Unsaturated Polyester Resins from Recycled Polyethyleneterephthalate

Tämän diplomityön tarkoituksena oli tutkia miten kuluttajien kierrättämästä polyeteenitereftalaatista ( PET ) voi valmistaa tyydyttymättömiä polyesterihartseja. Työssä valmistettiin yleiskäyttöön soveltuva laminointihartsi sekä 'gel coat' -hartsi jota käytetään esim. veneiden pintamaalina. Yleishartsin depolymerointiin käytettiin propyleeniglykolia ja 'gel coat' -hartsin valmistamiseen neopentyyliglykolia. Polykondensaatiovaiheessa reaktioon lisättiin maleiinihappoa ja lopuksi hartsit liuotettiin styreeniin. Kirjallisuusosassa esitetään eri menetelmiä PET:n depolymeroimiseksi. Lisäksi esitetään eri vaihtoehtoja glykolien, happojen, katalyyttien ja vinyylimonomeerien valitsemiseksi tyydyttymättömien polyesterihartsien valmistuksessa. Analyysimenetelmiä nestemäisten ja kovetettujen hartsien tutkimiseen ja vertailuun käydään läpi kuten myös erilaisia sovelluksia polyesterihartsien käyttämiseksi. Kokeellinen osa todisti että PET-pullojäte voidaan prosessoida hartsiksiilman uusia investointeja prosessilaitteistoon. PET:n glykolyysi kesti viidestäseitsemään tuntia ja polykondensaatiovaihe kahdesta ja puolesta viiteen tuntiin. Hartsien molekyylipainot ja mekaanisten testien tulokset olivat vertailukelpoisia kaupallisten hartsien antamien tulosten kanssa. Glykolyysivaiheen momomeeri- ja oligomeeripitoisuudet mitattiin geelipermeaatiokromatografialla, jotta nähtiin miten pitkälle depolymerisaatio oli edennyt. Tätä tietoa voidaan hyödyntää uusien hartsireseptin suunnittelussa. Polymeeriketjussa jäljellä olevien C=C kaksoissidosten määrä ja niiden isomeraatioaste maleaattimuodosta fumaraattimuotoon mitattiin 1H-NMR -menetelmällä. Tislevesien koostumus määritettiin kaasukromatografialla, ja tulokset kertoivat katalyytin sisältämän kloorin reagoineen glykolien kanssa, johtaen suureen glykolikulutukseen ja muihin ei-toivottuihin sivureaktioihin. Hartsien sietokykyä auringon valolle mitattiin niiden UV-absorption avulla. Kummastakin hartsista valmistettiin 'gel coat' -maalit jotkalaitettiin sääkoneeseen, joka simuloi auringonpaistetta ja vesisadetta vuorotellen. Näistä 'gel coateista' mitattiin niiden kellastumista. Kummastakin hartsista tehdyt valut asetettiin myös sääkoneeseen ja IR-spektreistä ennen jajälkeen koetta nähtiin että C=O ja C-O esterisidoksia oli hajonnut.

Optimisation of commercial production processes for polyester resins

DUE TO COPYRIGHT RESTRICTIONS ONLY AVAILABLE FOR CONSULTATION AT ASTON UNIVERSITY LIBRARY AND INFORMATION SERVICES WITH PRIOR ARRANGEMENT

Commercial batchwise production of polyester resins.

DUE TO COPYRIGHT RESTRICTIONS ONLY AVAILABLE FOR CONSULTATION AT ASTON UNIVERSITY LIBRARY AND INFORMATION SERVICES WITH PRIOR ARRANGEMENT

Modification of Unsaturated Polyester Resin by Polyurethane Prepolymers

Unsaturated polyester resins (UPRs) are extensively used by the fiber-reinforced plastic (FRPs) industry. These resins have the disadvantages of brittleness and poor resistance to crack propagation. In this study, UPRs were chemically modified by reactive blending with polyurethane prepolymers having terminal isocyanate groups. Hybrid networks were formed by copolymerisation of unsaturated polyesters with styrene and simultaneous reaction between terminal hydroxyl groups of unsaturated polyester and isocyanate groups of polyurethane prepolymer. The prepolymers were based on toluene diisocyanate (TDI) and each of hydroxy-terminated natural rubber (HTNR), hydroxy- terminated polybutadiene (HTPB), polyethylene glycol (PEG), and castor oil. Properties like tensile strength, toughness, impact resistance, and elongation-at-break of the modified UPRs show considerable improvement by this modification. The thermal stability of the copolymer is also marginally better

Epoxidized Phenolic Novolac: A Novel Modifier for Unsaturated Polyester Resin

Unsaturated polyester resins (UPRs) are used widely in the fiber-reinforced plastics (FRPs) industry. These resins have the disadvantages of brittleness and poor resistance to crack propagation. In this study, hybrid polymer networks (HPNs) based on UPR and epoxidized phenolic novolacs (EPNs) were prepared by reactive blending. A HPN is composed of a backbone polymer containing two types of reactive groups that can take part in crosslinking reactions via different mechanisms. EPNs were prepared by glycidylation of novolacs using epichlorohydrin. The novolacs had varying phenol: formaldehyde ratios. Blends of unsaturated polyester with EPN were then prepared. The physical properties of the cured blends were compared with those of the control resin. EPN shows good miscibility and compatibility with the resin and improves the toughness and impact resistance substantially. Considerable enhancement of tensile strength is also noticed at about 5% by weight of epoxidized novolac resin. TGA, DMA, and DSC were used to study the thermal properties of the toughened resin and the fracture behavior was studied using SEM. The blends are also found to have better thermal stability. Blending with EPN can be a useful and cost-effective technique for modification of UPR

Estudo de esmalte estufa aquoso definitivo

Mestrado em Engenharia Química

Desenvolvimento de estruturas fibrosas com comportamento auxético

Tese de Doutoramento Engenharia Têxtil

Desenvolvimento de têxteis técnicos para reforço de compósitos poliméricos

Materials denominated technical textiles can be defined as structures designed and developed with function to fulfill specific functional requirements of various industrial sectors as are the cases of the automotive and aerospace industries. In this aspect the technical textiles are distinguished from conventional textile materials, in which the aesthetic and of comfort needs are of primordial importance. Based on these considerations, the subject of this dissertation was established having as its main focus the study of development of textile structures from aramid and glass fibers and acting in order to develop the manufacture of composite materials that combine properties of two different structures, manufactured in an identical operation, where each structure contributes to improving the properties of the resulting composite material. Therefore were created in laboratory scale, textile structures with low weight and different composition: aramid (100%), glass (100%) and aramid /glass (65/35%), in order to use them as a reinforcing element in composite materials with polyester matrix. These composites were tested in tension and its fracture surface, evaluated by MEV. Based on the analysis of mechanical properties of the developed composites, the efficiency of the structures prepared as reinforcing element were testified by reason of that the resistance values of the composites are far superior to the polyester matrix. It was also observed that hybridization in tissue structure was efficient, since the best results obtained were for hybrid composites, where strength to the rupture was similar to the steel 1020, reaching values on the order of 340 MPa

Organofilização de uma Mg-bentonita da bacia do Parnaíba-Sul do Maranhão e sua utilização em poli (metacrilato de metila)

Bentonitas são argilas que tem como seu principal constituinte argilominerais do grupo da esmectita, predominantemente montmorillonita. De acordo com o cátion predominante no espaço intercamada da esmectita, a bentonita pode ser classificada como sódica, cálcica ou magnesiana. Essas argilas possuem vasta aplicação industrial, como fluidos de perfuração, pelotização, moldes de fundição, dentre outros. Para algumas aplicações mais específicas e que agregam maior valor ao produto final, como na síntese de nanocompósitos polímero/argila, faz-se necessário à intercalação de íons orgânicos na intercamada do argilomineral. No Brasil, a produção industrial de argilas organofílicas é pequena e voltada para os mercados de tintas, graxas e resinas de poliéster. Empresas do setor de bentonitas, que ainda não estão produzindo esse tipo de material, vêm mostrando crescente interesse nesta aplicação. Dentro desse contexto, este trabalho buscou avaliar o potencial da Bentonita Formosa, uma Mg-bentonita recentemente descrita e relativamente abundante no nordeste do Brasil, na produção de argilas organofílicas e sua aplicação em síntese de nanocompósitos polímero/argila. Para isso, foram realizadas sínteses variando a concentração dos íons surfactantes hexadeciltrimetilamônio (HDTMA⁺) e dodeciltrimetilamônio (DTMA⁺) em 0,7, 1,0 e 1,5 vezes o valor de CEC, com tempo de reação de 12 horas e variação de temperatura de 25 ºC e 80 ºC. A Mg-Bentonita in natura e ativada com carbonato de sódio foi utilizada como material de partida. Tanto o material de partida como as argilas organofílicas obtidas foram caracterizadas por DRX, DTA/TG e IV. As argilas que apresentaram melhores resultados de intercalação foram utilizadas nas proporções de 1%, 3% e 10% para a síntese de nanocompósitos poli(metacrilato de metila) (PMMA)/argila. As análises de DRX confirmaram a intercalação dos íons orgânicos no espaço intercamada da Mg-esmectita com e sem ativação. Com os resultados de IV foi possível observar que a razão de confôrmeros gauche/trans diminui com o aumento do espaçamento basal. Os resultados de DTA/TG confirmaram a estabilidade térmica das argilas organofílicas à temperatura máxima de 200 °C, o que possibilita a utilização desse material em síntese de nanocompósitos polímero/argila obtidos por processo de fusão. A análise de DRX confirmou a intercalação do PMMA no espaço intercamada da Mg-esmectita em todos os nanocompósitos produzidos. Com as análises de DSC foi possível observar o aumento da temperatura de transição vítrea para todos os nanocompósitos, quando comparados com PMMA puro. Com isso, é possível concluir que a Mg-Bentonita pode ser intercalada com íons alquilamônio, sem a necessidade prévia de ativação sódica, formando argilas organofílicas, assim como sua utilização em síntese de nanocompósitos. Essa possibilidade de utilização da Mg-bentonita in natura pode representar uma importante diferença em termos de custos de processo, na comparação com as bentonitas cálcicas existentes no Brasil, ou mesmo as importadas, que precisam ser ativadas durante o beneficiamento. Finalmente, acredita-se que a pesquisa deve avançar com a avaliação das propriedades mecânicas dos nanocompósitos produzidos neste trabalho, visando as diferentes possibilidades de aplicações desses materiais.

Avaliação de sistemas de pultrudados com diferentes tipos de matrizes para aplicação em cabos condutores

In the last decades it has been observed a substantial developing of the electrical energy demand in the societies all over the World. In consequence the electrical energy distribution companies are increasing the quantity of electrical energy through the electrical energy conductor cables, which had grown the sag in the towers of energy transmission. Furthermore, the construction of more transmission towers brings a lot of troubles due environmental protection laws. In this way, looking forward to increase the quantity of electrical energy transmitted through electrical cables conductors, reduce the need of constructing new transmission towers and the sag in them, we suggest in this work the replace of the traditional core of the conductors cables commonly used, made of steel, by a core made by a composite material, which one is made by carbon fibers pultruded with polymeric resins as matrix. In a order to evaluate if the resins more commonly used in structural composites can be applied as matrix to make possible to use the composite material as a core, we made carbon fibers systems pultruded with epoxy, phenolic and polyester resins as matrix and a mechanic and physic-chemistry characterization was done on the systems by Tensile and Poisson tests, differential sprobe calorimetry (DSC), thermogravimetric analysis (TGA) and Fourier transformed infrared spectroscopy (FTIR), following their correspondents standards

Some aspects of the microbiological properties of polymers and composite materials

The interaction of microorganisms with glass-reinforced polyester resins(GRP), both under laboratory and simulated operating conditions, has been examined following reports of severl! fungal biodeterioration. Although GRP was not previously associated with substantial microbial growth, small amounts of microbial activity would pose problems for products associated with comestible materials. The microbiology of the raw materials was investigated, two ingredients were supportive to microbial populations whilst five materials were biostatic or inhibitory in their action. Production laminate was not susceptible to microbial deterioration or inhibitory to microbes. Incorporation of zinc stearate, one of the supportive ingredients, at 300% manufacturing level or drastic undercuring produced laminate capable of supporting microbial growth but only after a non-biotic stage of degradation. Study of the long-term population dynamics of cisterns of GRP and competitive materials under conditions simulating in-service conditions, monitoring microbial numbers within the experimental vessels and comparing with the populations of the supply water, suggests that the performance of GRP cisterns is slightly superior to conventional competitive materials. An investigation of the biological performance of GRP cisterns in an isolated area of known microbiological hazard was conducted. Severe biodeterioration had been experienced with Preform GRP articles moulded using different production techniques, but substitution of current GRP articles resulted in no recurrence of the problem. All attempts to establish the fungal isolate responsible for the phenomena in cisterns under controlled conditions failed. Scanning Electron Microscopy of GRP surfaces showed that although differences exist between current and Preform laminates, these could not satisfactorily explain the differences in service behaviour. These results and the results of the British Plastics Federation Expert Working Group interlaboratory study are discussed in relation to the original report of gross fungal biodeterioration and, to the design of future testing programmes for the products of industrial concerns.

Thermal degradation of a brominated bisphenol a derivative

The thermal degradation of 2,6,2',6'-tetrabromo-4,4-pm-isoproylidene-di phenol (tetrabromobisphenol A) (TBBPA) has been investigated and a mechanism for its thermal degradation is suggested. TBBPA is a comonomer widely used in epoxy and in unsaturated polyester resins to impart fire retardance. These resins find a common use in electric and electronic equipment. The presence of bromine atoms is the key factor in fire retardant activity, while on the other hand it represents an ecological problem when pyrolytic recycling is programmed at the end of the useful life of such items. However, pyrolysis is the more advantageous recycling system for thermosetting resins and thus efforts should be made to control the pyrolysis in order to avoid or minimize the development of toxics. Homolytic scission of the aromatic bromine and condensation of aromatic bromine with phenolic hydroxyl are the main processes occuring in the range 270-340°C. A large amount of charred residue is left as a consequence of condensation reactions. HBr and brominated phenols and bisphenols are the main volatile products formed. Brominated dibenzodioxins structures are included in the charred residue and not evolved in the volatile phases.

Optimization process of polyester polymer mortars modified with recycled GFRP waste aggregates – application of factorial experiment design-

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both: cross-linked nature of thermoset resins, which cannot be remolded, and complex composition of the composite itself, which includes glass fibres, matrix and different types of inorganic fillers. Presently, most of the GFRP waste is landfilled leading to negative environmental impacts and supplementary added costs. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. There are several methods to recycle GFR thermostable materials: (a) incineration, with partial energy recovery due to the heat generated during organic part combustion; (b) thermal and/or chemical recycling, such as solvolysis, pyrolisis and similar thermal decomposition processes, with glass fibre recovering; and (c) mechanical recycling or size reduction, in which the material is subjected to a milling process in order to obtain a specific grain size that makes the material suitable as reinforcement in new formulations. This last method has important advantages over the previous ones: there is no atmospheric pollution by gas emission, a much simpler equipment is required as compared with ovens necessary for thermal recycling processes, and does not require the use of chemical solvents with subsequent environmental impacts. In this study the effect of incorporation of recycled GFRP waste materials, obtained by means of milling processes, on mechanical behavior of polyester polymer mortars was assessed. For this purpose, different contents of recycled GFRP waste materials, with distinct size gradings, were incorporated into polyester polymer mortars as sand aggregates and filler replacements. The effect of GFRP waste treatment with silane coupling agent was also assessed. Design of experiments and data treatment were accomplish by means of factorial design and analysis of variance ANOVA. The use of factorial experiment design, instead of the one factor at-a-time method is efficient at allowing the evaluation of the effects and possible interactions of the different material factors involved. Experimental results were promising toward the recyclability of GFRP waste materials as polymer mortar aggregates, without significant loss of mechanical properties with regard to non-modified polymer mortars.

Development of a new U 200 pultrusion die to produce GRP composite profiles using different thermosetting resins

In this work, a steel heated pultrusion die was designed, developed and manufactured to produce U200 glass fibre reinforced thermosetting matrix (GRP) profiles. The finite element analysis (FEA) was used to predict and optimise the developed die heating by using cylindrical electrical powered cartridges. To assess the new die performance it was mounted in the 120 kN pultrusion line of the Portuguese company Vidropol SA and used to produce continuously U200 profiles able to meet all requirements specified for the E23 grade accordingly to the European Standard EN 13706: 2002. After setting up the type, orientation and sequence of layers in laminate, orthophthalic, isophthalic and bisphenolic unsaturated polyester as well as vinylester resins were used to produce glass fibre reinforced U 200 composite profiles. An appropriated catalyst system was selected and the processing variables optimised for each case, namely, pultrusion pull-speed and die temperature. Finally, the produced U200 profiles were submitted to visual inspection, calcination and mechanical tests, namely, flexural, tensional and interlaminar shear strength (ILSS) tests, to assess their accomplishment with the EN 13706 requirements.

Using a new developed die and different types of thermosetting resins to produce U200 profiles by pultrusion

In this work, a new steel heated pultrusion die was designed, developed and manufactured to produce U200 glass fibre reinforced thermosetting matrix (GRP) profiles. The finite element analysis (FEA) was used to predict and optimise the developed die heating by using cylindrical electrical powered cartridges. To assess the new die performance it was mounted in the 120 kN pultrusion line of the Portuguese company Vidropol SA and used to produce continuously U200 profiles able to meet all requirements specified for the E23 grade accordingly to the European Standard EN 13706: 2002. After setting up the type, orientation and sequence of layers in the U 200 laminate, different types of thermosetting resins were used in its production. Orthophthalic, isophthalic and bisphenolic unsaturated polyester as well as vinylester resins were used to produce glass fibre reinforced U 200 composite profiles. All applied resins were submitted to SPI gel tests in order to select the more appropriated catalyst system and optimise the processing variables to be used in each case, namely, pultrusion pull-speed and die temperature. The best pultrusion operational conditions were selected by varying and monitoring the pull-speed and die temperature and, at the same time, measuring the temperature on the manufactured U 200 profile during processing. Finally, the produced U200 profiles were submitted to visual inspection, calcination and mechanical tests, namely, flexural, tensional and interlaminar shear strength (ILSS) tests, to assess their accomplishment with the EN 13706 requirements.