorganisms are involved not only in the increase in sensitivity to thermooxidation but also in the crosslinking phenomenon between isoprene chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermal degradation kinetics of isotactic and atactic polypropylene

The thermal degradation of isotactic and atactic polypropylene was investigated in bulk and in solution. The degradation in bulk was studied with thermogravimetric analysis, and the degradation in solution was studied by the dissolution of the polymer in paraffin oil. The degradation in solution was investigated from 230 to 350°C. The effect of the hydrogen donor on the degradation of the polymer in solution was also studied at 350°C. Continuous distribution kinetics were employed to model the degradation kinetics for the degradation in solution. The rate coefficients were obtained, and the activation energy was calculated from an Arrhenius plot. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2206–2213, 2003     

Effects of the type and concentration of alkylaluminum cocatalysts on the molar mass of polypropylene made with in situ supported metallocene catalysts

Propylene homopolymerizations were carried out with rac‐dimethylsilylenebis(indenyl)zirconium dichloride, methylaluminoxane‐modified silica, and common alkylaluminum cocatalysts. Supported catalysts were prepared by the in situ immobilization technique. The effects of the type and concentration (Al/Zr = 40–1000) of alkylaluminum on the propylene polymerization were evaluated with triethylaluminum (TEA), isoprenylaluminum (IPRA), and triisobutylaluminum (TIBA) as cocatalysts. The polymers were analyzed by gel permeation chromatography, differential scanning calorimetry, and ¹³C‐NMR. The polypropylene molar mass varied according to the nature of the alkylaluminum in the following order: TIBA > IPRA > TEA > no alkylaluminum. The polymers made with an in situ supported catalyst had lower crystallinities and melting points than the ones produced by homogeneous polymerization. The isotacticity was not affected by the polymerization conditions examined in this investigation. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1050–1055, 2005     

凝胶色谱法测定高聚物的平均分子量及分子量分布

介绍了用凝胶色谱法测定高聚物的平均分子量及分子量分布。     

Scale‐Free Power‐Law Distribution of Emulsion‐Polymerized Branched Polymers: Power Exponent of the Molecular Weight Distribution

Summary: The molecular weight distribution (MWD), formed in emulsion polymerization that involves the polymer transfer reaction during Interval II, may approach the power‐law distribution as polymerization proceeds. The power exponent, α, of the weight fraction distribution W(M) = M^?α conforms to the relationship, α = 1/P_b, where P_b is the probability that the chain end is connected to a backbone chain. The MWD of emulsion‐polymerized polyethylene reported in literature agrees reasonably well with the relationship, W(M) = M^?α with α = 1/P_b. This simple relationship could be used to estimate the P_b value from the MWD data, possibly leading to determining the polymer transfer constant under well‐designed experimental conditions. Because α > 1, the number‐average MW always approaches a finite value, but the weight‐ and higher order‐averages of MWD may continue to increase as the particle grows without limit depending on the magnitude of P_b. The power‐law distributions are self‐similar, possessing the nature of fractals and lacking a characteristic scale. The i‐th moment of the MWD for the present reaction system continues to increase without limit during Interval II for P_b ≥ 1/i.

Molecular weight distribution of the emulsion‐polymerized polyethylene.     

关于聚苯乙烯的摩尔质量分布与性能

对国内外聚苯乙烯瓣摩尔质量分布的渗透色谱法测定结果,结合有关性能进行了分析和讨论,表明了熔融指数不仅随重均摩尔质量的增高而变小,而且和摩尔质量分布有关。国内某些厂（批）的聚苯乙烯性脆问题与低聚物含量较多有关。     

Controlled Degradation of Poly(propylene) in Industrial Extruders

Summary: The main objective of this work was to study the controlled degradation of PP in industrial extruders at different operating conditions. Firstly, the investigation of certain key polymer properties, such as the MI and the MWD, revealed that the changes undergone by the polymer resin during the reactive extrusion depend strongly on the operating conditions. In the absence of oxygen, the results indicated that spontaneous thermal and/or mechanical degradation were not very important. Therefore, resin properties were not expected to change during extrusion if no peroxide was fed into the extruder, in the absence of oxygen. On the other hand, in the presence of oxygen, MWD analysis showed that the MWD could be shifted towards higher or lower molecular weights, indicating that both chain growth and chain scission were possible during extrusion. Finally, simple expressions are presented here in order to allow for the monitoring and control of the important final properties of the extruded resin.

The molecular weight distribution of polymer powder and polymer pellets during extrusion.     

动态平衡系统累积时间分布函数及其在聚合物分子量分布中的应用

The lumped time distribution functions were proposed,which can be used for describing the dynamic systems with two or more than two states of the end of growing polymer chain during chain addition polymerization.Numerical analysis of the lumped time distribution functions was carried out.The method for calculating molecular weight distribution of polymer in the stable free radical polymerization and more general cases was developed based on the lumped time distribution functions.     

Rheological properties of polypropylenes with different molecular weight distribution characteristics

Relationships between the rheological properties and the molecular weight distribution of two polypropylene series with different molecular weight distribution characteristics were studied. The end correction coefficient in capillary flow is determined by the molecular weight M_w and the molecular weight distribution M_w/M_n, and is higher as both characteristic values are larger. The die swell ratio at a constant shear rate depends on M_w, M_w/M_n, and M_z/M_w, and is higher as the three characteristic values are larger. The critical shear rate at which a melt fracture begins to occurs depends on the molecular weight M_w and the molecular weight distribution M_z/M_w, and is proportional to M_z/M_w² in a log–log plot. The critical shear stress does not depend on the molecular weight, and is higher as M_z/M_w is higher. The zero‐shear viscosity is determined by a molecular weight of slightly higher order than M_w, and the characteristic relaxation time is determined by M_z. The storage modulus at a constant loss modulus scarcely depends on the molecular weight, and is higher as the molecular weight distribution M_w/M_n is higher. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2128–2141, 2002     

宽分子量分布高聚合度PVC的合成和性能

针对高聚合度聚氯乙烯加工性能较差的缺点,采用２段聚合温度法合成了宽分子量分布的ＰＶＣ树脂,并对树脂的热稳定性、加工性能和力学性能进行了研究。     

Effect of Comonomer Content on the Behavior of Propylene Copolymer/Compatibilizer/Clay Nanocomposites

A set of isotactic propylene copolymers with either 1‐hexene or 1‐octadecene were synthesized using a metallocene catalyst, and their nanocomposites with 5 wt.‐% of clay and 15 wt.‐% of compatibilizer were prepared and characterized. Clay intercalation and dispertion depend on the comonomer content in the matrix which improves at high short‐chain‐branching levels. The presence of both clay and compatibilizer increased the crystallization temperature of the matrix. A strong correlation between the elastic modulus of the matrix and its relative increase in the nanocomposite was observed. By adding clay and compatibilizer to the copolymer, the modulus can be increased by a factor of two. The results open new perspectives in the understanding of the effect of polyolefin topology on nanocomposites properties.

     

超高效聚合物色谱法检测环氧树脂的分子量

超高效聚合物色谱法(APC)是一种高效率、高分辨的聚合物表征技术,该技术可在10 min内实现聚合物的高效分离,同时获得其平均分子量及其分布参数。以典型油溶性低聚物环氧树脂为研究对象,探索APC测试油溶性低聚物分子量及其分布参数的方法和条件。与传统的凝胶渗透色谱(GPC)相比,采用APC方法分辨率高、重现性强,相对标准偏差(RSD)均低于0.5%。实验还考察了不同进样体积对测试结果的影响。结果表明,在样品浓度为0.1%时,随着进样体积的增大,在保持优异的分辨率的同时,色谱峰增强更为显著。获得高分辨率的APC图谱具有独特的组成峰型,有望作为"指纹图谱",用于油溶性低聚物的合成和组成分析。     

Fabrication of Uniaxially Aligned Poly(propylene) Nanofibers via Handspinning

A straightforward method, which is termed novel handspinning, is reported for producing uniaxially aligned sPP nanofibers. As demonstrated by SEM analysis, the morphologies of handspun sPP nanofibers are strongly dependent upon the processing conditions such as spinning method and solvent system. Compared to the normal electrospun sPP nanofibers, the handspun sPP nanofibers show smoother morphologies. FT‐IR analysis demonstrates a significant difference in polymer chain conformation between the handspun and electrospun sPP nanofibers. Moreover, interestingly, the handspun sPP single nanofibers show higher Young's modulus and tensile strength than electrospun sPP single nanofibers.

     

丁二烯气相聚合产物分子量分布和粒径分布模型研究

对非均相催化的丁二烯气相聚合,基于聚合物多层模型,考虑催化剂颗粒间活性位初始浓度和粒径分布对聚合物分子量分布和粒径分布的影响,建立了聚合物分子量分布和粒径分布的数学模型。模拟了反应温度、催化剂颗粒间活性位初始浓度和粒径分布等因素的影响,结果表明。随着温度升高,聚合物颗粒平均粒径变小,粒径分布变窄,聚合物分子量变小,分子量分布变宽;催化剂颗粒间的活性组分负载越均匀,聚合物分子量越大,分子量分布和粒径分布越窄;随着催化剂平均粒径变大,聚合物分子量变小,分子量分布变宽,不存在催化剂颗粒粒径分布和聚合物颗粒粒径分布间的复制现象。模型模拟结果与实验结果吻合较好,可用于预测丁二烯气相聚合产物的分子量、分子量分布和粒径分布。     

Relationship between the structure and mechanical properties of polypropylene: Effects of the molecular weight and shear‐induced structure

A series of homopolymer polypropylenes (PPs), within a weight‐average molecular weight (M_w) range of 100–1600 kg/mol, were manufactured as dumbbell microspecimens. The effects of the molecular weight and shear‐induced crystallization on the mechanical properties and morphology were studied to gain a better understanding of the structure–property relationship. The results showed that the crystallinity decreased from 50 to 41% and the lamellar thickness increased as M_w increased. Tensile tests demonstrated that the stiffness and especially the tensile strength rose to extremely high values (Young's modulus = 2400 N/mm², stress at 30% strain = 120 N/mm²). Furthermore, the strain hardening effect was strongly affected by the lamellar thickness and highly oriented superstructures. Dynamic mechanical analysis demonstrated that the mobility of the molecular chains depended on M_w and on the lamellar thickness. In addition, the viscoelastic properties of unannealed and annealed samples indicated further the existence of shish‐kebab structures caused by shear‐induced crystallization during injection molding. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 519–533, 2007     

Thermal bonding of polypropylene nonwovens: Effect of bonding variables on the structure and properties of the fabrics

Properties of the point‐bonded nonwoven fabrics are dependent on the bonding conditions, in addition to those of the polymer/fiber. Thermally bonded carded webs were produced and characterized to investigate the role of bond area, bond size, and bonding temperature on the structure and properties of point‐bonded nonwoven fabrics. It was observed that the bond strength increases with bond area and bond size. The effects of bond area and bond size on fiber morphology were negligible. Significant morphological differences were observed in the bonded and the unbonded regions of the thermally bonded webs. To see how the staple fiber studies relate to the behavior of continuous filaments, similar sets of samples were produced and characterized by using the spunbond system. The observed trends for properties with respect to bonding conditions were similar for spunbond samples. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3593–3600, 2004