0000000000041392
AUTHOR
Pierluigi Magagnini
Compatibilization of blends of polyethylene with a semirigid liquid crystalline polymer by PE-g-LCP copolymers
The blends of thermoplastics with liquid crystalline polymers show, in general, poor properties because of the lack of adherence between the two phases. The use of ad hoc synthesized copolymers containing the monomer units of the two polymers has been recently considered by some of us for blend compatibilization, and the results appear promising. In this work, new PE-g-LCP copolymers, prepared either by the synthesis of the LCP in the presence of a functionalized PE, or by reactive blending of the latter polymer with preformed LCP, have been employed as compatibilizing additives for blends of PE with a semirigid LCP. The morphology and the rheological and mechanical properties of the ternar…
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…
Reactive compatibilization of PA6/LDPE blends with an ethylene–acrylic acid copolymer and a low molar mass bis-oxazoline
Abstract A sample of polyamide-6 (PA) was blended with low density polyethylene (LDPE) in the 80/20 wt/wt ratio, either without and with 2 phr of an ethylene–acrylic acid copolymer (EAA), Which was known to behave as a compatibilizer precursor, and the effect of the addition of small amounts (0.2 or 0.35 phr) of a fourth component, 2,2′-(1,3-phenylene)-bis(2-oxazoline) (PBO), was investigated. The reactions of PBO with EAA, PA and their blends were studied by recording as a function of time the torque applied to the blending apparatuses and by studying the solubility behavior of the products in formic acid. The PALDPE blends were prepared in a co-rotating twin screw extruder and were charac…
Torque rheometry investigation of model transreactions involving condensation polymers: I. Polyesters
The chemical transformations taking place when poly(ethylene terephthalate) (PET) or poly(ethylene naphthalate) (PEN) are blended in the melt with different low molar mass substances containing hydroxyl, carboxyl, or amine functional groups have been investigated as models of the transreactions, undergone by the polyesters in reactive blending operations. The polyester molecular weight changes caused by the alcoholysis, acidolysis, aminolysis, and esterolysis reactions have been monitored by torque-rheometry, using a Brabender Plasticorder static mixer. The degradation of the polyesters by hydrolysis was also studied, under similar conditions, by the addition of a water-releasing substance …
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.
Comparative Study of Different Maleic Anhydride Grafted Compatibilizer Precursors toward LDPE/PA6 Blends: Morphology and Mechanical Properties
The study deals with the effectiveness of maleic anhydride grafted styrene-b-ethylene-co-propylene copolymer (SEPMA) as compatibilizer precursor (CP) for blends of low density polyethylene (LDPE) with polyamide-6 (PA). The CP was produced by grafting MA onto SEP in the melt. The specific interactions between the CP and the blends components have been investigated through characterizations of the binary LDPE/CP and PA/CP blends. The compatibilizing efficiency of the MA-grafted SEP, as revealed by the thermal properties and the morphology of the compatibilized blends, has been shown to be excellent. The morphology, as well as the mechanical properties of the compatibilized with SEPMA 75/25 w/…
Synthesis, properties and processability of a new class of semirigid liquid crystalline copolyesteramides
Abstract A new family of semirigid main chain liquid crystalline polymers (LCPs), referred to as SBAN, characterized by fairly good processability and mechanical properties, and improved thermal resistance, have been synthesized by the melt polycondensation of sebacic acid (S), 4,4′-dihyhxybiphenyl (B), 4-aminobenzoic acid (A), and 2-hydroxy-6-naphthoic acid (N), in a wide range of compositions. The molar concentration of the A ahd N units, in these LCPs must be kept lower than ca 40 and 60%, respectively, in order to avoid the formation of homopolymeric blocks, which impair spinnability. The presence of A units grants the formation of hydrogen bonds between neighboring macromolecules, and …
On the use of PET-LCP copolymers as compatibilizers for PET/LCP blends
Copolyesters of poly[ethylene terephthalate) (PET) with a liquid crystalline polymer (LCP), SBH 1:1:2, have been synthesized by the polycondensation, carried out in the melt at temperatures up to 300 degrees C of sebacic acid (S), 4,4'-dihydroxybiphenyl (B), and 4-hydroxybenzoic acid (H) in the presence of PET. The PET-SBH copolyesters have been characterized by differential scanning calorimetry, scanning electron microscopy, X-ray diffraction, etc., and the relationships between properties and preparation conditions are discussed. The copolyesters show a biphasic nature, which is more evident for the products synthesized with a thermal profile comprising relatively lower temperatures (220-…
Liquid crystal polymer-based blends: “Universal grade” polymers?
Polymeric materials can be easily processed with different processing operations thanks to suitable rheological properties. Melt flow index, or grade, which is a measure of the fluidity of the polymers, is the most commonly parameter used to characterize the polymers from the point of view of their melt viscosity. Injection molding requires high grade materials, whereas low grade values are best suited for extrusion. Of course, it would be no doubt of interest if single “universal grade” materials could be used for all processing operations. In this paper it is demonstrated that the blends of low grade polymers with small amounts of liquid crystal polymers can be conveniently used for all p…
Effect of the Components Molar Mass and of the Mixing Conditions on the Compatibilization of PE/LCP Blends by PE-g-LCP Copolymers
The rheology, morphology, and mechanical properties of blends of high-density polyethylene (HDPE) with a semiflexible liquid crystalline copolyester (SBH) were studied in order to assess the compatibilizing ability of added PE-g-SBH copolymers, and its dependence on the molar mass of the PE matrix, and on the technique used for blend preparation. The PE-g-SBH copolymers were synthesized as described in previous articles, either by the polycondensation of the SBH monomers in the presence of a functionalized PE sample containing free carboxyl groups, or by reactive blending of the latter polymer with preformed SBH. Two samples of HDPE having different molar masses, and two samples of SBH with…
Morphology of nanocomposites from ethylene-acrylic acid copolymers
AbstractNew nanocomposites have been prepared by melt-compounding from commercial ethylene-acrylic acid copolymers (EAA) of different molar mass, molecular structure (branched or linear) and AA concentration, and a Zn-ionomer, with three commercial clays containing different proportions of the same organic modifier (dimethyldi(hydrogenated tallow)ammonium ion). Their morphology has been preliminarily investigated by X-ray scattering and transmission electron microscopy. The nanocomposites showed disordered intercalated morphology, with an expansion of the average gallery height, which appears to depend quite strongly on the molecular architecture of the EAA, whereas the other investigated v…
Liquid crystal polymers (LCP) as processing aids and reinforcing agents. A study of nylon 6/LCP blends
Influence de petites quantites d'un copolyesteramide thermotropique sur les proprietes mecaniques et la mise en œuvre du polyamide 6
Effects of organoclay on morphology and properties of nanocomposites based on LDPE/PA-6 blends without and with SEBS-g-MA compatibilizer
LDPE/PA-6 blends (75/25 wt/wt) were added with SEBS-g-MA (S) and/or an organoclay (20A) using different compounding sequences and the morphology and the properties of the blends or composites were investigated. An XRD study of the nanocomposites with pure polymers showed that 20A is intercalated by LDPE or PA-6 chains, whereas it is exfoliated by S if the clay concentration does not exceed 10 wt%. The SEM investigation showed that both S and 20A behave as efficient emulsifying agents for the LDPE/PA-6 blends. However, their effect on the mechanical properties was found to be opposite: S enhanced toughness but lowered the stiffness, whereas 20A improved the elastic modulus but impaired the i…
On the interlayer spacing collapse of Cloisite (R) 30B organoclay
Abstract When used as a nanofiller for the preparation of polymer/clay nanocomposites (PCNs), Cloisite® 30B (30B) often undergoes a d-spacing collapse, as demonstrated by a shift to wider angles of the XRD basal reflection. Such collapse has been variously attributed to organoclay contamination or, more often, to thermal degradation of the organic modifier with expulsion of the volatile products from the galleries. In this work, several PCNs loaded with 30B have been prepared by melt compounding, using different polymer matrices, and have subsequently been subjected to dissolution in appropriate solvents followed by precipitation in excess non-solvent and room temperature drying. An XRD ana…
Organoclay Nanocomposites from Ethylene-Acrylic Acid Copolymers
A study of the structure–property relationships for nanocomposites prepared by melt compounding from ethylene–acrylic acid copolymers of varied composition and molecular architecture, and organoclays modified with different ammonium ions has been made by DSC, POM, SEM, TEM, WAXD, and rheological and mechanical tests. Within the series of clays investigated, the best levels of dispersion were displayed by those organically modified with quaternary ammonium ions containing two long alkyl tails. The relevant nanocomposites were shown to possess mixed exfoliated and intercalated morphology. The spacing of the intercalated clay stacks, most of which comprise few silicate layers, was found to be …
Rheological behavior of a semirigid liquid crystal polymer
The rheological behavior of liquid crystal polymers is still far from completely clarified from both experimental and theoretical points of view. In this paper, the shear flow and the non-isothermal elongation flow behavior of a semi-rigid liquid crystal copolyester is discussed. The viscosity strongly decreases when the test temperature is increased above the crystal-nematic transition temperature; below this temperature the viscosity is very high. The thermal history strongly affects the shear viscosity. The elongational flow behavior depends also on temperature. Above the crystal-nematic transition temperature and the mesophase is easily spinnable, whereas below this temperature, the spi…
Reactive blending of a functionalized polyethylene with a semiflexible liquid crystalline copolyester
Reactive blends (50/50 w/w) of a low molar mass polyethylene containing free carboxylic groups (PEox) and a semiflexible liquid crystalline polyester (SBH 1 : 1 : 2, by Eniricerche) have been prepared at 240 degrees C in a Brabender mixer, in the presence of Ti(OBu)(4) catalyst, for different mixing times (15, 60, and 120 min). In order to prove the formation of a PE-g-SBH copolymer, the blends have been fractionated by successive extractions with boiling toluene and xylene. The soluble fractions and the residues have been analyzed by Fourier transform infrared (FTIR) spectroscopy, thermogravimetry (TG and DTG), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM)…
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 an…
Effect of adding new phosphazene compounds to poly(butylene terephthalate)/polyamide blends. I: Preliminary study in a batch mixer
Abstract Poly(butylene terephthalate) (PBT) and a sample of polyamide have been melt processed in the presence of two new phosphazene compounds, namely 2,2-dichloro-4,4,6,6-bis[spiro(2′,2″dioxy-1′,1″biphenyl)]cyclotriphosphazene (2Cl-CP) and 2,2-bis-(2-methoxy-4-methyleneoxy-phenoxy)-4,4,6,6,-bis[spiro(2′,2″dioxy-1′,1″biphenyl)]cyclophosphazene (CP-2EPOX). The blends were prepared by using polyamide 6 (PA6) at 25/75 w/w and 75/25 w/w composition. In order to perform a preliminary analysis on the behaviour of the blends, the materials were prepared in a batch mixer. The materials have been completely characterized from a rheological, morphological, mechanical point of view. The results indic…
Rheological behavior and thermal stability of poly(phenylene sulfide)/vectra-B950 blends
Blends of polyphenylene sulfide (PPS) with a commercial, wholly aromatic, liquid crystalline polymer (LCP), Vectra-B950, have been prepared by melt-blending. Their rheological behavior has been studied in order to determine if the LCP displays a processing aid ability, and under what conditions it gives rise to potentially reinforcing fibrils dispersed in the PPS matrix. The problem of the thermal stability of PPS/LCP blends, which has been considered by some authors as the main obstacle to the production of usable materials due to the evolution of gaseous substances during processing, has been discussed. © 1994 John Wiley & Sons, Inc.