环烯烃共聚物的生产工艺评述

介绍了生产环烯烃共聚物（COC）所采用的两种工艺过程,即开环移位聚合过程（ROMP）和茂金属催化加成共聚合过程(mCOC)。通过对单体、催化剂、生产工艺流程、聚合物性能等各方面的综合对比,认为采用ROMP法所制得的产物必须进行后续加氢反应以去除开环所带来的不饱和双键,一般氢化程度大于98%才能得到高质量的COC。而mCOC法则仅需一步反应即可,且催化活性很高,被认为是生产COC树脂最为经济、有效的方法。     

环烯烃共聚物的制备

评述了环烯烃与线性α-烯烃共聚物(COC)的主要生产厂家、结构与性能及制备方法等。着重介绍了加成聚合法中茂金属催化剂的结构对称性、配体的电子和体积效应、反应条件等对聚合活性、产物组成与序列分布及相关热性能的影响。     

New extensional rheometer for elongational viscosity and flow birefringence measurements: some results on polystyrene melts

A new extensional rheometer allowing the simultaneous measurement of elongational viscosity and flow birefringence is described. Polystyrene melts have been tested at different temperatures and strain rates. It appears that the time-temperature superposition principle holds for elongational tests in the temperature range investigated, with the same shift factors as for linear shear experiments. It has been verified that the stress optical behaviour of the melts is linear for small values of the stress whereas significant deviations appear at higher stresses.     

Rheological behavior of polypropylene/layered silicate nanocomposites prepared by melt compounding in shear and elongational flows

Melt rheology and processability of exfoliated polypropylene (PP)/layered silicate nanocomposites were investigated. The nanocomposites were prepared by melt compounding process in the presence or absence of a PP‐based maleic anhydride compatibilizer. PP/layered silicate nanocomposites showed typical rheological properties of exfoliated nanocomposites such as nonterminal solid‐like plateau behavior at low frequency region in oscillatory shear flow, higher steady shear viscosity at low shear rate region, and outstanding strain hardening behavior in uniaxial elongational flow. The melt processability of exfoliated PP/layered silicate nanocomposites was significantly improved due to good dispersion of layered silicates and increased molecular interaction between the PP matrix and the layered silicate organoclay. Small‐angle X‐ray scattering and transmission electron microscopy results revealed that the layered silicate organoclay was exfoliated and good interaction between PP matrix and organoclay was achieved by using the PP‐g‐MAH compatibilizer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3506–3515, 2007     

Phase transformation and dielectric properties of polyvinylidene fluoride/organic-montmorillonite nanocomposites fabricated under elongational flow field

Compounding montmorillonite (MMT) with polymorphic polyvinylidene fluoride (PVDF) by melt intercalation method can induce the crystal phase transformation of PVDF, which is of great significance to obtain the electroactive PVDF. In this research, PVDF/Organic-Montmorillonite (OMMT) nanocomposites were prepared by a novel vane mixer, which was dominated by the elongational flow field in the whole plasticizing. The dispersion of OMMT, the crystal phase transformation of PVDF, and the resulting properties of nanocomposites were experimentally studied. The results of TEM and WAXD evidenced that homogeneous dispersion and desirable intercalation structure of OMMT were formed in the PVDF matrix under the effect of the elongational flow field. WAXD, FTIR, and DSC tests demonstrated that large amounts of β-phase of PVDF was formed due to the introduction of OMMT. The intercalation structure of OMMT and the crystal transformation of PVDF increased the dielectric constant and piezoelectric properties of nanocomposites, while the dielectric loss still maintained at a very low level. Finally, the effect of unique ''double-layer peeling'' mechanism of OMMT on the properties of nanocomposites was discussed.     

Glass‐transition temperature determination by microhardness in norbornene‐ethylene copolymers

Vickers microhardness as a function of temperature was determined in a series of norbornene‐ethylene copolymers synthesized with a metallocene catalyst. The norbornene content in the samples ranges from 31 to 62 mol %, and all of them were found to be amorphous. The possibility of studying the glass‐transition temperature by plotting the microhardness‐temperature dependencies is discussed in addition to the limits and the reliability of the suggested method. Moreover, a linear dependency between microhardness at different temperatures and glass‐transition temperature was established. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3666–3671, 2003     

Temperature shifting of convergent flow measured effective elongational viscosity

The effective elongational viscosity data on a series of polyolefins as a function of temperature are shifted to a reference temperature using the approach for shifting shearing viscosity data. The temperature shift factors are obtained from complex and capillary shear rheology, and these are the same factors used for shifting the shear rheology. A Carreau rheological model was used to determine the zero shear rate viscosity at different temperatures, and an Arrhenius expression was used to determine the temperature shift factors. The same shift factors are shown to produce separate master curves for shear and elongational rheology at reference temperatures. The commercial grades of polyolefins studied include an extrusion grade of polypropylene and metallocene and conventionally catalyzed low and high density polyethylene materials. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1387–1396, 2003     

Elongational Rheology of Polymer/Clay Dispersions: Determination of Orientational Extent in Elongational Flow Processes

The purpose of the present contribution is to provide an efficient method that would help to quantify the orientational levels occurring in polymer/clay dispersions subjected to elongational flow. The extent of internal orientation developed in salt containing montmorillonite/poly(ethylene oxide) gels is investigated, combining shear and elongational rheology methods. Entropic changes indicate that the strength of the transient network present in each gel affects the orientational ability of clay particles and polymer chains. We found that an increased Hencky strain of the hyperbolic die leads to a higher variation of the calculated entropy of the material.

     

Low molecular weight block copolymers as plasticizers for polystyrene

Polystyrene‐b‐alkyl, polystyrene‐b‐polybutadiene‐b‐polystyrene, and polystyrene‐b‐poly(propylene glycol)monotridecyl ether were synthesized using macro initiators and atom transfer radical polymerization or by esterifications of homopolymers. The aim was a maximum molecular weight of 4 kg/mol and minimum polystyrene content of 50 w/w %, which by us is predicted as the limits for solubility of polystyrene‐b‐alkyl in polystyrene. DSC showed polystyrene was plasticized, as seen by a reduction in glass transition temperature, by block copolymers consisting of a polystyrene block with molecular weight of approximately 1 kg/mol and an alkyl block with a molecular weight of approximately of 0.3 kg/mol. The efficiency of the block copolymers as plasticizers increases with decreasing molecular weight and polystyrene content. In addition, polystyrene‐b‐alkyl is found to be an efficient plasticizer also for polystyrene‐b‐polyisoprene‐b‐polystyrene (SIS) block copolymers. The end use properties of SIS plasticized with polystyrene‐b‐alkyl, measured as tensile strength, is higher than for SIS plasticized with dioctyl adipate. The polystyrene‐b‐polybutadiene‐b‐polystyrene and polystyrene‐b‐poly(propylene glycol)monotridecyl ether series were only partially soluble in polystyrene and insoluble in the polystyrene phase of SIS. For the lowest molecular weight samples, this leads to measurable plasticization of polystyrene but no plasticization of SIS. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 981–991, 2005     

Poly(arylene ether nitrile) copolymers containing pendant phenyl: Synthesis and properties

A series of poly(arylene ether nitrile) copolymers (PENAPs) were synthesized with bisphenol A (BP-A), bisphenol AP (BP-AP) and 2,6-Dichlorobenzonitrile (DCBN) via a nucleophilic substitution polycondensation reaction. FTIR and ¹H-NMR were used to confirm the structure of PENAPs. Glass transition temperature (T_g) of PENAPs determined by differential scanning calorimetry (DSC) ranged from 154.2 to 200.8°C. The 5% weight lost temperature (T_5%) of PENAPs were 418.9–447.7°C. The tensile and DMA test indicated that PENAPs possessed excellent mechanical properties with tensile strength more than 92.8 MPa and storage modulus more than 1.0 GPa at about 150°C. The melt flowability was measured by rheology properties testing ranging from 80 to 1639 GPa at 290°C and under shear frequency 100 Hz, which indicated the copolymers had good flowability and thermal stability. Additionally, PENAPs could be dissolved in many solutions, which meant PENAPs had good solubility and can be processed by solution method.     

Transient uniaxial orientation of flexible polymer chains in a wide range of elongation rates

Affine evolution of chain end-to-end vectors distribution function is derived analytically for non-linear polymer liquids subjected to uniaxial elongational flow, controlled by time-evolution of chain deformation coefficients. Peterlin approximation for non-Gaussian chain elasticity is applied, with Padè approximation for the inverse Langevin function. The approach enables calculations of transient molecular deformation coefficients in entire range of elongation rates and times.Equations controlling time evolution of the molecular deformation coefficients in elongational flow are solved analytically with an assumption of dominating elongational component. The approach allows to decouple evolution equations and obtain an approximate closed form analytical formula describing time evolution of the molecular deformation with high accuracy, in particular at higher elongation rates, above the Gaussian limit.Predictions of the analytical formula are compared with numerical computations to evaluate the approximation and ranges of its validity.The analytical formula enables predicting evolution of average functions in non-linear systems, such as free energy, tensile stress, molecular orientation, etc. The formula is used to discuss molecular vs. macroscopic deformation in wide range of elongation rates and times, as well as evolution of stress, axial orientation factor, apparent elongational viscosity.     

Splitting of the phase transition in TGSe crystal under uniaxial stress

Changes in the velocity and attenuation coefficient of quasi-longitudinal waves propagating in TGSe crystal in the direction X induced by uniaxial stress σ_Y were measured in the temperature range of ferroelectric phase transition. The application of uniaxial stress was found to shift the phase transition temperature by ∂T_C/∂σ_Y = -0.18 K/MPa. For the stress greater than 2 MPa an additional anomaly in the wave velocity and attenuation appears, which has been interpreted as a splitting of the phase transition.     

Epoxy-based divinyl ester resin/styrene copolymers: Composition dependence of the mechanical and thermal properties

Epoxy-based divinyl ester resins (DVER) were obtained by reacting diglycidyl ether of bisphenol A (DGEBA) with methacrylic acid (MA) and characterized by FTIR and ¹H-NMR spectroscopies and gel permeation chromatography (GPC). The densities and viscosities of the DVER in styrene (S) solutions were measured at different temperatures, 25, 40, and 60°C and compositions, 3.4 to 100% by weight of styrene. Dynamic mechanical measurements (DMA) and differential scanning calorimetry (DSC) were used to determine the glass transition temperatures of the homopolymers and the DVER/S copolymers: 20, 40, 60, and 80% by weight of styrene. The values obtained are in the range limited by the homopolymers glass transition, 100°C for polystyrene and 173°C for the cured DVER. The data were well fitted if two contributions to the glass transition are taken into account: the “linear copolymer” contribution (Fox eq.) and the “crosslinking” contribution (Nielsen model). Uniaxial static compression tests were carried out to determine the modulus, yield stress, and ultimate stress in samples with different compositions. All the mentioned properties decrease with an increase in the styrene concentration in the final copolymer. It was found that the volumetric contraction during curing increases with styrene concentration. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1059–1066, 1997     

Syntheses and investigations of copolymers for improving the flow of middle distillate oils

The results of a review of the patent literature on polymeric flow improvers for distillate fuels showed that a diverse range of polymeric compositions is effective. Ethylene-containing compositions predominate and of these ethylene-vinyl acetate (EVA) copolymers are the most common. Ethylene-vinyl acetate copolymers were synthesised using a high pressure autoclave. The effectiveness of the copolymers varied greatly with the chemical composition of the copolymer. The techniques described in the literature for the determination of the composition of EVA copolymers are summarised and reviewed. A new technique using proton nuclear magnetic resonance was developed. A statistical analysis of the results is presented.     

Structural characterization of alpha methyl styrene‐butyl acrylate‐grafted polyetheretherketone films

Radiation‐induced graft copolymerization of alpha methyl styrene (AMS)‐butyl acrylate (BA) mixture onto poly(etheretherketone) (PEEK) was carried out to develop films of varying copolymer compositions. The characterization of films was carried out with fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), X‐ray diffraction analysis (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The presence of AMS and BA units within the film matrix was confirmed by FTIR. The intensity of the characteristic peaks for AMS and BA increased with the increasing grafted component in the films. The crystallinity of the films as observed from DSC and XRD decreased with the increasing graft levels. On the other hand, the melting temperature of the base polymer was almost unaffected by irradiation and the grafting process. The glass transition temperature (T_g) of the grafted film increased as compared to the virgin PEEK. Ungrafted film showed a stable thermogram up to ～500°C. However, the grafting introduced a new decomposition range in the copolymer, due to the presence of the AMS/BA. AFM images showed the formation of domains on the grafted PEEK film surface. The SEM also showed domain formation of the grafted component within the PEEK matrix. However, the fracture analysis did not show any prominent phase separation. Mechanical characterization of films in terms of tensile strength, elongation, and modulus was also carried out. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

聚合物加工流变学研究新动向

简要介绍了聚合物加工过程中伸长粘度与吹塑成型的关系、伸长流动非线性度与聚合物结构的关系,聚苯乙烯共混物,长玻璃纤维增强聚丙烯和热塑性淀粉的流变行为以及两种新型的流变测定仪。     

Short‐time fabrication of well‐mixed high‐density polyethylene/ultrahigh‐molecular‐weight polyethylene blends under elongational flow: morphology,mechanical properties and mechanism

As linear polyethylenes, ultrahigh‐molecular‐weight polyethylene (UHMWPE) and high‐density polyethylene (HDPE) have the same molecular structure, but the large difference in viscosity between them makes it difficult to obtain well‐mixed blends. An innovative eccentric rotor extruder (ERE) generating an elongational flow was used to prepare HDPE/UHMWPE blends within short processing times. Compared with the obvious two‐phase morphology of a sample from a twin‐screw extruder observed with a scanning electron microscope, few small UHMWPE particles were observed in the HDPE matrix for a sample from the ERE, indicating the good mixing on a molecular level of HDPE/UHMWPE blends achieved by the ERE during short processing times. The morphological changes of blends prepared using the ERE evidenced the good integration of HDPE and UHMWPE even though the UHMWPE content is up to 50 wt% in the blends. Moreover, all blends retained most of the intrinsic molecular weight. The good mixing was further confirmed from the thermal, crystallization and rheological behaviors determined using differential scanning calorimetry and dynamic rheological measurements. Importantly, the 50/50 blend presented improved mechanical properties, especially super‐impact strength of 151.9 kJ m^?2 with incomplete‐break fracture state. The strengthening and great toughening effects of UHMWPE on the blends were attributed to the addition of unwrapped UHMWPE long molecular chains. The effective disentanglement mechanism of UHMWPE chains under elongational flow was explained schematically by a non‐parallel three‐plate model. © 2019 Society of Chemical Industry     

Elongational flow studies of the conformation of DNA molecules in the globular state

Elongational flow‐induced birefringence of a T4‐phage DNA aqueous solution was measured with changing NaCl and polyethylene glycol (PEG) concentrations. DNA molecules are known to manifest a coil–globule transition with increasing PEG concentration. At certain PEG concentrations near the critical concentration of the transition, the globular DNA solution, which was expected to be nonbirefringent, showed flow‐induced birefringence. Strain‐rate dependence of the birefringence intensity, having a critical strain rate, was similar to that of the flexible polymer chain that manifests the coil–stretch transition. The flow‐induced birefringence pattern, however, suggested that the globular DNA molecules were rigid and optically anisotropic. At the critical strain rate, the globular DNA molecules in the solution of the particular PEG concentration were considered to collapse nonadiabatically to an optically anisotropic and mechanically rigid conformation. The overall shape of the collapsed conformation of the globular DNA was estimated to be an ellipsoid with an aspect ratio of about 0.7. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1351–1358, 2000     

Dielectric relaxation in vinylidene fluoride–hexafluoropropylene copolymers

The molecular mobility in copolymers of vinylidene fluoride–hexafluoropropylene VDF/HFP of 93/7 and 86/14 ratios has been investigated by means of broadband dielectric relaxation spectroscopy (10^?1–10⁷ Hz), differential scanning calorimetry DSC (?100 to 150°C), and of wide angle X‐ray diffraction WAXS. Four relaxation processes and one ferroelectric‐paraelectric phase transition have been detected. The process of the local mobility β‐ (at temperatures below glass transition point) is not affected by chemical composition of the copolymer and the formed structure. Parameters of segmental mobility in the region of glass transition (α_a‐relaxation) depend on the ratio of comonomer with lower kinetic flexibility. α_c‐relaxation is clearly observed only in VDF/HFP 93/7 copolymer, which is characterized by a higher crystallinity and a higher perfection of crystals of α‐ (α_p‐) phase. Diffuse order–disorder relaxor type ferroelectric transition connected with the destruction of the domains in low‐perfect ferroelectric phase in the amorphous regions has been detected for both copolymers. An intensive relaxation process (α‐process) was observed for both copolymers in high‐temperature region. DSC data shows that it falls on the broad temperature region of α‐phase crystals melting. It is considered to be connected with the space charge relaxation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007