Synthesis of polyolefin composition in the presence of supported catalysts

Polyolefins are basic materials in the plastics. Their application is limited by their low thermostability, adhesion, hardness and other physico-mechanical properties. The following treatments are known to improve and modify polyolefin properties: the incorporation of inorganic or organic fillers with a greater hardness and rigidity into the polyolefin matrix, the grafting of functional groups to polyolefins, and crosslinking with the formation of a network structure in the polyolefin matrix. In the case of polymers and inorganic materials, the activation of their surface by the functionalizing and fixing of transition metals allows one to perform polymerization of monomers on a surface to obtain a polymer–polymer composites and a highly filled polymer–inorganic composites.     

Crystallization behavior of poly(ε‐caprolactone)/multiwalled carbon nanotube composites

Differential scanning calorimetry (DSC), polarized optical microscopy, and X‐ray diffraction methods were used to investigate the isothermal crystallization behavior and crystalline structure of poly(?‐caprolactone) (PCL)/multiwalled carbon nanotube (MWNT) composites. PCL/MWNT composites were prepared via the mixing of a PCL polymer solution with carboxylic groups containing multiwalled carbon nanotubes (c‐MWNTs). Both Raman and Fourier transform infrared spectra indicated that carboxylic acid groups formed at both ends and on the sidewalls of the MWNTs. A transmission electron microscopy micrograph showed that c‐MWNTs were well separated and uniformly distributed in the PCL matrix. DSC isothermal results revealed that introducing c‐MWNTs into the PCL structure caused strongly heterogeneous nucleation induced by a change in the crystal growth process. The activation energy of PCL drastically decreased with the presence of 0.25 wt % c‐MWNT in PCL/c‐MWNT composites and then increased with increasing MWNT content. The result indicated that the addition of c‐MWNT to PCL induced heterogeneous nucleation (lower total activation energy) at a lower c‐MWNT content and then reduced the transportation ability of polymer chains during crystallization processes at a higher MWNT content (higher total activation energy). A correlation between the crystallization kinetics, melting behavior, and crystalline structure of PCL/c‐MWNT composites was also discussed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 598–606, 2006     

A MOF@COF Composite with Enhanced Uptake through Interfacial Pore Generation

Herein, we describe a new class of porous composites comprising metal–organic framework (MOF) crystals confined in single spherical matrices made of packed covalent‐organic framework (COF) nanocrystals. These MOF@COF composites are synthesized through a two‐step method of spray‐drying and subsequent amorphous (imine‐based polymer)‐to‐crystalline (imine‐based COF) transformation. This transformation around the MOF crystals generates micro‐ and mesopores at the MOF/COF interface that provide far superior porosity compared to that of the constituent MOF and COF components added together. We report that water sorption in these new pores occurs within the same pressure window as in the COF pores. Our new MOF@COF composites, with their additional pores at the MOF/COF interface, should have implications for the development of new composites.     

Structure and water sorption of polyurethane nanocomposites based on organic and inorganic components

Organic-inorganic polymer composites, consisting of a polyurethane organic phase and a mineral inorganic phase were prepared by the joint polymerization of the urethane oligomer with the water solution sodium silicate. The structure and the morphology of the composites, at a fixed weight fraction of the inorganic component of 20%, and of the corresponding pure polyurethane matrices were investigated by wide-angle and small-angle X-ray scattering (WAXS and SAXS, respectively). The results show similar size (5-7 nm) of the scale of heterogeneity of the composites due to the microphase separation of the rigid and the flexible blocks of the amorphous polyurethane matrix and due to the inorganic crystalline inclusions, i.e. the materials prepared are nanocomposites. The WAXS measurements indicate that the individual properties of the block inorganic component are lost in the nanocomposites, probably due to physical and chemical interactions between the two components. Water sorption from the liquid phase was studied gravimetrically in a composite and in the corresponding polyurethane. The results show high sorption capacity of the composite, due to the hydrophilicity of the inorganic phase and the elasticity of the polyurethane matrix, and allow to estimate the layer thickness of water adsorbed on the inorganic nanoparticle surface to about 20 nm, in reasonable agreement with a model adopted from the literature. WAXS and SAXS measurements on the swelled composite and the swelled-and-dried composite indicate changes in the structure of the inorganic component induced by water, which are, however, to a large extent reversible. These materials may find applications as gel electrolytes and as hydrogels in drug delivery systems.     

Surface engineering of nanoparticles for highly efficient UV‐shielding composites

Overexposure to ultraviolet (UV) with high energy can not only hurt human skin but also accelerate the degradation of organic matter. Hence, the preparation of polymer‐based UV‐shielding nanocomposites has attracted substantial attention due to the low cost, easy processing and wide applications. Notably, the highly efficient UV‐shielding polymer nanocomposites are still hindered by the agglomeration of inorganic anti‐UV nanoparticles (Nps) in polymer matrix and the narrow absorption range of UV‐shielding agents. To overcome the aforementioned bottlenecks, surface engineering of anti‐UV Nps including organic modification and inorganic hybridization has been extensively employed to enhance the UV‐shielding efficiency of composites. Herein, to deliver the readers a comprehensive understanding of the surface engineering of anti‐UV Nps, we systematically summarize the recent advances in surface organic modification and inorganic hybridization related to anti‐UV Nps. The UV‐shielding mechanism and the factors affecting UV‐shielding efficiency of polymer nanocomposites are also discussed. Finally, perspectives on remaining challenges and future development of highly efficient UV‐shielding composites are outlined.     

The acquirement of desirable dielectric properties of carbon nanofiber composites based on the controlled crystallization

This study focused on uncovering the relationship among nanofiller, crystallization behavior, and dielectric property of polymer composites. The effects of carbon nanofibers (CNFs) and heat treatment on the crystalline structures and dielectric properties of the semi‐crystalline polymers were analyzed by using high density polyethylene (HDPE) as a matrix, which is a representative of non‐polar polymer and contains only one crystal structure. The experimental results showed that the degree of crystallinity, size distribution of crystallity, and relative amount of different crystal planes in the HDPE matrix were changing due to the addition of CNFs. With the increase of CNF loading, the dielectric constant, dielectric loss and AC conductivity of the HDPE composites were increased, presenting a typical percolation characteristic, and the dependence of the dielectric constant on frequency became more obvious. All kinds of electronic transmission, polarization effect, and relaxation behaviors in CNF/HDPE composite system were deeply analyzed. After heat treatment, the degree of crystallinity of HDPE composites was decreased with the enhanced cooling rate. For the CNF/HDPE composites with nanofiller content slightly higher than the percolation threshold, the significant increase of the dielectric constant and the dramatical reduction of the dielectric loss over a wide frequency range were realized simultaneously through rapid cooling treatment. The research indicated that a general commercial polymer material with excellent dielectric properties, which exhibited a high dielectric constant and a low dielectric loss, can be obtained by a simple technical approach different from traditional fabrication method of threshold composites.     

Visual research filler network structure in polymer composites and its structure-activity relationship by fluorescent labeling and LSCM

For organic-inorganic composite materials, the spatial dispersion of inorganic fillers in the organic matrix is of great significance for designing and manufacturing high-performance composite materials. To improve the understanding of the micro-physical mechanism of the filler-reinforced polymer matrix, we studied the relationship between filler network structure and macro-mechanical properties of silicone rubber by using fluorescent labeling technology and three-dimensional (3D) visualization imaging. The experimental results showed that a good filler network structure in the polymer matrix can more effectively dissipate external mechanical energy, which generate a visible mechanical strengthening effect. Additionally, this visualization method truly reflects the macrodispersion of the filler and the evolution of the filler network structure under dynamic stress due to its non-invasive and intuitive characteristics, which provides new theoretical guidance for the design of high-performance composites.     

Thermomechanical behaviors and dielectric properties of polyaniline‐doped para‐toluene sulfonic acid/epoxy resin composites

Composites based on conductive organic/inorganic fillers dispersed in insulating matrix have been widely investigated because of their widespread applications such as electromagnetic shielding, electrostatic discharge, and sensors. In this context, novel composite materials based on epoxy resin matrix charged with polyaniline (PANI)‐doped para‐toluene sulfonic acid were elaborated. Fourier transform infrared spectroscopy, X‐ray diffraction and scanning electron microscopy were used to check the structure and the morphology of the samples. Viscoelastic behavior and thermal stability of the composites were explored by dynamic mechanical thermal analysis and thermogravimetric analysis. It was shown that the PANI particles exhibited a partial crystalline structure and were homogeneously dispersed in epoxy matrix. Consequently, this structure affected the thermal stability and viscoelastic properties of the composites. Furthermore, the dielectric and electrical properties were investigated up to 1 MHz. Measurements of dielectric properties revealed that with loading fillers in matrix, the dielectric parameters increased to high values at low frequency then decreased at values around 40 and 32 of real and imaginary parts, respectively, at 1 MHz with 15% of PANI content. Copyright © 2011 John Wiley & Sons, Ltd.     

Strengthening of liquid crystalline polymer by functionalized carbon nanotubes through interfacial interaction and homogeneous dispersion

Multiwalled carbon nanotubes (MWCNTs) were functionalized with two types of chemical moieties (i.e. carboxylic, ? COOH and hydroxyl benzoic acid groups, ‐HBA) on their sidewalls in order to improve their interaction with a liquid crystalline polymer (LCP) and dispersion in LCP. We have investigated the rheological, mechanical, dynamic mechanical, and thermal properties in detail with variation of HBA‐functionalized MWCNTs in the LCP matrix. Effect of the dispersion state of the functionalized MWCNTs in the LCP matrix on the rheological behavior was also studied. The composites containing HBA‐functionalized MWCNTs showed higher complex viscosity, storage, and loss modulus than the composites with the same loading of raw MWCNTs and MWCNT‐COOH. It was suggested that the HBA‐functionalized MWCNTs exhibited a better dispersion in the polymer matrix and formed stronger CNT‐polymer interaction in the composites than the raw MWCNTs and MWCNT‐COOH, which was also confirmed by FESEM and FTIR studies. As a result, the overall mechanical performance of the HBA‐MWCNT‐LCP composites could be improved significantly. For example, the addition of 4 wt% HBA‐MWCNT to LCP resulted in the considerable improvements in the tensile strength and modulus of LCP (by 66 and 90%, respectively). Copyright © 2010 John Wiley & Sons, Ltd.     

Preparation of Sheet‐like Polymer‐Encapsulated Composite Particles by Seeded Polymerization from Sub‐micrometer Sheets

Seeded polymerization has been widely used to fabricate polymer‐encapsulated inorganic particles (IPs). The most frequently used seeds are spherical, whereas nonspherical particles are not well documented. Recently, sheet‐like IPs have attracted much attention in the context of polymer composites. This article is therefore dedicated to understanding seeded polymerization from submicron sheets and focuses on the control of the overall morphology of the composite particles obtained. However, it was found that the composite particles only maintained the sheet‐like morphology of the seeds at a low polymer content, whereas they became hamburger‐like at a high polymer content owing to minimization of the interfacial energy. Interestingly, when cross‐linked, the sheet‐like morphology could be well preserved, even at a rather high polymer content. With the encapsulating polymer layer, the obtained sheet‐like composite particles showed improved compatibility with the polymer matrix and could be well dispersed in polymer matrix when simply blended.     

Contribution of oriented structure and rigid nanofillers to mechanical enhancement of die-drawn PP/MWCNT composites

Oriented structure, mainly controlled by processing conditions, is another efficient method of reinforcing polymer materials in addition to compounding with rigid inorganic fillers such as carbon nanotubes (CNTs). The mechanical properties of oriented polypropylene (PP)/multiwalled CNT (MWCNT) composites, which are vital to their application fields, are investigated extensively in this paper, with an aim to distinguish the contribution of MWCNTs contents from that of the oriented structure to the final performance of the composite. The results indicate that MWCNTs mainly increase the modulus of the composites by approximately 140%. The oriented structure formed during the die-drawing process contributes more to the enhancement of tensile strength, increasing up to 550%. The modulus and tensile strength can be further improved by increasing the drawing speed. Moreover, the tensile stress field in the die-drawing process can vastly improve the dispersion of the MWCNTs in the matrix, thus providing a new idea for improving the dispersion of nanofillers in the polymer matrix.     

Property tailoring of particulate polymer composites by reactive processing

This study explores reactive processing aimed at improving the mechanical properties of polyolefin/inorganic particulate filler based composites. Three different polymer matrix materials have been studied in combination with the nine inorganic particulate fillers with different particle size and of varying pH. The reactive modifier 1,3‐phenylene dimaleimide (BMI) has been shown in all cases to be very effective in terms of improving composite properties beyond those of the respective unmodified composites and in some cases beyond those of the unfilled matrix materials. The detrimental effect of BMI on melt viscosity can be overcome via judicious use of a suitable lubricant, and together with response surface methods, followed by optimization procedures, composite properties can be tailored for specific end use applications.     

Morphology of a Poly(imide siloxane) Segmented Copolymer/Silica Hybrid Composite

The role of polydimethylsiloxane (PDMS) as a compatibilizer of polyimide/silica hybrid composites was investigated. Introduction of PDMS into a polyimide matrix retards the phase separation of hybrid composites and also prevents the formation of high‐molecular‐weight silicate. PDMS interacts with silica because of the similarity of its structure with the sol‐gel glass matrix of the silica precursor, indicating that poly(imide siloxane)/silica might be a good candidate material for organic/inorganic hybrid composites.     

Polymer Composites for Thermoelectric Applications

This review covers recently reported polymer composites that show a thermoelectric (TE) effect and thus have potential application as thermoelectric generators and Peltier coolers. The growing need for CO₂‐minimizing energy sources and thermal management systems makes the development of new TE materials a key challenge for researchers across many fields, particularly in light of the scarcity or toxicity of traditional inorganic TE materials based on Te and Pb. Recent reports of composites with inorganic and organic additives in conjugated and insulating polymer matrices are covered, as well as the techniques needed to fully characterize their TE properties.     

Analysis on interfacial stress in impact of polyphenylene sulfide/CaCO3 composites

The interfacial stress and its distribution during impact of inorganic particulate‐filled polymer composites were analyzed in the present paper by means of a three‐dimensional (3D) finite element method, and the software used was the ANSYS/LS‐DYNA (ANSYS Inc., Canonsburg, PA, USA). The simulation results showed that the normal stress, the shear stress, and the equivalent stress reached the maximum at the particle equator, and then they reduced quickly toward the direction of the particle pole along the interface between the particle and the matrix and achieved the minimum from about 0.5 to 2.0 µm from the equator. Finally, they tended to gently or somewhat increase. Furthermore, the ways and mechanisms of the major fail or fracture of the polyphenylene sulfide (PPS)/calcium carbonate (CaCO₃) composites under impact load were discussed. The mechanism of impact fracture or failure of inorganic particle‐filled PPS composites might be that the matrix around the neighboring inclusions will first yield owing to the stress concentration in the interface between the inclusion and the matrix to induce crazes and extend quickly. Copyright © 2011 John Wiley & Sons, Ltd.     

原位自组装形成二氧化硅/十六烷基三甲基溴化铵纳米网络粒子

提出了以具有纳米尺寸孔径及孔壁厚度的MCM 48作为无机基体、以无机 有机原位自组装的方法形成纳米网络粒子 .研究结果表明 ,在一定实验条件下 ,有机相可进入无机相的三维孔道自组装形成立方有序结构的纳米网络复合粒子 .通过研究纳米网络粒子在极性介质和非极性介质中的分散发现 ,有机相的存在有利于纳米网络粒子的分散     

PLLA Based Composites with α-Tricalcium Phosphate and a PLLA-PEO Diblock Copolymer

Hybrid composites consisting of poly(L -lactide), PLLA, or blends of PLLA with a PLLA-poly(ethylene oxide) diblock copolymer (15–30 wt%), COP, as a biodegradable polymeric matrix and of bioactive α-tricalcium phosphate, α-TCP, microparticles as dispersed phase (25–40 wt-%) were prepared by melt extrusion and their thermal, mechanical and degradation behaviour was investigated. SEM analysis of surfaces broken in liquid N₂ showed a good dispersion of α-TCP in the polymer matrix. A lowering of the glass transition temperature of the polymer matrix and enhanced crystallization rates of PLLA, both from the melt and from the glassy state, were observed in the presence of COP. Ternary PLLA/COP/α-TCP composites containing about 10 wt-% of COP and 25–40 wt-% of α-TCP showed improved compressive strength and deformation at yield as compared to pure PLLA. Degradation experiments revealed that in simulated body fluid the presence of α-TCP particles promoted the formation of inorganic deposits of a poor crystalline apatitic phase on composite surfaces as compact sferoids.     

Superparamagnetic magnetite–divinylbenzene–maleic anhydride copolymer nanocomposites obtained by dispersion polymerization

Magnetite alternating copolymers divinylbenzene–maleic anhydride (DVB–MA) composites were prepared by dispersion polymerization. Because magnetite is used as a complex with oleic acid (Fe₃O₄OLA), the final hybrids show good dispersion of inorganic nanofillers in the polymer matrix. The obtained composites were analyzed by infrared absorption spectrometry, diffuse reflectance in visible light, thermogravimetry, X-ray fluorescence, X-ray diffraction, dynamic light scattering, scanning electron microscopy and vibrating sample magnetometry. The obtained results indicate the successful preparation of magnetite nanoparticles with an average size of about 23 nm dispersed in micrometer size copolymer spherical particles, which relative content can be controlled via the processing parameters. A relationship between the relative content of magnetite nanoparticles and the size of the polymer particles, with direct influence on the diffuse reflectance in the visible domain, was observed. A superparamagnetic behavior was evidenced at room temperature with a blocking temperature lower than as expected from the bulk anisotropy constant and the average size of the magnetite nanoparticles. Both the unexpected low blocking temperature and the observed low specific magnetizations were explained by a defected and poor crystalline structure of the magnetite nanoparticles, giving rise to spin disorder and diminished crystalline anisotropy constant.     

Simultaneous enhancement of electrical conductivity and impact strength via formation of carbon black‐filler network in PP/EPDM Blends

The electrical conductivity and impact strength of polypropylene(PP)/EPDM/carbon black ternary composites were investigated in this paper. Two processing methods were employed to prepare these ternary composites. One was called one‐step processing method, in which the elastomer and the filler directly melt blended with PP matrix. Another one was called two‐step processing method, in which the elastomer and the filler were mixed first, and then melt blended with pure PP. To get an optimal phase morphology that favors the electrical conductivity and impact strength, controlling the distribution of CB in PP/EPDM blend was a crucial factor. Thus the interfacial tension and the work of adhesion were first calculated based on the measurement of contact angle, and the results showed that CB tended to be accumulated around EPDM phases to form filler‐network structure. Expectably, the filler‐network structure was observed in PP/EPDM/CB(80/20/3) composite prepared by two‐step processing method. The formation of this filler‐network structure decreased the percolation threshold of CB particles in polymer matrix, and the electrical conductivity as well as Izod impact strength of the composite increased dramatically. This work provided a new way to prepare polymer composites with both improved conductivity and impact strength. Copyright © 2009 John Wiley & Sons, Ltd.     

Catalytic transformation of silicon tetraisocyanate Si(NCO)4 to a polymeric silylcarbodiimide

A new way for the preparation of inorganic polymeric carbodiimide‐based networks is presented which resembles the transformation of molecular isocyanates using 1‐phenyl‐3‐methyl‐2‐phospholene‐1‐oxide as a catalyst. The respective reaction sequence, well established in preparative organic chemistry, has been applied for the synthesis of carbodiimide‐based SiNC(O) materials. Starting from Si(NCO)₄ (silicon tetraisocyanate), a transformation to an insoluble extended inorganic array was achieved in boiling dodecan (T = 216 °C). Analysis of the polymer using X‐ray diffraction, FT‐IR, density measurement, matrix‐assisted laser desorption/ionization time of flight and TGA revealed that this highly moisture‐sensitive amorphous network consists of oligomers of high molar mass and exhibits a high density of around 1.5 g cm^?3, which corresponds quite well to the calculated density of crystalline Si(NCN)₂ reported in the literature. Degradation of this 'SiNC(O) phase' with the release of N₂ and (CN)₂ finally provided SiC as the only crystalline product. No indication of the formation of crystalline Si₃N₄ or intermediate crystalline 'SiC₂N₄', silicon carbodiimide (= Si(NCN)₂), was noticed. Copyright © 2013 John Wiley & Sons, Ltd.