Pierluigi Magagnini

Reactive Compatibilizer Precursors for LDPE/PA6 Blends, 1 Ethylene/Acrylic Acid Copolymers

Ethylene/acrylic acid copolymers (EAA) with different acrylic acid (AA) contents have been used as compatibilizer precursors (CPs) for blends of two grades of lowdensity polyethylene (LDPE) with polyamide-6 (PA). In the first part of the work, binary blends of the CPs with LDPE and with PA have been studied in order to get an insight into the interactions of the EAA copolymers with the blends components. It has been shown that the CPs form immiscible, yet highly compatible, blends with LDPE. Investigation of the binary CP/PA blends provided evidence that acidolysis reactions occur between the carboxyl groups of the CPs and the amine and amide groups of PA, with formation of CP/PA graft (CP-g-PA) copolymers, although these reactions need relatively long times to go to completion. In the second part of the work, ternary LDPE/PA/CP blends have been prepared and characterized with a number of techniques. It has been shown that the addition of only 1-2 phr of CP into the LDPE/ PA blends is sufficient to enhance interfacial adhesion, to improve the minor phase droplet dispersion and to hinder coalescence. The effectiveness of the investigated CPs increases with an increase of the AA content from 6 to 11 wt.-%. Partial neutralization of the carboxyl groups of EAA with zinc also seems to improve the CP efficiency and this effect is thought to result from an acceleration of the acidolysis reactions responsible for the formation of CP-g-PA copolymers.

Reactive compatibilizer precursors for LDPE/PA6 blends. III: ethylene–glycidylmethacrylate copolymer

Abstract The effectiveness of a commercial ethylene–glycidylmethacrylate copolymer (Lotader GMA AX 8840) as a compatibilizer precursor (CP) for blends of low density polyethylene (LDPE) with polyamide-6 (PA) has been evaluated by an investigation of the thermal properties and the morphology of binary (LDPE/CP and PA/CP) and ternary (LDPE/PA/CP) blends, as well as by solvent fractionation experiments. It has been demonstrated that the epoxy groups of the CP react quite easily, during melt blending, with both the amine and the carboxyl end groups of PA to give CP-g-PA copolymers, which, depending on the relative amounts of PA and CP, may be partially cross-linked. The composition of the graft copolymers has been approximately determined by gravimetric and calorimetric measurements. The compatibilizing efficiency of the CP employed in this work has been found to be comparable to that of the ethylene–acrylic acid copolymers, and lower than that of a maleic anhydride-functionalized polyethylene, which had been used in previous works.

Mesophase Formation in Polymers With Anisometric Side – Groups in Relation to Their Chemical and Stereochemical Structure

Abstract The influence of the flexibility of the polymer main chain on the smectic ordering has been investigated, by means of optical, diffractometric and calorimetric techniques, in several polymers carrying rigid anisometric side-groups. The effect of the chemical structure of the sidegroups has been examined throughout: atactic polymers with biphenylyl side-groups may be amorphous or mesomorphous depending on the nature of the groups linking the biphenylyl moiety to the backbone chain. Correlations between the molecular weight and the stereochemical structure of the macromolecules and the occurrence of a thermotropic smectic phase in a series of polyacrylates and polymethacrylates, have been reported.

Non-isothermal crystallization kinetics of poly(phenylene sulfide)/Vectra-B blends

Abstract The non-isothermal crystallization behaviour of blends of poly(phenylene sulfide) (PPS) with the thermotropic liquid-crystalline copoly(ester amide) Vectra-B950 (VB) was studied by means of differential scanning calorimetry. The PPS crystallization temperature and the crystallization rate coefficient were found to increase markedly upon addition of 2–50% VB. It was shown that the Ozawa equation is valid not only for neat PPS but also for the blends. The values of the Avrami exponents are in fair agreement with those found previously by isothermal analysis, and do not depend on the presence and the concentration of VB. It has been suggested that the slope of the plots of the cooling crystallization function versus T can be a criterion for the overall non-isothermal crystallization rate. It has been concluded that the non-isothermal crystallization of PPS is strongly accelerated by the presence of the VB phase, whereas the type of nucleation and the geometry of crystal growth do not change, and no reduction of the PPS degree of crystallinity could be noticed.

Shear viscosity of polybutyleneterephthalate/liquid crystal polymer blends

Viscosity measurements have been carried out on blends of polybuty-leneterephthalate (PBT) and a liquid crystalline copolyesteramide (LCP). The flow curves of the blends with LCP content larger than 20%, show a behavior similar to that of the pure LCP, with a rapid rise of the viscosity at low shear rates. The viscosity-composition curves exhibit a deep minimum at low LCP content which may be mainly attributed to the lack of interactions between the two phases.

One-dimensional order in atactic polyacrylates containing aromatic side groups

Abstract To help in the understanding of the relations between chemical structure and morphological order in polymers of the type of poly(p-biphenyl acrylate) (PPBA), some polymers of similar structure have been synthesized and some of their physical properties studied. These polymers are: poly(p-biphenyl methacrylate), poly(vinyl p-phenyl benzoate), poly(p-phenyl benzyl acrylate), poly(p-benzyl phenyl acrylate) and poly(p-cyclohexyl phenyl acrylate) (PPCPA). Only PPCPA has been shown to possess a one-dimensional order in the solid state for reasons which are briefly discussed. The effect of copolymerization on the structural order of PPBA has also been given preliminary study. Copolymers of p-biphenyl acrylate (PBA) with p-biphenyl methacrylate (PBMA), N-vinyl carbazole (NVC) and p-cyclohexyl phenyl acrylate (PCPA) have been prepared and their properties have been studied by DSC and X-ray techniques. Small concentrations of PBMA or NVC units are sufficient to cancel the order of PPBA. On the contrary, copolymers of PBA and PCPA of any composition display morphological order in the solid state.

Side-chain liquid crystalline polyesters for optical information storage†

We report erasable holographic recording with a resolution of at least 2500 lines/mm on unoriented films of sidechain liquid-crystalline polyesters. Recording energies of approximately 1 J/cm(2) have been used. We have obtained a diffraction efficiency of approximately 30% with polarization recording of holograms. The holograms can be erased by heating them to approximately 80 degrees C for approximately 2 min and are available for rerecording.

Synthesis of PP–LCP graft copolymers and their compatibilizing activity for PP/LCP blends

The aim of this work was the synthesis of new graft copolymers consisting of polypropylene (PP) backbones and liquid crystalline polymer (LCP) branches, to be used as compatibilizing agents for PP/LCP blends. The PP-g-LCP copolymers have been prepared by polycondensation of the monomers of a semiflexible liquid crystalline polyester (SBH 1 : 1 : 2), that is, sebacic acid (S), 4,4′-dihydroxybiphenyl (B), and 4-hydroxybenzoic acid (H) in the mole ratio of 1 : 1 : 2, carried out in the presence of appropriate amounts of a commercial acrylic-acid-functionalized polypropylene (PPAA). The polycondensation products, referred to as COPP50 and COPP70, having a calculated PPAA concentration of 50 and 70 wt %, respectively, have been fractionated with boiling toluene and xylene, and the soluble and insoluble fractions have been characterized by Fourier transform infrared and nuclear magnetic resonance spectroscopy, scanning electron microscopy (SEM), differential scanning calorimetry, and X-ray diffraction. All analytical characterizations have concordantly shown that the products are formed by intricate mixtures of unreacted PPAA and SBH together with PP-g-SBH copolymers of different composition. Exploratory experiments carried out by adding small amounts of COPP50 or COPP70 into binary mixtures of isotactic polypropylene (iPP) and SBH while blending have demonstrated that this practice leads to an appreciable improvement of the dispersion of the minor LCP phase, as well as to an increase of the crystallization rate of iPP.

Blends of poly(ethylene 2,6-naphthalate) with liquid-crystalline polymers: crystallization behavior and morphology

The isothermal crystallization behavior and morphology of blends of Poly(ethylene 2,6-naphthalate) (PEN) with two types of liquid-crystalline polymers (LCP) (rigid and semiflexible) have been studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM) and scanning electron microscopy (SEM). The blends posses a two-phase morphology due to immiscibility of the two components. The dispersion of the minor LCP phase is favored at a low LCP concentration (7 wt%). The PEN overall crystallization rate is enhanced strongly by the addition of LCPs. The maximum enhancing effect has been found to occur at a LCP concentration of ca. 7 wt%. The POM observations show that PEN spherulite dimensions decrease in the presence of LCPs. These results have been interpreted on the basis of a heterogeneous nucleation played by the crystallized LCP particles on the molten PEN matrix. The nucleation mechanism and the equilibrium melting temperature of PEN are not changed by the presence of a dispersed LCP phase. The relationship between blend morphology and nucleation phenomena has been discussed.

Oxazoline functionalization of polyethylenes and their blends with polyamides and polyesters

The compatibilization of blends of polyamide-6 (PA6) with linear low density polyethylene (LLDPE) and of poly(ethylene terephthalate) (PET) with high density polyethylene (HDPE), by functionalization of the polyethylenes with oxazoline groups was investigated. Chemical modification of LLDPE and HDPE was carried out by melt free radical grafting with ricinoloxazoline maleinate. Blends preparation was made either with a two-steps procedure comprising functionalization and blending, and in a single step in which the chemical modification of polyethylene with the oxazoline monomer was realized in situ, during blending. The characterization of the products was carried out by FTIR spectroscopy and scanning electron microscopy (SEM). The rheological and mechanical properties of the blends were also investigated. The results show that functionalization of the polyethylenes can be achieved by melt blending with ricinoloxazoline maleinate even in the absence of free radical initiators. The compatibilization of the blends enhances the dispersion of the minor phase significantly, increases the melt viscosity, and improves the mechanical properties. The one-step preparation of the compatibilized blends was also found to be effective, and is thought to be even more promising in view of commercial application.