On Toughness and Stiffness of Poly(butylene terephthalate) with Epoxide‐Containing Elastomer by Reactive Extrusion

Summary: To obtain a balance between toughness (as measured by notched impact strength) and elastic stiffness of poly(butylene terephthalate) (PBT), a small amount of tetra‐functional epoxy monomer was incorporated into PBT/[ethylene/methyl acrylate/glycidyl methacrylate terpolymer (E‐MA‐GMA)] blends during the reactive extrusion process. The effectiveness of toughening by E‐MA‐GMA and the effect of the epoxy monomer were investigated. It was found that E‐MA‐GMA was finely dispersed in PBT matrix, whose toughness was significantly enhanced, but the stiffness decreased linearly, with increasing E‐MA‐GMA content. Addition of 0.2 phr epoxy monomer was noted to further improve the dispersion of E‐MA‐GMA particles by increasing the viscosity of the PBT matrix. While use of epoxy monomer had little influence on the notched impact strength of the blends, there was a distinct increase in the elastic stiffness. SEM micrographs of impact‐fracture surfaces indicated that extensive matrix shear yielding was the main impact energy dissipation mechanism in both types of blends, with or without epoxy monomer, and containing 20 wt.‐% or more elastomer.

SEM micrographs of freeze‐fractured surfaces of PBT/E‐MA‐GMA blend illustrating the finer dispersion of E‐MA‐GMA in the presence of epoxy monomer.     

Waste and Virgin LDPE/PET Blends Compatibilized with an Ethylene‐Butyl Acrylate‐Glycidyl Methacrylate (EBAGMA) Terpolymer, 1

Summary: This work is aimed at studying the morphology and the mechanical properties of blends of low density polyethylene (LDPE) and poly(ethylene terephthalate) (PET) (10, 20, and 30 wt.‐% of PET), obtained as both virgin polymers and urban plastic waste, and the effect of a terpolymer of ethylene‐butyl acrylate‐glycidyl methacrylate (EBAGMA) as a compatibilizer. LDPE and PET are blended in a single screw extruder twice; the first extrusion to homogenize the two components, and the second to improve the compatibilization degree when the EBAGMA terpolymer is applied. Scanning electron microscopy (SEM) analysis shows that the fractured surface of both the virgin polymer and the waste binary blends is characterized by a gross phase segregation morphology that leads to the formation of large PET aggregates (10–50 µm). Furthermore, a sharp decrease in the elongation at break and impact strength is observed, which denotes the brittleness of the binary blends. The addition of the EBAGMA terpolymer to the binary LDPE/PET blends reduces the size of the PET inclusions to 1–5 µm with a finer dispersion, as a result of an improvement of the interfacial adhesion strength between LDPE and PET. Consequently, increases of the tensile properties and impact strength are observed.

SEM micrographs of the fracture surface of a waste 70/30 LDPE/PET blend (R30) and of its blend with 15 pph of EBAGMA (R30C). Magnification × 1 000.     

Thermal Characterization of Upper Critical Solution Temperature m‐LLDPE/Poly(ethylene‐ran‐butene) Elastomer Blends

Summary: The phase and thermal characteristics of blends consisting of linear low‐density polyethylene (LLDPE) (0.7 mol‐% hexene copolymer) and poly(ethylene‐ran‐butene) (PEB) (26 mol‐% butene copolymer) have been investigated using optical microscopy (OM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). An upper critical solution temperature of 162 °C was exhibited. The addition of PEB not only slowed the overall crystallization rate of LLDPE but also changed the distribution of lamellar thickness or perfection of LLDPE crystals. The equilibrium melting temperature of LLDPE in the blends was reduced and kept relatively constant in the bi‐phase state. The blends showed a single‐stage degradation and an intermediate thermal stability between those of the individual components. It could be attributed to their homogeneous states at degradation temperatures and the similar decomposing mechanisms of two components. The kinetic analysis of thermal degradation also confirmed the above results.

Phase diagram of LLDPE/PEB blends.     

Polyolefin/Lignosulfonate Blends, 9

Summary: In the present study, the compatibility, properties and degradability of polyolefin/lignin blends have been studied. Blends of three maleic anhydride grafted copolymers of ethylene‐propylene rubbers containing various content of functional groups with epoxy‐modified lignosulfonate have been investigated by microscopy, X‐ray diffraction, surface and mechanical indices determination, electron spin resonance, IR spectroscopy, differential scanning calorimetry and thermogravimetry. To assess the environmental degradation characteristics, the behavior of the blends during soil burial test has been investigated. The influence of the buried polymer blends on the physiological vegetative processes of the Vicia X Hybrida hort plant has been monitored.

Optical microscopy images of blend EP‐g‐MA 0.3/5 LER, undegraded (left) and degraded (right).     

Monodisperse Silica‐Polymer Core‐Shell Microspheres via Surface Grafting and Emulsion Polymerization

We describe a flexible method for preparing monodisperse silica‐polystyrene core‐shell microspheres. In this method, silica nanoparticles grafted with 3‐(trimethoxysilyl)propyl methacrylate (MPS) were employed as seeds in an emulsion polymerization. The thickness of the shells could be changed through varying the amount of the monomer. The monodispersity and diameters of the core‐shell microspheres were found to depend on the size of the grafted silica nanoparticles and the concentration of emulsifier. In addition, we investigated the formation mechanism of the core‐shell microspheres.

Schematic outline of the experimental procedure and TEM image of the monodisperse silica/PS core‐shell microspheres; inset: grafted silica nanoparticles (scale bar = 200 nm).     

Photocrosslinking Polymerization of Methacrylate Modified Triethoxysilanes Polycondensates and Multifunctional Methacrylates

Densely crosslinked polymer networks were prepared by fast, visible light‐induced polymerization at 20–22 °C. The two methacrylate functionalized triethoxysilanes polycondensates (MSiP) either alone, or in a mixture with methacrylate modified oxozirconium clusters, were polymerized separately and as comonomers to multimethacrylate monomers in a weight ratio of 1:0.9. Pure organic networks based on 1,6‐bis(2‐hydroxy‐3‐methacryloyloxyethoxycarbonylamino)‐2,2,4‐trimethylhexane (UDMA) were used for comparison in the same ratio to other comonomers. The networks based on organic bifunctional monomers showed high, around 85% conversion of double bonds. Nevertheless the non‐reacted monomer that migrates to the toluene amounts from 5.6 to 11.65 wt.‐%. Copolymerization of UDMA with tetrafunctional components resulted in networks with higher residual unsaturation up to 27.7%. This result points out the important role that functionality and the spacer structure between the monomer double bonds play in the extent of reaction. Based only on modified inorganic Si? O? Si nano‐structures the networks are characterized by nearly complete building up of MSiP in the network, extreme crosslinks density, and mostly less than 1 wt.‐% of soluble substances. However, residual unsaturations exceeded 22%. The advantage of copolymerization of MSiP with proper organic comonomers as potential solvent free matrices for dental composites was demonstrated by a network consisting of MSiP II and UDMA. The 13.7% of unreacted double bonds and 99.65 wt.‐% gel content approximated efforts to minimize residual unsaturation and maximize monomer conversion in cured networks.

Monomers used for the synthesis of the densely crosslinked polymer.     

Molecular and Morphological Characterization of Immiscible SAN/EPDM Blends Filled by Nano Filler

The compatibilizing effect of nano sized calcium carbonate filler on immiscible blends of styrene‐co‐acrylonitrile/ethylene propylene diene (SAN/EPDM) was examined. The surface energy of the calcium carbonate was modified by stearic acid. The compatibility of SAN/EPDM blends was studied by following the glass transition temperature T_g by DSC. SEM was used to observe the blend morphology and the X‐ray analyzer was used to detect the calcium from filler in samples. Mechanical properties of the blends were determined, and related to changes of polymer‐filler interactions and morphology. The results suggest that the morphology of the SAN/EPDM blends studied was affected by the reduction of surface energy of the filler.

SEM micrograph of an SAN/EPDM blend with 5% of maximally treated filler.     

Novel Glass Fiber‐Reinforced Composites Having a UV and Peroxy Curable Fluoropolymer Matrix

Novel glass fiber‐reinforced composites were prepared from E‐glass fibers and perfluoropolyether (PFPE), polyurethane acrylate, and methacrylate resins. The PFPE resins were synthesized by a two‐step process and formulated with reactive acrylic diluents obtaining two compositions with different viscosity and fluorine content. These formulations were photocrosslinked by UV‐A radiation and characterized by tensile and dynamic‐mechanical properties as well as by impact resistance. The two UV cured fluoropolymer compositions are high modulus (> 1 GPa), polyphasic materials characterized by a fracture toughness higher than conventional polymer matrices, like epoxies and unsaturated polyesters. Unidirectional laminate composites were also prepared by hand lay‐up and crosslinked both photochemically and thermally. Mechanical characterization of glass fiber‐reinforced composites was carried out by tensile tests and shear adhesion measurements, showing a good fluoropolymer‐glass adhesion strength (ca. 9 MPa). Surface characterization of composites by static contact angle measurements allowed the calculation of the total surface tension γ_s according to Wu's harmonic mean approximation. Surface tension is very low (< 20 mN/m) suggesting a preferential stratification of PFPE segments at the material‐air interface.

     

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.     

Preparation and Characterization of Hybrid Quaternized Chitosan/Acrylic Resin Emulsions and their Films

An acrylic resin emulsion containing a quaternary ammonium salt (hybrid q‐chitosan/acrylic resin emulsion) was prepared by emulsion polymerization using an acrylic monomer with and without DAAM. DAAM was used to incorporate a functional keto group into the acrylic resin emulsion. Furthermore, a hybrid chitosan/acrylic resin emulsion was prepared for comparison. The elution of q‐chitosan in water from the acrylic resin film with a keto group was less than that from the acrylic resin emulsion without a keto group. In addition, the mechanical properties of the hybrid q‐chitosan/acrylic resin film could be modified by q‐chitosan that was crosslinked between acrylic resin particles. Furthermore, hybrid q‐chitosan/acrylic resin films had adsorption ability for formaldehyde, and the antimicrobial properties of these films were superior to those of the hybrid chitosan/acrylic resin film.

     

Interpenetrating Polymer Networks of Hydrocarbon and Fluorocarbon Polymers: Epoxy/Fluorinated Acrylic Macromonomers

A fluorinated acrylic resin was synthesized for use as a co‐monomer with a commercially available epoxy resin for UV‐cured interpenetrating polymer network preparation. Hybrid IPN networks were achieved with morphology ranging from a co‐continuous IPN to complete phase separation simply by changing monomer ratios. Highly hydrophobic coatings with good adhesion properties on glass substrates were obtained.

     

New Polylactide/Layered Silicate Nanocomposites, 6

The measurement of rheological properties of any polymeric material under molten state is crucial to gain fundamental understanding of the processability of that material. In the case of polymer/layered silicate nanocomposites, the measurements of rheological properties are not only important to understand the knowledge of the processability of these materials, but is also helpful to find out the strength of polymer‐layered silicate interactions and the structure‐property relationship in nanocomposites. This is because rheological behaviors are strongly influenced by their nanoscale structure and interfacial characteristics. In order to get this knowledge in the case of polylactide/montmorillonite nanocomposites, we have studied melt rheological properties of these materials in detail. On the basis of rheological data, we have conducted foam processing of pure polylactide and one representative nanocomposite by a newly developed pressure cell technique using carbon dioxide as a physical‐blowing agent.

The time variation of the elongational viscosity of one of the intercalated polylactide/montmorillonite nanocomposites.     

A New Method for Producing High Melt Strength Poly(propylene) with a Reactive Extrusion

Summary: A new class of melt blend material was prepared by extruding a mixture of 3‐aminopropyltriethoxysilane (APTES), maleic anhydride‐grafted poly(propylene) (PP‐g‐MA) with different molecular weight and MA content and poly(propylene) powder produced with a TiCl₃‐based catalyst (PP‐A). A suitable selection of PP‐g‐MA provided extremely high melt strength (MS) of resultant blend materials. Such a superior melt property was caused by the synergy between the present melt reaction and the higher molecular weight portion containing PP‐A. The gel content measurements of typical blend materials and PP‐g‐MA/APTES blends indicated that an excessive amount of inert PP suppresses the formation of gels. The reaction between PP‐g‐MA and APTES was then investigated by analyzing crystalline polymer fractions separated from the atactic PP/PP‐g‐MA/APTES and atactic PP/PP‐g‐MA blends. The FT‐IR analysis of the fractions revealed that the NH₂ group in APTES readily reacts with MA grafted on PP and the reaction leads to the formation of imide linkage. Moreover, the GPC analysis of the fraction showed that higher molecular weight polymers were formed in the presence of APTES. Since a trace amount of water surely produces in the vicinity of active silyltriethoxy groups during the reactive extrusion, such polymers were formed by the condensation between hydrolyzed APTES‐grafted polymer chains. These results led us to the conclusion that long‐chain‐branched PP (LCB‐PP) was certainly produced and its formation is essential for the increase in MS of the present blend materials.

Relationship between log(MS) and log(MFR) for PP/PP‐g‐MA/APTES and commercial PP resins.     

Core‐Sheath Structure in Electrospun Nanofibers from Polymer Blends

Summary: Electrospinning of polymer blends offers the potential to prepare functional nanofibers for use in a variety of applications. This work focused on control of the internal morphology of nanofibers prepared by electrospinning polymer blends to obtain core‐sheath structures. Polybutadiene/polystyrene, poly(methylmethacrylate)/polystyrene, polybutadiene/poly(methylmethacrylate), polybutadiene/polycarbonate, polyaniline/polycarbonate, and poly(methylmethacrylate)/polycarbonate blends were electrospun from polymer solutions. It was found that the formation of core‐sheath structures depends on both thermodynamic and kinetic factors. Incompatibility and large solubility parameter difference of the two polymers is helpful for good phase separation, but not sufficient for the formation of core‐sheath structures. Kinetic factors, however, play a much more important role in the development of the nanofiber morphology. During the electrospinning process, the rapid solvent evaporation requires systems with high molecular mobility for the formation of core‐sheath structures. It was found that polymer blends with lower molecular weight tend to form core‐sheath structures rather than co‐continuous structures, as a result of their higher molecular mobility. Rheological factors also affect the internal phase morphology of nanofibers. It was observed the composition with higher viscosity was always located at the center and the composition with lower viscosity located outside.

TEM image of electrospun polybutadiene/polycarbonate nanofibers at 25/75 wt.‐% ratio after staining by osmium tetroxide. The dark regions are polybutadiene and the light region is polycarbonate.     

A Novel Route to Multiphase Polymer Systems Containing Nano‐Droplets: Radical Polymerization of Vinylic Monomers in Gelled Water‐in‐Oil Miniemulsions

Summary: A new strategy for the synthesis of composite polymers with larger volume fraction of aqueous inclusions less than 1 µm in diameter is presented. A water‐in‐oil miniemulsion of aqueous droplets in a continuous, cross‐linkable monomer phase is prepared. The addition of an organo‐gelator allows the immobilization of the droplets in a solid gel, thus avoiding the usual demixing upon polymerization of the continuous phase. This pregelled system is then converted into a composite polymer by photoinitiated free radical polymerization. Such coatings may be used for an improved climate control of buildings or as a deposit for the controlled release of actives from polar nano‐droplets.

SEM image of a cross‐linked composite polymer showing controlled droplet inclusions with a maximal diameter of 500 nm.     

Research on Preparation,Structure and Properties of TiO2/Polythiourethane Hybrid Optical Films with High Refractive Index

Hybrid optical films of TiO₂‐triethoxysilane‐capped polythiourethane (TCPTU) with high refractive indices have been prepared via an in situ sol‐gel method. The high refractive index triethoxysilane‐capped polythiourethane (TCPTU) was synthesized by polyaddition of the triethoxysilane‐modified trimercaptothioethylamine (TMTEA) and 2,2′‐dimercaptoethylsulfide (MES) with 2,4‐tolylene diisocyanate (TDI). The titania content in the hybrid films can be adjusted from 0 to 80 wt.‐% by the feed ratio of titania precursor [Ti(OBu)₄] to polymer (TCPTU). Both FTIR and DSC analyses indicate that there is chemical bonding between the titania domain and the polymer chain. TGA results suggest that the titania of high content was successfully incorporated into polymer matrices and this series of hybrid films have good thermal properties. AFM measurements indicate that in the hybrid films the titania domains are of nanosize scale and the domain size averagely decreases from 60–80 nm to 5–20 nm with increasing content of titania, and the variation of surface roughness for the hybrid films has the same trend. These may be relative to the content of TCPTU and the interaction between titania and polymer (TCPTU). The refractive indices of the hybrid films at 632.8 nm increased from 1 632 to 1 879 as the titania content varied from 0 to 80 wt.‐%.

AFM image of the hybrid film.     

Blends of a Main Chain Liquid‐Crystalline Polyester with a Diepoxide and with a Diepoxide/Amine Mixture Prepared in a Twin‐Screw Extruder

Summary: Blending of the commercial LC‐polyester Rodrun LC‐3000 with the bisphenol‐A‐diglycidyl ether based diepoxide DOW D.E.R.330 alone and with the mixture of the diamine (MCDEA) and D.E.R.330 by means of a twin‐screw extruder has been investigated. Conditions to suppress curing of epoxide and amine during blending have been established. Due to the very low solubility of Rodrun in the diepoxide only LCP‐rich blends with a minimum content of 60 wt.‐% Rodrun could be obtained. The blends were investigated by SEM and thermal analysis (DSC, DMTA). Binary blends are immiscible while ternary blends appear miscible from DMTA up to 30 wt.‐% of epoxy/amine.

SEM micrograph of Rodrun moulded at 230 °C.     

Open Cell Microcellular Foams of Polylactic Acid (PLA)‐based Blends with Semi‐Interpenetrating Polymer Networks

Microcellular biodegradable polymer foam with an open porous structure was prepared from amorphous poly‐L,D ‐lactic acid (P_{L ,D} LA) blended with polystyrene (PS), or polymethyl methacrylate (PMMA). The blends were prepared by polymerizing either styrene or methyl methacrylate (MMA) in a P_{L ,D} LA matrix. The styrene and MMA monomers are good cell‐opening agents and constituents for an IPN. Pressure‐quench batch foaming was conducted using carbon dioxide as a foaming agent at 80 °C under 10 MPa. The effects of monomers and a cross‐linking agent on the foamability and OCC were investigated. Manipulation of the monomer and the cross‐linking agent concentrations was able to change the viscoelasticity and partial miscibility of the blend and control the cell size at the micron scale as well as open pore content in the range of 20–90%.

     

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.

     

Steady‐State Model for Olefin Polymerization With a Two‐Site Vanadium Catalyst in a Continuous Stirred‐Tank Reactor

Summary: In this study, a process for continuous EP(D)M production is examined and a mechanistic kinetic model is developed to explain the behavior exhibited by this vanadium‐catalyzed solution polymerization process. The catalyst system without promoter and without hydrogen, produces polymer with bimodal molecular weight distributions (MWDs), while the addition of catalyst promoter causes an order of magnitude increase in catalyst productivity and eliminates the higher‐MW component in the MWD. The addition of hydrogen also precludes bimodal MWDs, regardless of the presence of promoter. In all cases, the polymerization rate has a zero‐order rather than a first‐order response to monomer concentration. The zero‐order response of polymerization rate to monomer concentration is described using a mechanism of monomer coordination to form a stable complex prior to insertion. The bimodal MWDs at high monomer feeds (corresponding to low monomer conversion), in the absence of catalyst promoter and hydrogen, are explained by a two‐site type catalyst model in which both monomer insertion and the formation of the second‐site type occur after the monomer forms a stable coordinated complex with the first catalyst site type. The model reconciles the molecular weight development with these seldom‐discussed features of vanadium catalysis.

Propylene acting as a coordinating ligand at a coordinatively unsaturated vanadium catalyst site (adapted from ref.^[7]).