Synthesis of Fluorinated Hyperbranched Polymers and Their Use as Additives in Cationic Photopolymerization

Summary: A fluorine containing hyperbranched polymer was synthesized by modifying an aromatic‐aliphatic hyperbranched polyester with a semifluorinated alcohol via a Mitsunobu reaction and was subsequently used as an additive in cationic photopolymerization of an epoxy resin. The remaining OH groups of the fluorinated hyperbranched polymer interact with the polymeric carbocation through a chain‐transfer mechanism inducing an increase in the final epoxy conversion. The fluorinated HBP induces modification of bulk and surface properties, with an increase in T_g and surface hydrophobicity already reached at very low concentration. The HBFP additive can, therefore, protect the coatings from aggressive solvents, increases hardness, and allows the preparation of a low energy surface coating.

Synthesis of fluorinated hyperbranched polyester.     

Structure and Mechanical Properties of Polyurethane/Silica Hybrid Coatings

Summary: Polyurethane/silica hybrid coatings were prepared via in situ (IS) or blending (BL) method using different acidic silica sols. The effects of preparation methods, silica types, and content on the structure and mechanical properties of the hybrid coatings were investigated. It was found that there existed two types of silica phases in the hybrid coatings: silica‐rich agglomerate and primary silica‐rich phase, whose size and compactness depended upon the silica types and the preparation methods. Introducing silica could result in obvious changes in surface free energy, atomic composition, and mechanical properties of the hybrid coatings.

Typical SEM image of the fractured surface of hybrids obtained by the in situ method.     

Morphology,Thermal and Mechanical Properties of Poly(propylene) Fibre‐Matrix Composites

Preparation and properties of poly(propylene)‐poly(propylene) composites have been investigated. Poly(propylene) fibres of varying diameter have been incorporated in a random ethylene co‐poly(propylene). The composites prepared from the same semi‐crystalline polymer in the matrix and reinforcement have lead to inherently strong interfacial bonding between the two phases of the same polymer. The composites demonstrated enhanced stiffness, which increased with fibre diameter. The structure, thermal, static and mechanical properties of poly(propylene) long fibre reinforced random co‐poly(propylene) composites have been studied with reference to the fibre diameter. The matrix and fibre components retained their separate melting temperatures. After melting, the two phases remained separate and showed their individual crystallization temperatures on cooling, and melting temperatures on a second heating. The melting temperature of the poly(propylene) fibres increased after formation of the composites. The compression molding of the composites at a temperature below the melting temperature of the fibres caused annealing of the fibre crystals. By incorporation of long poly(propylene) fibre into random co‐poly(propylene), the glass transition, storage and static modulus have been found to be increasing and composite with the largest fibre diameter shows better properties. Transcrystallization of the matrix poly(propylene) was observed.

Optical microscopy of composites with fibre diameter 68 μm.     

Aligned Nafion® Nanocomposites: Preparation and Morphological Characterization

A novel nanocomposite based on Nafion® (ionomer) and a layered silicate is studied. An innovative approach of processing a composite under electric field to induce orientation of the inorganic filler was carried out and accomplished in the present work. The morphology of oriented composites was analyzed by scanning electric potential microscopy (SEPM) and transmission electron microscopy (TEM). Films based on both plain ionomer and composite displayed fine contrast in SEPM, differentiating the phases, which could not be achieved using conventional atomic force microscopy. The orientation of the silicates in the composites is evident from the SEPM picture.

AFM of Nafion®/montmorillonite composite films prepared by solution casting under electric field (Image obtained by SEPM).     

A Novel Impact Modifier for Nylon 6

A new carboxylated styrene‐butadiene rubber (CSBR) in ultrafine powder form was used to modify the properties of nylon 6. The nylon 6/CSBR blends possessed higher toughness than nylon 6/maleic anhydride‐grafted polyethylene‐octene elastomer (POE‐g‐MAH) system. TEM micrographs revealed the fine dispersion of CSBR particles with a diameter of 150 nm. The effective toughening of nylon 6 with CSBR was attributed to the good interface, fine dispersion, and shear yielding.

TEM photograph of undeformed Nylon 6/CSBR (80/20) blend (×40 000).     

Photoinduced Polymerization in the Wall of Hollow Capsules

Summary: Novel light‐sensitive hollow capsules were fabricated from the small molecule 3‐sulfopropylacrylate potassium (SPA) and poly(allylamine hydrochloride) (PAH). With UV irradiation, SPA could be photopolymerized in the wall of hollow capsules. After photopolymerization the capsule size and surfaces showed pronounced differences. The capsules became much more rigid as indicated by an increase in the modulus of more than a factor of 5.

CLSM image of SPA/PAH hollow capsule emission at 554 nm, from rhodamine B after photopolymerization.     

A Novel Phosphorus‐Containing Polymer as a Highly Effective Flame Retardant

Summary: A novel phosphorus‐containing polymeric retardant, WLA‐3, was synthesized from phenylphosphonic dichloride (PPD) and 2‐(6‐oxido‐6H‐dibenz〈c,e〉〈1,2〉oxaphosphorin‐6‐yl) 1, 4‐benzenediol (ODOPB). The flame‐retardant element, phosphorus, was bonded both in the main chains and in the pendant chains of flame‐retardant polymer molecules, and reached a content of 13.8%. The high phosphorus content and rich aryl group structures of WLA‐3 contribute an excellent flame retardancy to poly(ethylene terephthalate) (PET) without a considerable decrease of mechanical properties. WLA‐3 is also very effective in improving flame retardancy of epoxy resin and unsaturated polyester.

     

Improvement of Flex‐Fatigue Life of Carbon‐Black‐Filled Styrene‐Butadiene Rubber by Addition of Nanodispersed Clay

Summary: The flex‐fatigue life of carbon‐black‐filled SBR was dramatically improved by incorporation of 4–5 phr nanodispersed clay. Addition of clay did not decrease the degree of crosslinking of the composite but improved the hysteresis and tearing energy. ESEM observation of the flexing‐fracture morphology indicated that nanodispersed clay layers had the advantage over carbon black in that they could blunt the crack.

Effect of the clay amount on the flex fatigue life of the composites.     

External Stimuli‐Responsive Characteristics of Ionic Poly[(N,N‐diethylaminoethyl methacrylate)‐co‐(N‐vinyl‐2‐pyrrolidone)] Hydrogels

Summary: Polyelectrolyte hydrogels containing diprotic acid moieties sensitive to ionic strength changes of the swelling medium were synthesized from N,N‐diethylaminoethyl methacrylate (DEAEMA), N‐vinyl‐2‐pyrrolidone (VP) and itaconic acid (IA) by using ammonium persulfate (APS) as a free radical initiator in the presence of the cross‐linker, methylenebisacrylamide (MBAAm). The swelling behavior of the ionic poly[(N,N‐diethylaminoethyl methacrylate)‐co‐(N‐vinyl‐2‐pyrrolidone)] [P(DEAEMA/VP)] hydrogels were investigated in pure water; in NaCI solutions with pH 4 and 9; and in water‐acetone mixtures depending on the IA content in the hydrogel. The average molecular mass between cross‐links ( ) and polymer‐solvent interaction parameter (χ) of the hydrogels were determined from equilibrium swelling values. The pulsatile swelling behavior was also observed in response to solvent changes between the solution in water and in acetone. The equilibrium swelling ratio of these hydrogels was basically unaffected with change in temperature. The swelling variations were explained according to the swelling theory based on the hydrogel chemical structure.

Pulsatile swelling behavior of ionic P(DEAEMA/VP) hydrogels in response to solvent changes between water and acetone at 25 °C.     

Toughening of Polystyrene with Ethylene‐Propylene‐Diene Terpolymer (EPDM) Compatibilized by Styrene‐Butadiene‐Styrene Block Copolymer (SBS)

Summary: Polystyrene (PS) was toughened with ethylene‐propylene‐diene terpolymer (EPDM) in the presence of styrene‐butadiene‐styrene block copolymer (SBS). Incorporation of SBS into the PS/EPDM blends clearly improved the impact properties. For PS/EPDM/SBS (mass ratio: 69/21/10) blends, the notched Charpy impact strength reached a maximum value of 26.3 kJ/m². Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that SBS was distributed on the interface between PS and EPDM. Butanone extraction and FTIR analysis found that there was a grafting reaction between PS and EPDM phase during melt compounding. Shearing and processing rheological behaviors of blends were evaluated with a Haake capillary rheometer and a torque rheometer, respectively.

     

A Novel Inorganic Polymer as Cathode Material for Secondary Lithium Batteries

Summary: This paper introduces a new inorganic poly(phosphazene disulfide) material. With unique element composition and molecular structure, the polymer has noncombustible safety and preferable conductivity. When used as cathode material for rechargeable lithium batteries, the polymer's first discharge capacity is as high as 467.9 mAh · g^?1, which can be retained at 409.9 mAh · g^?1 after 60 repeated cycles. Therefore, it has a great application potential in the field of lithium batteries.

Replacement of the Cl atoms by S? S groups by refluxing Na₂S₂ and linear poly(dichloro‐phosphazene).     

Morphology,Electrical, and Rheological Properties of Silane‐Modified Silver Nanowire/Polymer Composites

Electrically conducting films containing AgNws, hydrophilic and hydrophobic resins were prepared. FT‐IR reveals that the interface between the AgNws and epoxy could be successfully modified by APTES. XPS shows that the AgNws were attracted by hydrogen bonds of ? NH₂ and ? NH? groups after APTES modification. SEM analysis shows that the AgNws were well dispersed in the resin. The AgNws were also blended with hydrophilic and acrylic resins, and the resulting blends were compared with AgNws/epoxy blends. Results show that AgNw/PVA‐resin films possess the lowest surface electrical resistance. The AgNw/PVA‐resin and silane‐modified AgNw/epoxy resin conductive films possess a similar electrical percolation threshold.

     

A Semi‐Batch Process for Nitroxide Mediated Radical Polymerization

Summary: A semi‐batch process using nitroxide mediated polymerization, was explored for the design of low molecular weight solvent‐borne coatings, typical of those used in the automotive industry. While living radical polymerization (LRP) offers many advantages in the control of polymer chain microstructure that may confer important physical and chemical property benefits to coatings, adapting LRP to a semi‐batch process poses significant challenges in the design and operation of the process. Using styrene monomer, various two‐component initiating systems (free radical initiator, 4‐hydroxy‐TEMPO) were studied to understand the effects of different initiators on the course of polymerization. In addition, an alkoxyamine was synthesized and used as the initiating source. The initiators Luperox 7M75 and Luperox 231 give higher polymerization rates and reasonable control over polymerization, while benzoyl peroxide (BPO), Vazo 67, and the alkoxyamine are less effective. The number of polymer chains in the final product is always less than the theoretical value, reflecting poor initiation efficiency, probably resulting from undesirable termination reactions that become important due to the nature of the semi‐batch process. Adding camphorsulfonic acid (CSA) or charging initiator concurrently with monomer during semi‐batch feed, can increase the polymerization rate while maintaining the living character of the polymerization. The copolymerization of styrene and butyl acrylate is also shown to exhibit living character.

Schematic representation of the exchange reaction to produce N‐TEMPO capped polymer chains.     

Resistivity and Thermal Reproducibility of the Carbon Black and SnO2/Sb Coated Titanium Dioxide Filled Silicone Rubber Heaters

Summary: Flexible heaters were prepared by extruding platinum‐catalyzed silicone rubber compound with electroconductive carbon black (CB) and SnO₂/Sb coated titanium dioxide (TiO₂). Two types of acicular‐shaped TiO₂ with average particle sizes of 1.7 and 5.2 µm, and two types of spherical‐shaped TiO₂ with average particle sizes of 0.3 and 2.5 µm were selected. Thermoelectric switching phenomena were investigated for the silicone rubber/CB/TiO₂ system. Positive temperature coefficient (PTC) was significant when the acicular filler was added rather than spherical ones. Resistivity change and thermal reproducibility of the extruded heaters were also investigated by applying periodically AC voltage of 220 V. The heaters containing acicular‐shaped TiO₂ exhibited excellent electrical reproducibility.

Scanning electron micrograph of the fractured surface of the extruded composites.     

Extrusion Monitoring of Polymer Melts Using a High‐Temperature Surface‐NMR Probe

Summary: Extrusion is one of the major ways of polymer processing, and extrusion monitoring is important to control or improve the extrusion process and the product quality. Especially methods for in‐line monitoring are desired because those enable the fastest possible response and a localization of chemical reactions in reactive processing. Methods of optical and acoustic spectroscopy have successfully been implemented so far. NMR provides a wealth of information. Surface NMR mostly gives access to molecular mobility via relaxation times. These can be correlated to temperature, composition and homogeneity which are substantial indicators for the product quality. NMR is a non‐destructive method, which does not require direct contact with the sample and it is not restricted to optical transparent materials and is therefore suitable for extrusion monitoring. The problem for the adaptation is the hostile environment in and in front of an extruder for polymer melts. Here, a NMR surface probe is presented sustaining this environment in front of an extruder. First measurements with this device are shown.

High‐temperature surface‐NMR probe.     

Improved Design of Shearing Sections with New Calculation Models Based on 3D Finite‐Element Simulations

New models for the Maddock and spiral shearing sections have been developed, employing three‐dimensional finite element analysis (3D FEA). These models describe the pressure‐throughput and power consumption behavior of the shearing sections for both the extrusion and the injection molding process and have been implemented in the REX 6.0 and PSI 4.0 simulation software. As a consequence it is now possible to describe the process behavior of these shearing sections within just a few seconds with the accuracy of FEA calculations.

Actual Maddock shearing section (left) and actual spiral shearing section (right).     

The Solid State Postcondensation of PET, 3

Summary: It was demonstrated that it is possible to produce prepolymers with a number‐average degree of polymerisation on the order of 5–40 directly in a liquid‐liquid dispersion in less than three hours. It was also shown that prepolymers made via this route and rapidly crystallised by the addition of a dispersant at ambient temperature are more porous than prepolymers made in an industrial liquid melt process.

SEM micrograph of prepolymers pLL‐PTA with \overline {DP} _{\rm n} = 28, d_p ∈ 63–125 μm.     

Study of the Fire Performance of Magnesium Hydroxide Sulfate Hydrate Whisker Flame Retardant Polyethylene

Summary: Halogen‐free, flame retardant low density polyethylene (LDPE) composites, using magnesium hydroxide sulfate hydrate (MHSH) whiskers as a flame retardant, combined with microencapsulated red phosphorous (MRP) as a synergist, have been prepared using a two‐roll mill. Their fire properties were determined by using the limiting oxygen index (LOI), the UL‐94 test and cone calorimetry. The results showed that MRP was a good synergist in improving the flame retardance of the LDPE/MHSH whisker system. Poly[ethylene‐co‐(vinyl acetate)] (EVA), used as a compatibilizer, increased the fire performance of LDPE/MHSH whisker composites.

HRR curves for LDPE/MHSH whisker composites.     

Coaxial Electrospinning with Triton X‐100 Solutions as Sheath Fluids for Preparing PAN Nanofibers

Coaxial electrospinning using surfactants as sheath fluid for preparing high‐quality polymer nanofibers is studied. PAN nanofibers are fabricated using this process with Triton X‐100 solutions in DMF. FESEM demonstrates that the Triton X‐100 solution has a significant influence on the quality of the nanofibers. The nanofiber diameters can be controlled by adjusting the concentration of Triton X‐100 in the sheath fluids with a scaling law D = 640 C^?0.32. The mechanism of the influence of Triton X‐100 solutions on the formation of PAN fibers is discussed and it is demonstrated that coaxial electrospinning with surfactant solution is a facile method for achieving high‐quality polymer nanofibers.

     

The Effect of Particle Matrix Adhesion on the Mechanical Properties of Silica Filled Cyanate Ester Composites

Summary: The effect of silica and its surface treatment on the mechanical properties of composites was studied as part of the evaluation of cyanate ester matrices as potential electronic encapsulants. Three filler surface treatments were used, as a qualitative interfacial adhesion scale, in an attempt to gauge the magnitude of interfacial adhesion between untreated filler and the cyanate ester matrix. There was strong interfacial adhesion between matrix and untreated filler. The level of silica content most affected composite modulus and fracture toughness. Filler surface treatment most affected composite strength and fracture toughness/energy. Composite fracture was found to occur via crack pinning and/or crack blunting depending on the strength of adhesion. The composites evaluated were found to possess suitable mechanical properties for potential use as electronic encapsulants.