Preservation of initial polymer/catalyst particle morphology under air, was examined using stopped‐flow Ziegler–Natta polymerization with various quenching conditions and post‐chemical treatments. The exposure of the initial particles to air caused the fast formation of cracks on the surface, finally leading to significant reformation of the particle shape, when polymerizing particles were washed with heptane at ?65 °C under N2 or under CO2. On the other hand, when the particles were washed with heptane containing an appropriate amount of tetrahydrofuran under CO2, the particle morphology under air was almost completely maintained even after 1 h exposure. The present results are useful for various ex situ characterizations of unstable initial polymer/catalyst particles.
This communication reports a strategy for scale‐up of an in situ polymerization technique for polyolefin‐based nanocomposites preparation, taking layered silicate (clay) and multi‐walled carbon nanotubes (MWCNTs) as examples of nanofillers. The strategy is realized by transforming the nanofillers into granular “nanosupports” for Ziegler‐Natta catalysts. With a catalyst to polymer replication effect on particle morphology, the in situ prepared nanocomposites are of controlled granular particle morphology. With the polymer particle morphology controlled, the in situ polymerization technique becomes suitable for industrial olefin polymerization processes for mass production of polyolefin nanocomposites.
Summary: A new strategy was developed to prepare disorderly exfoliated nanocomposites, in which a soft siloxane surfactant with a weight‐average molecular weight ( ) of 1 900 was adopted to modify the clay. The modified clay slurry was then mixed with silicone rubber by hand, and exfoliation was achieved. The proposed mechanism thereof was verified by TEM and XRD. The physical entanglement of the soft siloxane surfactant plays a vital role in the diffusion and intercalation of the matrix molecules during the compounding of the slurry‐polymer mixture. This simple method is applicable to other silicone‐based materials reinforced by clay.
TEM micrograph of silicone rubber/clay‐sil nanocomposite. 相似文献
Summary: This paper reports a facile route to fabricate high‐surface area hybrid carbon‐polymer nanocomposites following a template technique. The method presented here allows large amounts of polymer to be deposited inside one of the pore systems of a highly ordered carbon, while the other is kept empty. Such prepared composite has large polymer loadings (≈50%), high surface area (≈1 000 m2 · g−1), and a uniform porosity made up of mesopores.
This paper focuses on the attachment of densely grafted polymer layers (polymer brushes) to various inorganic and polymeric substrates by the “grafting to” method. A brief overview of synthesis of polymer brushes by the method is first provided, with emphasis on chemical approaches to polymer attachment. The second part of the paper covers the synthesis of polymer layers via a recently developed macromolecular anchoring layer approach. Several examples of application of the grafting technique are presented for generation of hydrophobic, hydrophilic, gradient, and switchable surfaces.
We report the results of the experimental study of the preparation of hybrid porous polymer material carrying gold nanorods (NRs) on the surface of pores. The material was prepared by utilizing two effects occurring concurrently: the photoinitiated polymerization‐induced phase separation in the polymer–solvent mixture and the migration of the NRs to the interface between the polymer and the porogen solvent. We show that the enrichment of the interface with the NRs is enhanced at high polymerization rate leading to the rapid phase separation. By contrast, more rapid increase in viscosity achieved at high polymerization rate does not have a significant effect on the segregation of NRs to the surface of pores.
Double helical microropes of polyvinylpyrrolidone (PVP) with diameters of less than 10 µm and lengths of up to 5 cm were fabricated using a new electrospinning technique. In contrast to the typical electrospinning set‐up, a negatively charged rotating collector tip was used in this work, so that the two jets from two positively charged spinnerets were induced to two bundles that met at the rotating collector tip, leading to the formation of microropes. The pitch of microropes could be monitored by simply adjusting the distance between the two spinnerets.
This paper describes random branching theory, a model for the solution structure of hyperbranched polymers. In this model, the hyperbranched polymer is assumed to be composed of units whose structure is simpler than the resulting polymer. These simple units can have any structure of chemical functionality, from monomers to linear chains or spherical particles. This paper outlines how this theory is constructed, describes the underlying assumptions and parameters, and summarizes the most basic form. It is shown how variations in the parameters change the behavior of the model, and described how to fit an experimental data series. This demonstrates how the model can be used to fit other data series, and how it can be used as a test for whether a polymer is randomly hyperbranched.
Summary: We describe an interesting approach to the fabrication of wettability gradients from hydrophobicity to superhydrophobicity in low‐density polyethylene (LDPE) films by first forming high porosity surfaces and placing the specimens onto linear temperature gradients. While the polymer chosen for the study is non‐polar, its microporous layer provides sufficient superhydrophobicity. Lateral gradient heating of the layer results in partial melting of the polymer and correspondingly decreases porosity thus decreasing hydrophobicity.
Two polythiophene derivatives with electron‐donating alkylthio side chains, poly[(3‐hexylthio)thiophene] (P3HST) and poly[(3‐hexylthio)thiophene‐alt‐thiophene] (P3HST‐co‐Th) have been synthesized and characterized. Both P3HST and P3HST‐co‐Th show broader absorption peaks than poly(3‐hexylthiophene). Meanwhile, the alkylthio side chains decrease the HOMO energy level of the polymers, which benefits the higher open circuit voltage of the polymer solar cells (PSCs) based on the polymer as donor. PSCs have been fabricated with the polymers as donor and [6,6]‐phenyl C61 butyric acid methyl ester as acceptor (1: 1, w/w). The devices based on P3HST and P3HST‐co‐Th show an open circuit voltage of 0.63 V, and a power conversion efficiency of 0.34% and 0.5%, respectively, under the illumination of AM1.5, 80 mW · cm−2.
A model is developed to predict the viscoelastic behavior of polyolefins produced in catalytic polymerization reactors. The approach is based on the solution of different sub‐models (e.g., a kinetic model, a single particle model, a macroscopic reactor model and a rheological model). From the calculated rheological curve, the polymer melt index is determined. The ability of the proposed model to predict the viscoelastic behavior of linear polymer melts quantitatively is examined for the operation of a catalytic olefin polymerization cascade‐loop reactor process. In addition, the transient rheological properties of polyolefins produced in a Ziegler‐Natta gas‐phase olefin polymerization fluidized‐bed reactor are calculated.
A “click” polymerization of dialkynes that contain an ester linkages and diazides to has been performed to synthesize various polyesters, termed “click polyesters” with a high of 1.0 × 104 to 7.0 × 104 in an excellent yield. This polymerization accompanied a formation of 1,4‐disubstituted triazoles in the polyester main chain by a CuI catalyst. The triazole ring formation in the polyester main chain leads to improved thermal properties and enhancement of the even–odd effect of methylene chain length of the produced click polyesters. This report is the first report of the application of click chemistry to synthesize a series of polyesters under mild conditions.
Ring‐opening metathesis polymerization (ROMP) was used to synthesize novel ring‐opened poly[5‐(2‐phenylethylnorbornene)]. Hydrogenation can produce two different saturated derivatives, with the phenyl groups either preserved or saturated to cyclohexyl groups. These two different hydrogenated products allowed us to compare the effect of replacing the pendant phenyl groups with cyclohexyl groups on properties such as the glass transition temperature (Tg). We found that Tg decreased by only 2 °C (from 28 to 26 °C) upon replacement of the phenyl groups. This contrasts with the effect of saturating the phenyl groups in the addition polymer of 5‐(2‐phenylethylnorbornene), where the Tg increased by 34 °C, from 215 to 249 °C, a remarkable difference in magnitude and direction compared with the ROMP polymers.
Summary: The success of metathesis chemistry techniques has sparked a tremendous interest in polymer and material chemistry. This contribution provides an overview of the state of the art in ring opening metathesis polymerisation (ROMP). It is intended to provide the reader with useful information on the interplay of initiators, monomers, and reaction conditions, thus aiding polymer chemists to utilise the ROMP toolbox. Prominent and illustrative examples from current research are given in the article.
Smectic‐A elastomers combine the positional long‐range order of mesogenic molecules in one dimension with the rubber elasticity of a polymer network. Upon mechanical deformation, completely different responses of the phase structure have been reported. We present a highly distorted system which shows a breakdown of smectic layering but no reorientation under deformation along the layer normal, while the phase structure stays unaffected under uniaxial stress in the perpendicular direction. The thermoelastic properties, macroscopic dimensions and stress–strain behaviour are investigated parallel and perpendicular to the layer normal. SAXS measurements supply evidence for a breakdown of the macroscopically ordered layer structure indicated by the small angle intensities and correlation length, whereas the orientational order is preserved. We propose defects in the smectic layer structure to be the origin of the different responses of different smectic elastomers.
A fluorene diol derivative, 9,9‐bis[4‐(2‐hydroxyethoxy)phenyl]fluorene ( 1 ), reacted with diisocyanates such as 1,3‐bis(isocyanatomethyl)cyclohexane ( 2a ), 1,6‐diisocyanatohexane ( 2b ), and 1,3‐bis(isocyanatomethyl)benzene ( 2c ) under temperature‐controlled microwave irradiation to form the corresponding polyurethanes with being 30 000 to 60 000, measured by GPC with reference to polystyrene standards within 5 to 10 min at 160 to 200 °C. In the reactions of 2a and b , the molecular weights were 15 to 20 times higher than those obtained by conventional oil bath heating. For a solvent of the microwave‐promoted reaction, a hydrocarbon compound, decalin, is preferably used to undergo the polymerization cleanly without unfavorable coloration and/or gelation.
A pathway for marking of polymer chains with radical spin traps during pulsed laser polymerization in free radical polymerization is presented. By introducing a so‐called marker that forms a non‐propagating radical at (or shortly after) the incidence of a laser pulse, a polymer subdistribution is generated by specifically terminating propagating radicals via combination with such a marker radical. The generated polymer subdistribution can subsequently be imaged by modern soft‐ionization mass spectrometry. Herein, the general methodology of the method in which such marker is generated via reaction of an initiating radical with a nitrone is demonstrated on the examples of BA and VAc.
This study reports a spontaneous selective localization of molecules in crosslinked particles during electrospraying and electrospinning polymer solutions containing the particles. It provides a facile way of preparing microcapsules and fibers with controlled release. The dye molecules were phase separated from the crystalline polymer matrix during the electrohydrodynamic process and moved to the solvent‐rich crosslinked particles. The position of the particles in the microcapsules and fibers could be controlled by adjusting compatibility of the particles with the matrix polymer. The microcapsules and fibers did not show the initial burst release of the molecules and gave considerably prolonged release behavior.
Equilibrium P–V–T properties of randomly crosslinked amorphous polymer networks are modeled via molecular dynamics simulation for connectivity ratios between 1.0 and 1.5. The relation between connectivity ratio and network shrinkage is studied over a wide range of temperatures and pressures. The simulation results are compared to a mean‐field Flory–Huggins lattice model.
