EFFECT OF ETHYLENE-PROPYLENE COPOLYMER WITH RESIDUAL PE CRYSTALLINITY ON MECHANICAL-PROPERTIES AND MORPHOLOGY OF PP/HDPE BLENDS

Morphology and mechanical properties of polypropylene (PP)/high density polyethylene (HDPE) blends modified by ethylene-propylene copolymers (EPC) with residual PE crystallinity were investigated. The EPC showed different interfacial behavior in PP/HDPE blends of different compositions. A 25/75 blend of PP/HDPE (weight ratio) showed improved tensile strength and elongation at break at low EPC content (5 wt %). For the PP/HDPE = 50/50 blend, the presence of the EPC component tended to make the PP dispersed phase structure transform into a cocontinuous one, probably caused by improved viscosity matching of the two components. Both tensile strength and elongation at break were improved at EPC content of 5 wt %. For PP/HDPE 75/25 blends, the much smaller dispersed HDPE phase and significantly improved elongation at break resulted from compatibilization by EPC copolymers. (C) 1995 John Wiley & Sons, Inc.

A rheology study of high-energy radiolysis of a semicrystalline ethylene-propylene copolymer containing DOP mobilizer

The ractiolysis of a poly(ethylene-co-propylene), Elpro grade P 750 J, marketed by Thai Polypropylene Co. Ltd. for the manufacture of medical goods, was investigated at ambient temperature and melt rheology measured. The roles of calcium stearate, blended with the Elpro as a processing aid, and dioctyl phthalate (DOP), added in various amounts as a radical scavenger, were assessed. Following radiolysis, G' and the viscosity of the polymer melts at 453 K both decreased with increasing radiation dose, even when the mobilizer was present. The results indicated that although the DOP did scavenge radicals, it did not protect the polymer from net chain scission in a low-dose regimen. The value of (G(S) - 4G(X)) was approximately 0.6-0.7. (c) 2006 Wiley Periodicals, Inc.

Reactive processing of polymers:melt grafting of glycidyl methacrylate on ethylene propylene copolymer in the presence of a coagent

Glycidyl methacrylate (GMA) was grafted on ethylene-propylene copolymer during melt processing with peroxide initiation in the presence and absence of a more reactive comonomer (coagent), trimethylolpropane triacrylate (Tris). The characteristics of the grafting systems in terms of the grafting reaction yield and the nature and extent of the competing side reactions were examined. The homopolymers of GMA (Poly-GMA) and Tris (Poly-Tris) and the GMA-Tris copolymer (GMA-co-Tris) were synthesized and characterized. In the absence of the coagent, high levels of poly-GMA, which constituted the major competing reaction, was formed, giving rise to low GMA grafting levels. Further, this grafting system resulted in a high extent of gel formation and polymer crosslinking due to the high levels of peroxide needed to achieve optimum GMA grafting and a consequent large drop in the melt index (increased viscosity) of the polymer. In the presence of the coagent, however, the grafting system required much lower peroxide concentration, by almost an order of magnitude, to achieve the optimum grafting yield. The coagent-containing GMA-grafting system has also resulted in a drastic reduction in the extent of all competing reactions, and in particular, the GMA homopolymerization, leading to improved GMA grafting efficiency with no detectable gel or crosslinking. The mechanisms of the grafting reactions, in the presence and absence of Tris, are proposed.

Characterization of High Melt Strength Polypropylene Synthesized via Silane Grafting Initiated by In Situ Heat Induction Reaction

High melt strength polypropylene (HMSPP) was synthesized by in situ heat induction reaction, in which pure polypropylene (PP) powders without any additives were used as a basic resin and vinyl trimethoxysilane (VTMS) as a grafting and crosslinking agent. The grafting reaction of VTMS with PP was confirmed by FTIR. The structure and properties of HMSPP were characterized by means of various measurements. The content of grafted silane played a key role on the melt strength and melt flow rate (MFR) of HMSPP. With increasing the content of grafted silane, the melt strength of HMSPP increased, and the MFR reduced. In addition, due to the existence of cross-linking structure, the thermal stability and tensile strength of HMSPP were improved compared with PP.

C-13 NMR study of ethylene/propylene/octene-1 terpolymers synthesized with TiCl4/MgCl2/i-Bu3Al as the catalyst

The theory of chemical shift effect of substituent was applied to the assignment of the C-13 NMR spectra of the ethylene/propylene and ethylene/octene-1 copolymers. Using the parameters derived above and the DEFT technique, we then entirely assigned the C-13 NMR spectra of the ethylene/propylene/octene(-1) terpolymers synthesized in the presence of the same heterogeneous supported Ziegler-Natta catalyst, TiCl4/MgCl2/i-Bu3Al. The present paper also covers the terpolymer composition and the monomer sequence distributions of a series of ethylene/propylene/octene-1 terpolymers.

Preparation of polymer-supported zirconocene catalysts and olefin polymerization

A novel polymer-supported metallocene catalyst with crosslinked poly(styrene-co-acrylamide) (PSAm) as the support has been prepared and characterized. The probability of long sequences of acrylamide (Am) in PSAm is still low even at an Am amount of 32.8 mol %, implying the relatively homogeneous distribution of Am. The infrared spectra of PSAm and the supported catalyst substantiate that an amide group in PSAm coordinates with methylaluminoxane through both oxygen and nitrogen atoms. Ethylene/alpha-octene copolymerization showed that the catalytic activity is not markedly affected by adding alpha-octene. C-13 NMR analysis of the ethylene/alpha-octene copolymer indicated that the composition distribution of the copolymer is uniform. (C) 1999 John Wiley & Sons, Inc.

Crystallization behavior of the novel LLDPE and its molecular characteristics

Crystallization behavior of the single-site catalysed ethylene-octene-1 copolymer (LLDPE) has been investigated. The results indicate that the distribution of branches in the novel LLDPE is more homogeneous and regular than that in materials prepared with Ziegler-Natta catalysts. However, there is still some variability in inter-branch separation. The work has confirmed that branches trend to be excluded from crystals formed by branched polyethylene, but it is dependent on branch distribution and crystallization dynamics.

THE CRYSTALLIZATION BEHAVIOUR OF BLOCK COPOLYMER/HOMOPOLYMER BLENDS I. INFLUENCE OF NONSPHERICAL MICELLE ON CRYSTALLIZATION BEHAVIOUR IN DILUTE SOLID SOLUTIONS

The effect of micelle on crystallization behaviour of dilute poly(methyl methacrylate-b-tetrahydrofuran) diblock copolymer/tetrahydrofuran homopolymer, dilute poly (ethylene-b-styrene-b-ethylene) triblock copolymer/ethylene homopolymer solutions has been studied. The results show that with the structural teansitions from spherical to nonspherical micelle in the blends, great changes in the nucleation and spherulite morphologies take place.

Reactive processing methods for functionalisation of polymers and in-situ compatibilisation of poly(ethylene terephthalate)-based blends

One of the main objectives of this study was to functionalise various rubbers (i.e. ethylene propylene copolymer (EP), ethylene propylene diene terpolymer (EPDM), and natural rubber (NR)) using functional monomers, maleic anhydride (MA) and glycidyl methacrylate (GMA), via reactive processing routes. The functionalisation of the rubber was carried out via different reactive processing methods in an internal mixer. GMA was free-radically grafted onto EP and EPDM in the melt state in the absence and presence of a comonomer, trimethylolpropane triacrylate (TRlS). To optinuse the grafting conditions and the compositions, the effects of various paranleters on the grafting yields and the extent of side reactions were investigated. Precipitation method and Soxhlet extraction method was established to purifY the GMA modified rubbers and the grafting degree was determined by FTIR and titration. It was found that without TRlS the grafting degree of GMA increased with increasing peroxide concentration. However, grafting was low and the homopolymerisation of GMA and crosslinking of the polymers were identified as the main side reactions competing with the desired grafting reaction for EP and EPDM, respectively. The use of the tri-functional comonomer, TRlS, was shown to greatly enhance the GMA grafting and reduce the side reactions in terms of the higher GMA grafting degree, less alteration of the rheological properties of the polymer substrates and very little formation of polyGMA. The grafting mechanisms were investigated. MA was grafted onto NR using both thermal initiation and peroxide initiation. The results showed clearly that the reaction of MA with NR could be thermally initiated above 140°C in the absence of peroxide. At a preferable temperature of 200°C, the grafting degree was increased with increasing MA concentration. The grafting reaction could also be initiated with peroxide. It was found that 2,5-dimethyl-2,5-bis(ter-butylproxy) hexane (TIOI) was a suitable peroxide to initiate the reaction efficiently above I50°C. The second objective of the work was to utilize the functionalised rubbers in a second step to achieve an in-situ compatibilisation of blends based on poly(ethylene terephthalate) (PET), in particular, with GMA-grafted-EP and -EPDM and the reactive blending was carried out in an internal mixer. The effects of GMA grafting degree, viscosities of GMAgrafted- EP and -EPDM and the presence of polyGMA in the rubber samples on the compatibilisation of PET blends in terms of morphology, dynamical mechanical properties and tensile properties were investigated. It was found that the GMA modified rubbers were very efficient in compatibilising the PET blends and this was supported by the much finer morphology and the better tensile properties. The evidence obtained from the analysis of the PET blends strongly supports the existence of the copolymers through the interfacial reactions between the grafted epoxy group in the GMA modified rubber and the terminal groups of PET in the blends.

异氰酸醋官能化乙丙共聚物的制备及其与尼龙6共混体系的研究

本工作合成了一种含异氰酸酷功能基团的不饱和单体，（3-异氰酸酯基-4-甲基）苯氨基甲酸-2-丙烯配（TAI）。以过氧化二异丙苯（OCP）为引发剂，该单体被用于乙烯丙烯共聚物（EPM）的自由基溶液接枝官能化。纯化后的接枝产物（EPM-g-TAI）的傅立叶变换红外光谱中存在2273cm-l异氰酸酷基团（-NCO），表明异氰酸醋单体已经接枝到乙丙共聚物上。接枝率采用化学滴定和红外光谱的方法确定。与EPM相比，EPM-g-TAl的分子量分布（MMO）变窄。采用旋转流变仪测定了EPM-g-TAl的流变行为。EPM-g-TAl的表观粘度高于EPM且随接枝率的增加而增加。采用接触角测定的表面分析表明，对于给定的的极性测定液体接枝产物的接触角随接枝率的增加而增大；我们同时得到接枝产物的表面自由能（75）以及表面自由能的色散分量（γs）和表面自由能的极性分量（γsρ），这些参数随接枝率提高而增大的趋势使我们可以定量估计接枝反应对改善极性的贡献。本工作研究了（3一异氰酸酯基-4-甲基）苯氨基甲酸-2-丙烯醋（TAl）官能化乙烯丙烯共聚物（EPM-g-TAI）与尼龙6（PA6）的反应共混。傅立叶变换红外光谱表明，由于EPM-g-TAl中的异氰酸醋基（-NCO）与尼龙6中的端胺基（-NH2）之间的化学反应：EPM-g-TAI／PA6谱图中3299cm-1处的阵日伸缩振动峰变窄变高，1640cm-1处阵日变形振动峰和1547cm-1处阵日弯曲振动峰变强。同时研究了共混体系的热性能、流变性能、机械性能和形态特征。OSC结果表明，在相同的共混组成下，EPM-g-TAI／PA6共混体系中尼龙6的结晶烩（△Hc）到氏于EPM／PA6共混体系中的尼龙6，这种差别随着共混物中乙烯丙烯共聚物含量的增加而增大，说明反应共混体系中尼龙6的结晶受到一定的限制；EPM-g-TAI／PA6共混体系的复数粘度和贮能模量高于相应的EPM／PA6共混体系；与相同组成的EPM／PA6相比，EPM-g-TAI／PA6中分散相的粒子尺寸更小，粒子分布更均匀，界面粘合更强；反应共混后的机械性能如拉伸强度、杨氏模量，弯曲强度和模量、缺口及非缺口冲击强度均随着接枝率的提高而增加。

Mass transfer resistance in the production of high impact polypropylene

Mass transfer resistance in the production of high impact polypropylene (hiPP) produced by a two-stage slurry/gas polymerization was investigated by field-emission scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. It is found that the formation of ethylene-propylene copolymer (EPR) phases in polypropylene (iPP) particle produced in the first stage slurry polymerization exhibits a developing process from exterior to interior

Multilayered core-shell structure of the dispersed phase in high-impact polypropylene

The multiphase morphology of high impact polypropylene (hiPP), which is a reactor blend of polypropylene (PP) with ethylene-propylene copolymer, was investigated by transmission electron microscopy, selected area electron diffraction, atomic force microscopy, and field-emission scanning electron microscopy techniques in conjunction with an analysis of the hiPP composition and chain structure based on solvent fractionation, C-13-NMR, and differential scanning calorimetry measurements.

Synthesis of biodegradable thermo- and pH-responsive hydrogels for controlled drug release

Novel intelligent hydrogels composed of biodegradable and pH-sensitive poly(L-glutamic acid) (PGA) and temperature sensitive poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) (PNH) were synthesized and characterized for controlled release of hydrophilic drug. The influence of pH on the equilibrium swelling ratios of the hydrogels was investigated. A higher PNH content resulted in lower equilibrium swelling ratios. Although temperature had little influence on the swelling behaviors of the hydrogels, the changes of optical transmittance of hydrogels as a function of temperature were marked, which showed that the PNH part of hydrogel exhibited hydrophobic property at temperature above the lower critical solution temperature (LCST). The biodegradation rate of the stimuli-sensitive hydrogels in the presence of enzyme was directly proportional to the PGA content. Lysozyme was chosen as a model drug and loaded into the hydrogels.

Evolution of phase morphology of high impact polypropylene particles upon thermal treatment

Solvent fractionation and differential scanning calorimetry (DSC) results show that high impact polypropylene (hiPP) produced by a multistage polymerization process consists of PP homopolymer, amorphous ethylene-propylene random copolymer (EPR), and semicrystalline ethylene-propylene copolymer. For the original hiPP particles obtained right after polymerization, direct transmission electron microscopy (TEM) observation reveals a fairly homogeneous morphology of the ethylene-propylene copolymer (EP) phase regions inside, while the polyethylene-rich interfacial layer observed between the EP region and the iPP matrix supports that EP copolymers form on the subglobule surface of the original iPP particles. Compared with that in original hiPP particles, the dispersed EP domains in pellets have much smaller average size and relatively uniform size distribution, indicating homogenization of the EP domains in the hiPP by melt-compounding. Upon heat-treatment, phase reorganization occurs in hiPP, and the dispersed EP domains can form a multiple-layered core-shell structure, comprising a polyethylene-rich core, an EPR intermediate layer and an outer shell formed by EP block copolymer, which accounts to some extent for the good toughness-rigidity balance of the material.