Cocrystalline copolyimides of poly(ethylene 2,6-naphthalate)

Copolycondensation of N,N′-bis(2-hydroxyethyl)-biphenyl-3,4,3′,4′-tetracarboxylic diimide (5–25 mol %) with bis(2-hydroxyethyl)-2,6-naphthalate affords a series of cocrystalline, poly(ethylene 2,6-naphthalate) (PEN)-based poly(ester imide)s. The glass transition temperature rises with the level of comonomer, from 118 °C for PEN itself to 148 °C for the 25% diimide copolymer. X-ray powder and fiber diffraction studies show that, when 5 mol % or more of diimide is present, the α-PEN crystal structure is replaced by a new crystalline phase arising from isomorphic substitution of biphenyldiimide for PEN residues in the polymer crystal lattice. This new phase is provisionally identified as monoclinic, C2/m, with two chains per unit cell, a = 10.56, b = 6.74, c = 13.25 Å, and β = 143.0°.

Avaliação do comportamento ao desgaste de compósitos poliméricos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Poly(lactide): from hyperbranched copolyesters to new block copolymers with functional methacrylates

The prologue of this thesis (Chapter 1.0) gives a general overview on lactone based poly(ester) chemistry with a focus on advanced synthetic strategies for ring-opening polymerization, including the emerging field of organo catalysis. This section is followed by a presentation of the state-of the art regarding the two central fields of the thesis: (i) polyfunctional and branched poly(ester)s in Chapter 1.1 as well as (ii) the development of new poly(ester) based block copolymers with functional methacrylates (Chapter 1.2). Chapter 2 deals with the synthesis of new, non-linear poly(ester) structures. In Chapter 2.1, the synthesis of poly(lactide)-based multiarm stars, prepared via a grafting-from method, is described. The hyperbranched poly(ether)-poly(ol) poly(glycerol) is employed as a hydrophilic core molecule. The resulting star block copolymers exhibit potential as phase transfer agents and can stabilize hydrophilic dyes in a hydrophobic environment. In Chapter 2.2, this approach is expanded to poly(glycolide) multiarm star polymers. The problem of the poor solubility of linear poly(glycolide)s in common organic solvents combined with an improvement of the thermal properties has been approached by the reduction of the total chain length. In Chapter 2.3, the first successful synthesis of hyperbranched poly(lactide)s is presented. The ring-opening, multibranching copolymerization of lactide with the “inimer” 5HDON (a hydroxyl-functional lactone monomer) was carefully examined. Besides a precise molecular characterization involving the determination of the degree of branching, we were able to put forward a reaction model for the formation of branching during polymerization. Several innovative approaches to amphiphilic poly(ester)/poly(methacrylate)-based block copolymers are presented in the third part of the thesis (Chapter 3). Block copolymer build-up especially relies on the combination of ring-opening and living radical polymerization. Atom transfer radical polymerization has been successfully combined with lactide ring-opening, using a “double headed” initiator. This strategy allowed for the realization of poly(lactide)-block-poly(2-hydroxyethyl methacrylate) copolymers, which represent promising materials for tissue engineering scaffolds with anti-fouling properties (Chapter 3.1). The two-step/one-pot approach forgoes the use of protecting groups for HEMA by a careful selection of the reaction conditions. A series of potentially biocompatible and partially biodegradable homo- and block copolymers is described in Chapter 3.2. In order to create a block copolymer with a comparably strong hydrophilic character, a new acetal-protected glycerol monomethacrylate monomer (cis-1,3- benzylidene glycerol methacrylate/BGMA) was designed. The hydrophobic poly(BGMA) could be readily transformed into the hydrophilic and water-soluble poly(iso-glycerol methacrylate) (PIGMA) by mild acidic hydrolysis. Block copolymers of PIGMA and poly(lactide) exhibited interesting spherical aggregates in aqueous environment which could be significantly influenced by variation of the poly(lactide)s stereo-structure. In Chapter 3.3, pH-sensitive poly(ethylene glycol)-b-PBGMA copolymers are described. At slightly acidic pH values (pH 4/37°C), they decompose due to a polarity change of the BGMA block caused by progressing acetal cleavage. This stimuli-responsive behavior renders the system highly attractive for the targeted delivery of anti-cancer drugs. In Chapter 3.4, which was realized in cooperation, the concept of biocompatible, amphiphilic poly(lactide) based polymer drug conjugates, was pursued. This was accomplished in the form of fluorescently labeled poly(HPMA)-b-poly(lactide) copolymers. Fluorescence correlation spectroscopy (FCS) of partially biodegradable block copolymer aggregates exhibited fast cellular uptake by human cervix adenocarcinoma cells without showing toxic effects in the examined concentration range (Chapter 4.1). The current state of further projects which will be pursued in future studies is addressed in Chapter 4. This covers the synthesis of biocompatible star block copolymers (Chapter 4.2) and the development of new methacrylate monomers for biomedical applications (Chapters 4.3 and 4.4). Finally, the further investigation of hydroxyl-functional lactones and carbonates which are promising candidates for the synthesis of new hydrophilic linear or hyperbranched biopolymers, is addressed in Chapter 4.5.

Wear of PEEK-Ti6Al4V systems under micro-abrasion and linear sliding conditions

Dissertação de mestrado integrado em Engenharia Biomédica

A novel approach to processing high-performance polymers that exploits entropically driven ring-opening polymerization

Blends of the poly(ether sulfone) derived from 4,4'-biphenol and 4,4'-dichlorodiphenylsulfone (Radel-R(TM)) with its homologous macrocyclic oligomers show greatly lowered melt viscosities relative to that of the parent polymer, potentially enabling more facile production and fabrication of fiber-reinforced composite materials. The macrocycles can then undergo entropically driven ring-opening polymerization in situ. The required blends can be obtained easily in one step, by carrying out polycondensations at concentrations lower than those usually used for polymer synthesis.

Dithioacetalisation of PEEK: a general technique for the solubilisation and characterisation of semi-crystalline aromatic polyketones

The family of semi-crystalline, aromatic, high-temperature thermoplastics known as poly(ether-ketone)s are insoluble in conventional organic solvents, but undergo completely general and quantitatively reversible reactions with alkanedithiols in strong acid media, to give soluble poly(dithioacetal)s, which are readily characterisable by GPC and light scattering techniques.

Extreme complementarity in a macrocycle-tweezer complex

Interaction of a novel pyrene-based tweezer molecule with a macrocyclic ether-imide-sulfone results in formation of a strongly bound complex (K-a = 24 000 M-1) in which binding results not only from pi-pi stacking interactions involving pyrene units as donors and macrocyclic naphthalene-tetracarboximide and biphenylenedisulfone groups as acceptors but also from N-(HO)-O-... and C-(HO)-O-... hydrogen bonds and from "reverse" pi-stacking of the electron-poor isophthaloyl residue of the tweezer with an electron-rich 3-aminophenoxy residue of the macrocyclic imide.

Direct iminization of PEEK

Semi-crystalline poly(ether ketone)s are important high-temperature engineering thermoplastics, but are difficult to characterize at the molecular level because of their insolubility in conventional organic solvents. Here we report that polymers of this type, including PEEK, react cleanly at high temperatures with low-volatility aralkyl amines to afford stable, noncrystalline poly(ether-imine)s, which are readily soluble in solvents such as chloroform, THF and DMF and so characterizable by conventional size-exclusion chromatography.

Desgaste de polímeros estruturais de engenharia em contato de deslizamento com cilindro metálico

Present work proposed to map and features the wear mechanisms of structural polymers of engineering derived of the sliding contact with a metallic cylindrical spindle submitted to eccentricity due to fluctuations in it is mass and geometric centers. For this it was projected and makes an experimental apparatus from balancing machine where the cylindrical counterbody was supported in two bearings and the polymeric coupon was situated in a holder with freedom of displacement along counterbody. Thus, the experimental tests were standardized using two position of the two bearings (Fixed or Free) and seven different positions along the counterbody, that permit print different conditions to the stiffness from system. Others parameters as applied normal load, sliding velocity and distance were fixed. In this investigation it was used as coupon two structural polymers of wide quotidian use, PTFE (polytetrafluroethylene) and PEEK (poly-ether-ether-ketone) and the AISI 4140 alloy steel as counterbody. Polymeric materials were characterized by thermal analysis (thermogravimetric, differential scanning calorimetry and dynamic-mechanical), hardness and rays-X diffractometry. While the metallic material was submitted at hardness, mechanical resistance tests and metallographic analysis. During the tribological tests were recorded the heating response with thermometers, yonder overall velocity vibration (VGV) and the acceleration using accelerometers. After tests the wear surface of the coupons were analyzed using a Scanning Electronic Microscopy (SEM) to morphological analysis and spectroscopy EDS to microanalysis. Moreover the roughness of the counterbody was characterized before and after the tribological tests. It was observed that the tribological response of the polymers were different in function of their distinct molecular structure. It were identified the predominant wear mechanisms in each polymer. The VGV of the PTFE was smaller than PEEK, in the condition of minimum stiffness, in function of the higher loss coefficient of that polymer. Wear rate of the PTFE was more of a magnitude order higher than PEEK. With the results was possible developed a correlation between the wear rate and parameter (E/ρ)1/2 (Young modulus, E, density, ρ), proportional at longitudinal elastic wave velocity in the material.

Processing of high performance composites based on peek by aqueous suspension prepregging

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Ferroelectric ceramic/polymer composite for measuring X-ray intensity in the ortovoltage range

Pyroelectric sensors work as a thermal transducer converting the non-quantified thermal flux into the output measurable quantity of electrical charge, voltage or current. Ferroelectric ceramics and ferroelectric polymers have been extensively used as thermal detectors. More recently the research in the field of pyroelectricity has been concentrated on discovering materials with higher figures of merit (FOM), which means better sensing materials. Composite materials obtained with ferroelectric ceramics embedded in polymer host have received great attention because of their formability, mechanical resistance and the possibility to change their dielectric property varying the volume fraction of ceramic particles. In this work composite films made of modified lead titanate (PZ34) and poly(ether-ether-ketone) (PEEK) were characterized and used as sensing element to measure X-ray intensity in the ortovoltage range (120 - 300 kVp). The sensor response varies from 2.70 V to 0.80 V in the energy fluency range of 6.30 to 37.20 W/m(2). Furthermore the absorbed energy was analyzed as a function of the ionizing energy. The results indicate that the PZ34/PEEK composite with 60/40 vol.% can be useful to monitor X-ray radiation therapy.

PTCa/PEEK composite acoustic emission sensors

Composites made of Calcium-modified lead titanate (PTCa) and poly (ether-etherketone) (PEEK) high performance polymer matrix were prepared in the film form using a hot press. The ceramic volume fraction reaches up to 60 percent providing a composite with 0-3 and 1-3 mixed connectivities due to the high ceramic content and the resulting materials could be considered PEEK-bonded PTCa particulate composite. The composites were characterized using piezoelectric spectroscopy and ultrasonic immersion techniques. Values up to 38.5 pC/N were obtained for the longitudinal d33 piezoelectric coefficient. The composite was surface-mounted on a carbon fiber plate-like specimen and the ability of the PTCa/PEEK composite to detect acoustic emission (AE) is reported. © 2006 IEEE.

Caracterização de filmes finos de polímeros entrecruzáveis como camada dielétrica em dispositivos de eletrônica orgânica

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Preparo, caracterização e aplicação do compósito PTCa (Titanato de chumbo modificado com cálcio)/PEEK (Poliéter éter cetona) como sensor de radiação

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Filmes finos híbridos orgânicos-inorgânicos para fotônica

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)