原位聚合法制备超疏水的聚乙烯纳米复合材料

采用一种新方法将Ziegler-Natta催化剂组分TiCl4和MgCl2负载到蒙脱土(MMT)的层间,制备了TiCl4/MgCl2/MMT插层型催化剂.利用Ziegler-Natta催化剂特有的"形态复制效应",通过乙烯原位聚合制备出了表面具有花瓣状形态的聚乙烯纳米复合材料.这种聚乙烯纳米复合材料的表面与水的接触角达到(152.2±0.8)°,呈现超疏水性质.

Synthesis, structural characterization, and ethylene polymerization behavior of the vanadium(III) complexes bearing salicylaldiminato ligands

Vanadium(III) complexes bearing salicylaldiminato ligands (2a-k) [RN=CH(Ar0)]VCl2(THF)2 (Ar C61714, R = Ph, 2a; p-CF3Ph, 2b; p-CH3Ph, 2c; 2,6-Me2Ph, 2d; 2,6-iPr2Ph, 2e; cyclohexyl, 2f; Ar = C6H3tBu(2), R = Ph, 2g; 2,6-iPr2Ph, 2h; Ar = C6H2tBU2(2,4), R = Ph, 2i; 2,6-iPr2Ph, 2j; Ar = C6H2Br2, R = Ph, 2k) were prepared from VC13(THF)3 by treating with 1.0 equiv of (RN=CH)ArOH in tetrahydrofuran (THF) in the presence of excess triethylamine (TEA).

磷酸三苯酯作为内给电子体的聚丙烯催化剂研究

在各种聚丙烯催化剂中, 应用最为广泛的是Ziegler-Natta(Z-N)催化体系。而作为Z-N催化剂的重要组分之一,内给电子体是影响催化剂活性和聚合物立构规整性的重要因素,因此Z-N催化剂的发展从另一方面看就是内外给电子体的发展,调整催化剂中内给电子体组分的组成和结构是改善钛、镁为主体的Z-N聚丙烯催化剂的催化性能及聚丙烯产品性能的有效手段之一。本文以磷酸三苯酯作为内给电子体, 制备了Ziegler-Natta高效载体催化剂,通过红外光谱确定了磷酸三苯酯在催化剂中与活性中心的络合。聚合结果表明：此催化剂具有较高的聚合活性, 聚合产物聚丙烯具有较高的堆积密度和等规度,并且分子量分布较宽,此研究为制备具有良好加工性能与力学性能的聚丙烯及其共聚产品提供了新的技术支持。

Effect of Copolymerization Time on the Microstructure and Properties of Polypropylene/Poly(ethylene-co-propylene) In-Reactor Alloys

Three Polypropylene/Poly(ethylene-co-propylene) (PP/EPR) in-reactor alloys produced by a two-stage slurry/gas polymerization had different ethylene contents and mechanical properties, which were achieved by controlling the copolymerization time. The three alloys were fractionated into five fractions via temperature rising dissolution fractionation (TRDF), respectively. The chain structures of the whole samples and their fractions were analyzed using high-temperature gel permeation chromatography (GPC), Fourier transform infrared (FT-IR), C-13 nuclear magnetic resonance (C-13 NMR), and differential scanning calorimetry (DSC) techniques. These three in-reactor alloys mainly contained four portions: ethylenepropylene random copolymer (EPR), ethylene-propylene (EP) segmented and block copolymers, and propylene homopolymer. The increased copolymerization time caused the increased ethylene content of the sample. The weight percent of EPR, EP segmented and block copolymer also became higher.

Enhanced crystallization of the gamma-form of propylene-ethylene copolymer in its miscible blends with propylene homopolymer

BACKGROUND: How to promote the formation of the gamma-form in a certain propylene-ethylene copolymer (PPR) under atmospheric conditions is significant for theoretical considerations and practical applications. Taking the epitaxial relationship between the alpha-form and gamma-form into account, it is expected that incorporation of some extrinsic alpha-crystals, developed by propylene homopolymer (PPH), can enhance the crystallization of the gamma-form of the PPR component in PPR/PPH blends.RESULTS: The PPH component in the blends first crystallizes from the melt, and its melting point and crystal growth rate decrease with increasing PPR fraction. On the other hand, first-formed alpha-crystals of the PPH component can induce the lateral growth of PPR chains on themselves, indicated by sheaf-like crystal morphology and positive birefringence, which is in turn responsible for enhanced crystallization of the gamma-form of the PPR component.

Synthesis, Structural Characterization, and Olefin Polymerization Behavior of Vanadium(III) Complexes Bearing Tridentate Schiff Base Ligands

Vanadium(III) complexes bearing tridentate salicylaldiminato ligands (2a-f) [OC6H4CH=NL]VCl2(THF) (L = CH2CH2OMe, 2a; CH2CH2NMe2, 2b; CH2C5H4N, 2c; 8-C9H6N (quinoline), 2d; 2-MeSC6H4, 2e; 2-Ph2PC6H4, 2f) and tridentate beta-enaminoketonato ligands [OC6H8CH=N-2-Ph2PC6H4]VCl2(THF) (2g) and [O(Ph)C=CHCH=N-2-Ph2PC6H4]VCl2(THF) (2h) were prepared from VCl3(THF)(3) by treating with 1.0 equiv of the deprotonated ligands in tetrahydrofuran (THF). These complexes were characterized by FTIR and mass spectrometry as well as elemental analysis. Structures of complexes 2e, 2f, and 2h were further confirmed by X-ray crystallographic analysis. These complexes were investigated as catalysts for olefin polymerization in the presence of organoaluminum compounds. On activation with Et2AlCl, complexes 2a-h exhibited high catalytic activities toward ethylene polymerization (up to 20.64 kg PE/mmol(v) center dot h center dot bar) even at high temperature, suggesting these catalysts possess high thermal stability.

Ethylene Polymerization and Ethylene/Hexene Copolymerization with Vanadium(III) Catalysts Bearing Heteroatom-Containing Salicylaldiminato Ligands

A series of novel vanadium(III) complexes hearing heteroatoill-containing group-substituted salicylaldiminato ligands [RN=CH(ArO)]VCl2(THF)(2) (Ar = C6H4, R = C3H2NS, 2a; C7H4NS, 2c; C7H5N2, 2d; Ar = C(6)H(2)tBu(2) (2,4), R = C3H2NS, 2b) have been synthesized and characterized. Structure of complex 2c was further confirmed by X-ray crystallographic analysis. The complexes were investigated as the catalysts for ethylene polymerization in the presence of Et2AlCl. Complexes 2a-d exhibited high catalytic activities (up to 22.8 kg polyethylene/mmolv h bar), and affording polymer with unimodal molecular weight distributions at 25-70 degrees C in the first 5-min polymerization, whereas produced bimodal molecular weight distribution polymers at 70 degrees C when polymerization time prolonged to 30 min. The catalyst structure plays an important role in controlling the molecular weight and molecular weight distribution of the resultant polymers produced in 30 min polymerization. In addition, ethylene/hexene copolymerizations with catalysts 2a-d were also explored in the presence of Et2AlCl, which leads to the high molecular weight and unimodal distributions copolymers with high comonomer incorporation.

Novel vanadium(III) complexes with bidentate N,N-chelating iminopyrrolide ligands: synthesis, characterization and catalytic behaviour of ethylene polymerization and copolymerization with 10-undecen-1-ol

A series of novel vanadium(III) complexes bearing iminopyrrolide chelating ligands [2-(RN=CH)C4H3N]V(THF)(2)Cl-2 (2a: R = cyclohexyl; 2b: R = Ph; 2c: R = 2,6-iPr(2)C(6)H(3); 2d: R = p-CF3C6H4; 2e: R = C6F5) have been synthesized and characterized. Single-crystal X-ray diffraction revealed that complexes 2a, 2c and 2e adopt an octahedral geometry around the vanadium center. In the presence of Et2AlCl as a co-catalyst, these complexes displayed high catalytic activities up to 48.6 kg PE mmol(V)(-1) h(-1) bar(-1) for ethylene polymerization, and produced high molecular weight polymers. 2a-e/Et2AlCl catalytic systems were tolerant to elevated temperature (70 degrees C) and yielded unimodal polyethylenes, indicating the single site behaviour of these catalysts. By pre-treating with equimolar amounts of alkylaluminums, functional alpha-olefin 10-undecen-1-ol can be efficiently incorporated into polyethylene chains. 10-Undecen-1-ol incorporation can easily reach 15.8 mol% under the mild conditions.

Effect of swelling response of the support particles on ethylene polymerization

Macroporous and modified macroporous poly(styrene-co-methyl methacrylate-co-divinylbenzene) particles (m-PS and mm-PS) supported Cp2ZrCl2 were prepared and applied to ethylene polymerization using methylaluminoxane (MAO) as cocatalyst. The influences of the swelling response of the support particles on the catalyst loading capabilities of the supports as well as on the activities of the supported catalysts were studied. It was shown that the Zr loadings of the supports and the activities of the supported catalysts increased with the swelling extent of the support particles. The m-PS or mm-PS supported catalysts exhibited very high activities when the support particles were well swollen, whereas those catalysts devoid of swelling treatment gave much lower activities. Investigation on the distribution of the supports in the polyethylene by TEM indicated that the swelling of the support particles allowed the fragmentation of the catalyst particles. In contrast, the fragmentation of the support particles with poor swelling was hindered during ethylene polymerization.

Evolution of the interfacial tension between polydisperse "immiscible" polymers in the absence and in the presence of a compatibilizer

The interfacial tension sigma between two polyisobutylenes (PIB) of dissimilar polydispersity and two polydisperse samples of poly(dimethylsiloxane) (PDMS) was measured as a function of time by means of a pendent drop apparatus at different temperatures ranging from 30 to 110 degreesC. In addition to three of the four possible binary blends, the time evolution of sigma was also determined for one ternary system, where the PIB phase contained 0.03 wt % of a diblock copolymer poly(isobutylene-b-dimethylsiloxane). The pronounced decrease of sigma with advancing time, observed in all cases, is attributed to the migration of the interfacially active lower molecular weight components of the homopolymers and of the compatibilizer into the interphase. Several days are normally required until a becomes constant. These time independent values are not considered as equilibrium data, but accredited to stationary states. A kinetic model is established for sigma(t), which enables a detailed investigation of the rates of transport of the different migrating species of average molar mass of M.

Zirconocene catalyst well spaced inside modified montmorillonite for ethylene polymerization: role of pretreatment and modification of montmorillonite in tailoring polymer properties

Zirconocene catalyst was heterogenized inside an organosilane-modified montmorillonite (MMT) pretreated by calcination and acidization, for supported catalyst systems with well-spaced alpha-olefin polymerization active centers. The varied pretreatment and modification conditions of montmorillonite are efficient for supported zirconocene catalysts in control of polyethylene microstructures, in particular, molecular weight distribution. In contrast to other supported catalyst systems, Cp2ZrCl2/modified montmorillonite(MMT-7)-supported catalysts with a distinct interlayer structure catalyzed ethylene homopolymerization and copolymerization with I-octene activated by methylaluminoxane (MAO), resulting in polymers with a bimodal molecular weight distribution (MWD).

茂金属线形低密度聚乙烯的热降解研究

研究了光敏剂钴化合物存在时茂金属催化剂和Ziegler Natta催化剂生产的线形低密度聚乙烯 (m PE LLD和PE LLD)的热降解行为 ,测定了降解后产品的熔体流动速率、红外光谱和氧化诱导温度。结果表明 :光敏剂使得加工过程中的降解反应增强 ,氧化诱导温度降低 ,氧化曲线形状发生改变 ;与PE LLD相比 ,光敏剂对增强m PE LLD的降解反应和降低加工后样品的热稳定性的作用更强。

Ethylene polymerization with porous polystyrene spheres supported Cp2ZrCl2 catalyst

A catalyst with porous polystyrene beads supported Cp2ZrCl2 was prepared and tested for ethylene polymerization with methylaluminoxane as a cocatalyst. By comparison, the porous supported catalyst maintained higher activity and produced polyethylene with better morphology than its corresponding solid supported catalyst. The differences between activities of the catalysts and morphologies of the products were reasonably explained by the fragmentation processes of support as frequently observed with the inorganic supported Ziegler-Natta catalysts. Investigation into the distribution of polystyrene in the polyethylene revealed the fact that the porous polystyrene supported catalyst had undergone fragmentation during polymerization.

Characterization of the microstructure of biaxially oriented polypropylene using preparative temperature-rising elution fractionation

Two commercial biaxially oriented polypropylene (BOPP) resins, resin A and resin B, having different processing properties, were fractionated by preparative temperature-rising elution fractionation (TREF). The TREF fractions were further characterized by gel permeation chromatography (GPC), gel permeation chromatography coupled with light scattering (GPC-LS), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). GPC-LS did not find visible long-chain branching in either resin A or B. The results from TREF and DSC indicate that the fractional melting parameter f(T) may be used to predict the profile of the TREF cumulative weight distribution curve. GPC results show that the molecular weights of the fractions tend to increase with elution temperature. WAXD and DSC data show that the crystallinity of fractions does not increase monotonically with increase of elution temperature. There appears to be a maximum in the plot of crystallinity versus elution temperature. The high-speed BOPP resin A has a lower isotacticity but a homogeneous isotacticity distribution and a higher molecular weight but a broader molecular weight distribution than resin B.

Synthesis and characterization of polypropylene/montmorillonite nanocomposites via an in-situ polymerization approach

Polypropylene/montmorillonite (PP/MMT) nanocomposites were prepared by in-situ polymerization using a MMT/MgCl2/TiCl4-EB Ziegler-Natta catalyst activated by trietbylaluminum (TEA). The enlarged layer spacing of MMT was confirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components. X-ray photoelectron spectrometry (XPS) analysis proved that TiCl4 was mainly supported on MgCl2 instead of on the surface of MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXD patterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).