宽峰聚乙烯／蒙脱土纳米复合材料的制备

利用2种不同的方法制备了2种氢调敏感性不同的蒙脱土／氯化镁／四氯化钛（MMT／MgCl2／TiCl4）催化剂,利用这2种催化剂及其混配催化剂,通过原位聚合法,制备出一系列宽峰聚乙烯纳米复合材料,采用X_射线衍射仪（XRD）、凝胶色谱测试分析（GPC）及力学性能测试等方法对催化剂及聚合产物进行分析,结果表明,2种催化剂以及按照不同比例混合的混配催化剂均表现出较高的聚合活性,XRD测试结果表明,蒙脱土片层在乙烯聚合过程中发生了插层及剥离,以单片层或几层共存的形式分散于聚乙烯基质中;用混配催化剂可制得宽峰聚乙烯纳米复合材料,Mw／Mn=7．23,并且聚合物的堆积密度达到工业生产的标准,宽峰聚乙烯纳米复合材料的综合力学性能较工业产品5000S及工业上应用的管材料有很大的提高。     

Effects of molecular weight distribution and long-chain branching on the viscoelastic properties of high- and low-density polyethylene melts

Using the Han slit/capillary rheometer, rheological measurements were taken of several commercially available low- and high-density polyethylene melts, namely, three low-density polyethylene samples of Chemplex Corp. (CX 1005, CX 1016, and CX 3020), three low-density polyethylene samples of U.S. Industrial Chemicals Co. (NA 205, NA 244, and NA 279), two high-density polyethylene samples of Union Carbide Corp. (DMDJ 5140 and DMDJ 4306), and two high-density polyethylene samples of Mitsui Petrochemical Industries, LTD. Molecular characterization of these samples was carried out by the resin suppliers. The rheological measurements included (1) entrance pressure drop, (2) exit pressure, (3) pressure gradient, (4) die swell ratio. These then permitted us to determine the shear viscosity and normal stress differences. The rheological measurements were interpreted to identify the effects of long-chain branching and molecular weight distribution on the rheological properties of polyethylenes in the light of the existing molecular viscoelasticity theories. It was found that fluid elasticity is greater for polymers having a broader molecular weight distribution and that, for polymers having more long-chain branching, viscosities are lower while elasticities are higher.     

Branching and molecular weight distribution of polyethylene SRM 1476

A method of determining the distribution of branching in a polymer is developed employing limiting viscosity numbers (intrinsic viscosity), gel permeation chromatography (GPC), and absolute molecular weight determinations of fractions of the whole polymer. A molecular weight calibration of the GPC column set is first determined empolying these fractions. From the limiting viscosity number measurements of these fractions and their molecular weight distribution determined from the GPC chromatogram, the viscosity–molecular weight relationship is determined by a nonlinear least-squares fitting procedure. For the same molecular weight, the limiting viscosity number of the branched polymer is less than the limiting viscosity number of the linear polymer. From the ratio of the two, the number of branches per unit molecular weight of the branched polymer is calculated. The method was applied to SRM 1476, the standard reference branched polyethylene issued by the National Bureau of Standards. The branching density for the constituents of SRM 1476 rise from zero at molecular weights less than 10,000 to about 6 to 8×10^?5 at molecular weights of 50,000 and above. The branching of SRM 1476 was also determined by the method of Drott and Mendelson, giving a result in fair agreement with the above method.     

The effect of molecular weight distribution on polyethylene film properties

Polymer molecular weight heterogeneity affects the rheological properties of polymer melts such as melt viscosity, fracture and die swell. These rheological properties affect the conversion of the polymer from the bulk resin state to its final usable form. In this particular study, the effect of molecular weight distribution on polyethylene blown film characteristics was studied. The effect of the molecular weight heterogeneity on the rheological characteristics of the polymer in the molten state and its effect on the film properties is presented. The properties studied included film gloss, haze, tear resistance and film impact strength. This study shows that broadening the molecular weight distribution increases haze and reduces film gloss. Further, it was shown that a linear relationship exists between film gloss and external haze. Both values are measures of surface irregularities in the film which are affected by the drawing characteristics of the polymer. A broader molecular weight distribution results in increased impact strength as measured by the Dart Drop Impact Test. This is, it is believed, a result of the increase in long chain branching of the higher molecular weight fractions of the polymer which cause a higher degree of molecular weight entanglement at the branch sites. In contrast the tear strength is reduced as the molecular weight distribution broadens because of the low molecular weight fraction in the broad spectrum material which tend to decrease resistance to tear.     

Ultrahigh molecular weight polyethylene as used in articular prostheses (a molecular weight distribution study)

Currently there is widespread use of ultrahigh molecular weight polyethylene (UHMWPE) acetabular components in total joint replacement prostheses. What has been most surprising about the wear of UHMWPE under such circumstances is the occurrence of brittle fracture. Such fracture had not been observed in the usual engineering tests done in the laboratory on UHMWPE. It was only when prosthese which had been removed from patients were examined or run in hip joint simulators with serum or synovial fluid as the lubricant, that brittle fracture was encountered. The problem of environment-enhanced brittle fracture in plastics dates back to 1946. Interestingly, the phenomenon was first described in polyethylene. The prime variables involved are polymer molecular weight, sensitizing environment, stress filed, and temperature. Other things being equal, brittle behavior in polyethylene is extremely sensitive to the amount of low molecular weight polymer present. In the light of the foregoing we have studied the molecular weight distribution in six commercially available UHMWPE components. These were obtained from six different manufacturers. The specimens were characterized both on their bearing (wear) surfaces and in their interior bulk. The results obtained indicate that:

• 1 The UHMWPE components contain substantial amounts of low molecular weight polymer.
• 2 The UHMWPE components differ significantly in molecular weight distribution.
• 3 The UHMWPE components contain substantial amounts of crosslinked polymer.

     

Sizes of long-chain branches in a high-pressure low-density polyethylene as a function of molecular weight

The mean length and the indices of long-chain branches (LCBs) of a high-pressure lowdensity polyethylene (HPLDPE) as a function of molecular weight have been determined for its molecular-weight-tractionated parts by the ¹³C-NMR analysis and the viscosity measurements. The mean LCB length of the fractions was of the order of 200–300 carbons in length. The size of LCBs increases with increasing molecular weight, but the size of LCBs relative to the overall macromolecular size decreases with increasing molecular weight. The LCB sizes as a function of molecular weight determined for the fractions of one parent HPLDPE are in good agreement with those previously reported for HPLDPE whole polymers.     

Correlation between steady state flow curve and molecular weight distribution for polyethylene melts

This article uses Graessley's theory of viscosity to predict the flow curve for several high-density and low-density polyethylene melts using the molecular weight distribution data obtained from the gel permeation chromatograph. The agreement with the experimental flow curve obtained from the Weissenberg rheogoniometer and the Instron rheometer was not quantitative for many high-density polyethylenes studied here. For the low-density polyethylenes, it was shown that the agreement between the theory and the experiment was good even though the molecular weight distribution data were not corrected for long-chain branching. For these samples, the experimental relaxation time τ₀ obtained by superposition of the data with the theoretical master curve was of the order of the Rouse relaxation time τ_R. The systematic increase in the ratio τ_R/τ₀ was ascribed to the increase in the molecular weight or to the increased number of long-chain branches.     

Control of molecular weight distribution of polyethylene in gas-phase fluidized bed reactors

This paper presents a feasibility study of the broadening of polyethylene molecular weight distribution produced using a multisite Ziegler-Natta catalyst in a fluidized-bed reactor. A nonlinear model predictive control algorithm, applied to a validated model of the reactor, is used for the on-line control of the entire molecular weight distribution of the produced polymer. Control of a target chain-length distribution is achieved by selecting a collection of points in the distribution and using them as set points for the control algorithm. An on-line Kalman filter is used to incorporate infrequent and delayed off-line molecular weight measurements. Through simulation the control algorithm is evaluated, under tracking conditions as well as plant-model mismatch. The results demonstrate that the control algorithm can regulate the entire molecular weight distribution with minimum steady state error. However, the efficiency of this approach is highly dependent on the dynamics of hydrogen inside the reactor.     

Fracture behavior of bimodal polyethylene: Effect of molecular weight distribution characteristics

A series of bimodal polyethylenes with different molecular weight distribution characteristics were prepared by melt blending, and the fracture behavior of these bimodal polyethylenes was studied by the method of essential work of fracture. The results show that specific essential work of fracture, w_e, increases obviously with the molecular weight distribution characteristic, A_L/U, indicating the improvement of the resistance to crack propagation. By means of successive self-nucleation and annealing analysis, obvious variations in the crystal structures of bimodal polyethylenes with increasing A_L/U have been found. That is, the crystal size and the amount of relatively thick lamellas increase with A_L/U, but no large variation of crystallinities has been observed. So, the influence of A_L/U is mainly on the crystal perfection, the improvement of which produces an enhancement of fracture toughness since more energy would be dissipated in the superior network structure constructed from crystalline zones and amorphous zones.     

A model relating the elastic properties of high-density polyethylene melts to the molecular weight distribution

An earlier model relating the variation of the steady-shear melt viscosity of high-density polyethylene to the molecular weight distribution is applied toward predicting the steady-shear elastic compliance, the first normal stress difference, and relaxation spectrum as a function of shear rate from the molecular weight distribution. The model envisions the cutting off of longer relaxation times as the shear rate is raised such that at any shear rate ${\rm \dot \gamma }$ the molecular weights and their corresponding maximum relaxation times τ_m are partitioned into two classes; the relaxation times are partitioned into operative and inoperative states, depending on whether they are less than or greater than τ_c, the maximum relaxation time allowed at ${\rm \dot \gamma }$. Equations relating molecular weight and relaxation time to the steady-shear elastic compliance and viscosity are assumed valid at nonzero shear rates, except for the partitioning effect of shear rate. The shear rate dependence of the first normal stress difference and the steady-shear viscosity for polyethylene melts is successfully predicted over the range covered by the cone-and-plate viscometer. The assumed proportionality constant between τ_c and 1/${\rm \dot \gamma }$ was determined to be 1.7. Using this relation, the maximum relaxation time at 190°C for a polyethylene molecule of molecular weight M is given by τ_m = 1.4 × 10^?19 (M)^3.33. Reasonable agreement has been obtained between the experimentally determined relaxation spectrum of a polyethylene melt and that predicted from the molecular weight distribution. The agreement is best at the longest relaxation times.     

Thermal and rheological properties of polyethylene blends with bimodal molecular weight distribution

Polyethylene blends with bimodal molecular weight distribution were prepared by blending a high molecular weight polyethylene and a low molecular weight polyethylene in different ratios in xylene solution. The blends and their components were characterized by the high temperature gel permeation chromatograph (GPC), different scanning calorimetry (DSC), and small amplitude oscillatory shear experiments. The results showed that the dependence of zero‐shear viscosity (η₀) on molecular weight followed a power law equation with an exponent of 3.3. The correlations between characteristic frequency (ω₀) and polydispersity index, and between dynamic cross‐point (G_x) and polydispersity index were established. The complex viscosity (η^*) at different frequencies followed the log‐additivity rule, and the Han‐plots were independent of component and temperature, which indicated that the HMW/LMW blends were miscible in the melt state. Moreover, the thermal properties were very similar to a single component system, suggesting that the blends were miscible in the crystalline state. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of polyethylene with controlled bimodal molecular weight distribution using zirconium complexes

Four zirconium complexes containing fully deprotonated 2-(2H-benzo[d][1,2,3]triazol-2-yl)-4,6-di-tert-pentylphenol were used as catalysts for the polymerization of ethylene. In the presence of methylalumoxane (MAO) as a cocatalyst, the precursors were highly active for polyethylene with bimodal or multimodal molecular weight distribution.     

Processing of ultrahigh molecular weight polyethylene

The extent of recrystallization of nascent UHMWPE powder is easily measured by calorimetry. Melting and recrystallization of nascent UHMWPE at 140°C can be suppressed by compression molding. Crystals of UHMWPE prepared from dilute solution show a peak melting temperature of 140°C and exhibit crystallinity up to 75.5% depending on crystallization temperature. Large changes in crystallinity result from drawing single crystal mats or compression-molded films.     

Melting of ultrahigh molecular weight polyethylene

On heating in DSC, samples of UHMWPE show a single, fairly sharp, melting endotherm which may be increased to a peak temperature of 147°C and 77% crystallinity by annealing at elevated temperatures. An irreversible conversion of nascent to folded crystals, between 134 and 142°C, was observed by heating nascent UHMWPE powder in the calorimeter. In the presence of n-hexatriacontane, the melting endotherm of UHMWPE was depressed and broadened and the conversion of nascent to melt-crystallized polyethylene facilitated on heating. A melt-crystallized mixture of ordinary linear polyethylene (HDPE) and UHMWPE was not resolved on remelting. After annealing this mixture for 12 h at 130°C, HDPE was fractionated and the melting of UHMWPE was sharpened. Crystals of UHMWPE, prepared from dilute solution in xylene, show a single sharp melting endotherm and high crystallinity, but the melting peak is reduced in temperature compared to nascent crystallized powder.     

Viscosity and molecular weight distribution of ultrahigh molecular weight polyethylene using a high temperature low shear rate rotational viscometer

To obtain accurate measurements of the limiting viscosity number (LVN) or the intrinsic viscosity [η] of solutions of ultrahigh molecular weight polyethylene (UHMWPE), a low shear floating-rotor viscometer of the Zimm-Crothers type was constructed to measure viscosities at elevated temperatures (135°C) and near zero shear rate. The zero shear rate measurements for UHMWPE whole polymer and UHMWPE fractionated by hydrodynamic crystallization were compared with viscosity measurements at moderate and high shear rates (up to 2000 _s^?1) carried out in a capillary viscometer. The limiting viscosity number of UHMWPE decreases, as expected, with shear rate. The higher shear rate data could not be extrapolated to yield the correct zero-shear rate viscosities. Fractionation of UHMWPE gave 10 fractions ranging in LVN from 9 to 50 dL/g. A tentative integral molecular weight distribution for the whole polymer was calculated on the basis of the Mark-Houwink equation, but because it had been previously established only for lower molecular weight polyethylenes, it may not be accurate. A correlation was found between the LVNs for the fractions in the two types of viscometers.     

A cooperative molecular weight distribution test

The development of gel permeation chromatography (GPC) has provided a convenient tool for the rapid determination of molecular weight distribution. The question has arisen as to the suitability of the method for specification purposes. The present work, suggested by the Naval Air Systems Command, represents an attempt to assess the precision of the method through a series of tests carried out by a number of laboratories using identical procedures on the same samples. Ten laboratories agreed to take part. Naval Ordnance Station, Indian Head, worked out standard conditions for operation of the chromatograph, for calibration of the columns, and for analysis of the GPC curves. Two samples of polystyrene were used by the various organizations for calibration of their instruments. Number-average molecular weight, heterogeneity index, and cumulative molecular weight distribution curves were determined on four samples of carboxyl-terminated polybutadiene (CTPB) and two samples of hydroxyl-terminated polybutadiene (HTPB), all unidentified except by letter code. All laboratories used identical directions for setting up CTPB and HTPB calibration curves which were based on curves determined from vapor-pressure osmometer molecular weights and GPC count numbers of fractionated material. Variation among the different laboratories was 0.15 in heterogeneity index, and a maximum of 1200 in molecular weight provided one aberrant set of values was eliminated. The six samples had heterogeneity indices from 1.15 to 1.54, while molecular weight varied from approximately 3000 to 6000. The average coefficient of variation of the molecular weight values was 6.2 ± 0.7%, which is quite acceptable. Variation in heterogeneity index was too great for specification purposes when considered among the different laboratories, but may be sufficiently good when measured by any one laboratory.     

Optimal process operation for the production of linear polyethylene resins with tailored molecular weight distribution

An optimization model is presented to determine optimal operating policies for tailoring high density polyethylene in a continuous polymerization process. Shaping the whole molecular weight distribution (MWD) by adopting an appropriate choice of operating conditions is of great interest when designing new polymers or when improving quality. The continuous tubular and stirred tank reactors are modeled in steady state by a set of differential‐algebraic equations with the spatial coordinate as independent variable. A novel formulation of the optimization problem is introduced. It comprises a multi‐stage optimization model with differential‐algebraic equality constraints along the process path and inequality end‐point constraints on product quality. The resulting optimal control problem is solved at high computational efficiency by means of a shooting method. The results show the efficiency of the proposed approach and the benefit of predicting and controlling the complete MWD as well as the interplay between operating conditions and polymer properties. © 2010 American Institute of Chemical Engineers AIChE J, 2011